US20050009982A1 - Compound having silsesquioxane skeleton and its polymer - Google Patents

Compound having silsesquioxane skeleton and its polymer Download PDF

Info

Publication number
US20050009982A1
US20050009982A1 US10/798,872 US79887204A US2005009982A1 US 20050009982 A1 US20050009982 A1 US 20050009982A1 US 79887204 A US79887204 A US 79887204A US 2005009982 A1 US2005009982 A1 US 2005009982A1
Authority
US
United States
Prior art keywords
replaced
carbon atoms
optional
alkyl
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/798,872
Inventor
Jyun-ichi Inagaki
Yasuyuki Sasada
Takashi Kato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JNC Corp
JNC Petrochemical Corp
Original Assignee
Chisso Petrochemical Corp
Chisso Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chisso Petrochemical Corp, Chisso Corp filed Critical Chisso Petrochemical Corp
Assigned to CHISSO CORPORATION, CHISSO PETROCHEMICAL CORPORATION reassignment CHISSO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INAGAKI, JYUN-ICHI, KATO, TAKASHI, SASADA, YASUYUKI
Publication of US20050009982A1 publication Critical patent/US20050009982A1/en
Priority to US11/704,253 priority Critical patent/US7705105B2/en
Priority to US12/659,478 priority patent/US8236917B2/en
Priority to US13/423,548 priority patent/US8420764B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/21Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/30Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/045Polysiloxanes containing less than 25 silicon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Definitions

  • the present invention relates to a compound having a silsesquioxane skeleton, a polymer obtained using the compound, and uses of the polymer.
  • Polyorganosiloxane has excellent heat resistance, weatherability and surface-modifying function, and therefore it is used for semiconductor insulating protective films, flame retardants and coating material additives.
  • a coating agent prepared by blending an organic polymer with polyorganosiloxane can provide the surface of a material coated with the agent with functions such as water repellency.
  • the representative examples of the organic polymer are acryl resins, polyurethanes and alkid resins. In general, however, these polymers do not have a good compatibility with polyorganosiloxane. Accordingly, there have been the problems that the coating agent is liable to become cloudy by blending polyorganosiloxane, and that a coating film obtained from the coating agent is liable to be whitened. That is, an addition amount of polyorganosiloxane has been restricted.
  • the patent document 1 is a process in which a polysiloxane-containing polymer is radically copolymerized with other addition-polymerizable monomers to thereby produce a polysiloxane graft copolymer having a polysiloxane structure in a side chain.
  • Polysilsesquioxane having a structure in which 1.5 oxygen atom is bonded to one silicon atom is disclosed in the patent document 2.
  • a polysilsesquioxane derivative having a polymerizable unsaturated bond and two or more functional groups such as hydroxyl group and alkoxy group is copolymerized with other addition-polymerizable monomers to thereby obtain a vinyl polymer into which a siloxane side chain is introduced. All of them are considered to be excellent in heat resistance, water repellency and weatherability as compared with the homopolymers of the other addition-polymerizable monomers.
  • An object of the present invention is to provide a useful polysilsesquioxane derivative in order to solve the problems described above, and another object is to provide a novel polymer obtained by using the derivative. Still another object is to provide a coating agent, a plastic substrate and an optical material each obtained by using the polymer.
  • the present invention is constituted by the following items [1] to [40].
  • Q 1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—, and optional
  • R 1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen;
  • Q 1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, —CH ⁇ CH— or
  • R 1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine
  • Q 1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • R 1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine
  • Q 1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
  • a 1 , A 2 , A 3 and A 4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or
  • R 1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine
  • Q 1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
  • a 1 , A 2 , A 3 and A 4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group,
  • R 1 is phenyl
  • Q 1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • R 1 is phenyl
  • Q 1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
  • a 1 , A 2 , A 3 and A 4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent for 1,4-phenylene, optional —CH 2 — which is not adjacent to each other may be replaced by —
  • R 1 is phenyl
  • Q 1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional hydrogen may be replaced by fluorine
  • a 1 , A 2 , A 3 and A 4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent for 1,4-phenylene, optional —CH 2 — which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z 0 , Z 1 , Z
  • R 1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine
  • Q 1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; and in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • R 1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine
  • Q 1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
  • a 1 , A 2 , A 3 and A 4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or a condensed ring group having 6 to 10 carbon atoms which is
  • R 1 is phenyl
  • Q 1 is cyclopentyl, cyclohexyl, alkyl having 1 to 5 carbon atoms, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
  • a 1 , A 2 , A 3 and A 4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of 1,4-phenylene, optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
  • polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31], wherein the polymer is polyimide, polyamic acid, polyester, an epoxy resin, polyacrylate or polymethcylate.
  • a composition comprising at least one of the polymers as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • a coating agent comprising the polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • a varnish composition comprising the polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • the compound represented by Formula (1) shall be designated as the compound (1), and the polymer having the structural unit represented by Formula (3) shall be designated as the polymer (3).
  • Compounds and polymers represented by other formulas shall be designated by the same abbreviation.
  • a silsesquioxane skeleton shall be designated as a PSQ skeleton.
  • the compound of the present invention has a silsesquioxane skeleton and is represented by Formula (1).
  • R 1 in Formula (1) is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen.
  • the preferred examples of R 1 are phenyl and phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms. More preferred examples of R 1 are phenyl and phenyl in which at least one hydrogen is replaced by alkyl having 1 to 5 carbon atoms. The most preferred example of R 1 is phenyl.
  • Q 1 in Formula (1) is hydrogen, halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl having 1 to 10 carbon atoms, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—, —CH ⁇ CH— or —C and optional hydrogen may be replaced by halogen.
  • Q 1 are hydrogen, halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl having 1 to 10 carbon atoms in which optional —CH 2 —, which is not adjacent to each other, may be replaced by —CH ⁇ CH—, and phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—.
  • optional hydrogen may be replaced by halogen.
  • Q 1 are hydrogen, —F, —Cl, —CF 3 , —OCF 3 , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxymethyl, methoxypropyl, ethoxylpropyl, propoxypropyl, 2-fluoroethyl, 3-fluoropropyl, vinyl, 1-propenyl, 2-propenyl, allyl, 3-butenyl, 3-pentenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl.
  • Q 2 in Formula (1) is a group represented by Formula (2).
  • a code ⁇ represents a bonding point with silicon.
  • a 1 , A 2 , A 3 and A 4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—
  • optional —CH ⁇ may be replaced by —N ⁇ .
  • it is not preferred that two adjacent —CH 2 — are replaced in the form of —O—O—.
  • 1,4-cyclohexylene in which —CH 2 — is replaced by —O— are 1,3-dioxane-2,5-diyl and 1,4-dioxane-2,5-diyl.
  • the examples of 1,4-phenylene in which —CH ⁇ is replaced by —N ⁇ are pyridine-2,5-diyl, pyrimidine-2,5-diyl and pyridazine-3,6-diyl.
  • optional hydrogen may be replaced by halogen, —CN, —NO 2 or alkyl having 1 to 5 carbon atoms.
  • —CH 2 — which is not adjacent to each other, may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—, and optional hydrogen may be replaced by halogen.
  • a 1 to A 4 are a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[3.1.0]hex-3,6-diyl, bicyclo[2.2.2]oct-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms, and 1,4-phenylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms.
  • a 1 to A 4 are a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine or methyl, and 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine, methyl, ethyl or propyl.
  • a 1 to A 4 are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 3-methyl-1,4-phenylene, 3-ethyl-1,4-phenylene and 3-propyl-1,4-phenylene.
  • Z 0 , Z 1 , Z 2 , and Z 3 in Formula (2) are bonding groups. They are independently a single bond, —CH ⁇ CH—, —C COO—, —OCO—, or alkylene having 1 to 20 carbon atoms.
  • Optional —CH 2 —, which is not adjacent to each other, in the alkylene may be replaced by —O—, —S—, —NH—, —SiR 2 2 —, —SiR 2 2 O—, —OSiR 2 2 —, —OSiR 2 2 O—, —SiR 2 2 OSi R 2 2 —, —COO—, —OCO—, ⁇ CH ⁇ CH— or —C
  • the alkylene may have asymmetric carbon and may be optically active.
  • R 2 described above is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl having 1 to 10 carbon atoms, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—, —CH ⁇ CH— or —C ⁇ C—, and optional hydrogen may be replaced by halogen.
  • Z 0 to Z 3 are a single bond, —(CH 2 ) a —, —O(CH 2 ) a —, —(CH 2 ) a O—, —O(CH 2 ) a O—, —(CH 2 ) a O(CH 2 ) b—, —O(CH 2 ) a O(CH 2 ) b ⁇ C—, —C H— and C—OCO—.
  • the terms a and b are independently an integer of 1 to 18, and the preferred range thereof is 1 to 10.
  • Z 0 to Z 3 are a single bond, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —(CH 2 ) 6 —, —(CH 2 ) 7 —, —(CH 2 ) 8 —, —(CH 2 ) 9 —, —(CH 2 ) 10 —, —OCH 2 —, —O(CH 2 ) 2 —, —O(CH 2 ) 3 —, —O(CH 2 ) 4 —, —O(CH 2 ) 5 —, —O(CH 2 ) 6 —, —O(CH 2 ) 7 —, —O(CH 2 ) 8 —, —O(CH 2 ) 9 —, —O(CH 2 ) 10 —, —CH 2 O—, —(CH 2 ) 2 O—, —(CH 2 ) 2 O
  • Z 4 in Formula (2) is a single bond, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO— or, alkylene having 1 to 20 carbon atoms.
  • alkylene having 1 to 20 carbon atoms optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—.
  • the preferred example of Z 4 is alkylene in which the number of carbon atoms is 1 to 20 and optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
  • the steric configurations may be any one of cis, trans and a mixture thereof.
  • the bonds of R 1 , Q 1 and Q 2 to the PSQ skeleton are not restricted in terms of a steric configuration.
  • Y 1 in Formula (1) is halogen, —OM 1 , —SM 1 , —CHO, —COOR 3 , —CSOR 3 , —CSSR 3 , —NHR 4 1 , —COX 1 , —CSX 1 , —OCOX 1 , —OCOOR 3 , —N ⁇ C ⁇ O, ⁇ CN, —CR 5 ⁇ CH 2 , —CR 5 ⁇ CR 6 COOR 3 , —CH ⁇ CR 5 CR 6 ⁇ CH 2 —, —SO 2 X 1 , —SiR 2 2 X 1 , —SiR 2 2 OR 3 , —SiR 2 2 OCOR 7 , —SiR 2 2 OC ⁇ CH 2 CH 3 , —SiR 2 2 ON ⁇ CR 7 R 8 , —SiR 2 2 NR 7 R 8 , or any one of groups shown below:
  • M 1 is hydrogen or alkaline metal.
  • R 3 is hydrogen, alkaline metal or alkyl having 1 to 10 carbon atoms. In the alkyl having 1 to 10 carbon atoms, optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen.
  • R 4 is hydrogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen, or alkyl having 1 to 5 carbon atoms.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—, —CH ⁇ CH— C—C, and optional hydrogen may be replaced by halogen.
  • X 1 is halogen, and chlorine and bromine are preferred.
  • R 5 , R 6 and X 2 are independently hydrogen, halogen, —CN, or alkyl having 1 to 10 carbon atoms.
  • R 5 , R 6 and X 2 are hydrogen, methyl, —F, —CF 3 and phenyl.
  • R 7 and R 8 are independently alkyl having 1 to 10 carbon atoms.
  • R 9 is hydrogen or alkyl having 1 to 5 carbon atoms.
  • the preferred examples of R 9 are hydrogen, methyl and ethyl.
  • G 1 is a trivalent organic group. This is a part of a tetracarboxylic acid's residue when the compound having a PSQ skeleton is tetracarboxylic anhydride.
  • Y 1 is —OM 1 , —CHO, —COOR 3 , —NHR 4 , —COX 1 , —OCOX 1 , —N ⁇ C ⁇ O, —CR 5 ⁇ CH 2 , 1,2-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
  • Y 1 is —OM 1 , —COOR 3 , —NHR 4 , —COX 1 , —N ⁇ C ⁇ O, —CR 5 ⁇ CH 2 , 1,2-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
  • Y 1 is —OH, —COOR 3 , —NH 2 , —COCl, oxiranyl, oxetanyl or a group shown below:
  • Y 1 is an addition-polymerizable group
  • an addition-polymerizable group is not contained in Q 1 of Formula (1). It is preferred as well that an addition-polymerizable group is not contained in a substituent of a ring constituting Q 2 .
  • Q 1 in Formula (1) is a group which do not react with Y 1 . It is preferred as well that a group which reacts with Y 1 is not contained in a substituent of a ring constituting Q 2 and a bonding group connecting rings.
  • Formula (2) can be specified to preferred formulas such as Formula (1-1) to Formula (1-86) shown below. Codes in these formulas mean the same as described above. Groups showing 1,4-cyclohexylene, 1,4-phenylene and pyridine-2,5-diyl each represent groups shown by the following formulas:
  • Formula (1-1) to Formula (1-80) are more preferred, and Formula (1-1) to Formula (1-58) are further more preferred.
  • Isotopes such as heavy hydrogen and 13 C may be contained in the compound (1) in a larger proportion than those of naturally present ones. In such case, the compounds make little difference in physical properties.
  • the polymer of the present invention is a polymer having a PSQ skeleton and has a structural unit represented by Formula (3):
  • R 1 and Q 1 are groups defined in the same manner as these codes in Formula (1), and the preferred examples of them are the same as in Formula (1).
  • Q 3 is a group represented by Formula (4): Codes in the formula are groups defined in the same manner as these codes in Formula (2) excluding Z 5 , and the preferred examples of them are the same as in Formula (2).
  • Z 5 is a single bond, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO—, or a group represented by —W 1 -T 1 -.
  • W 1 is a single bond or alkylene having 1 to 20 carbon atoms.
  • optional —CH 2 — which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—.
  • W 1 is alkylene in which the number of carbon atoms is 1 to 20 and optional —CH 2 —, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
  • T 1 is —O—, —S—, —SiR 2 2 —, —SiR 2 2 O—, —OSiR 2 2 —, —OSiR 2 2 O—, —SiR 2 2 OSiR 2 2 —, —CO—, —COO—, —OCO—, —CSO—, —OCS—, —CONR 10 —, —NR 10 CO—, —CONR 10 O—, —ONR 10 CO—, —OCONR 10 —, —NR 10 CONR 10 —, —NR 10 COO—, —OCOO—, —CH(OH)CH 2 —, —CH 2 CH(OH)—, —CH ⁇ CH—, —CH 2 CR 5 ⁇ CR 6 CH 2 —, —SO 2 —, —SO 2 O—, —OSO 2 —, —SO 2 S—, —SSO 2 —, —SO 2 NR 10 —, —
  • R 10 is hydrogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 10 carbon atoms, optional hydrogen may be replaced by halogen.
  • alkyl having 1 to 5 carbon atoms which is a substituent of phenyl optional —CH 2 —, which is not adjacent to each other, may be replaced by ⁇ O—, —CH ⁇ CH— or —C, and optional hydrogen may be replaced by halogen.
  • R 10 are hydrogen, methyl, ethyl, propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl.
  • R 5 , R 6 and X 2 have the same meanings as these codes in the definitions related to Y 1 , and the preferred examples thereof are the same as described above.
  • G 1 is a trivalent organic group. This is a part of tetracarboxylic acid's residue when the structural unit having a PSQ skeleton is derived from tetracarboxylic acid-derivative having a PSQ skeleton.
  • G 2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue. This shows a part of polybasic acid-derivative's rsidue which are the target of the reaction when the structural unit having a PSQ skeleton is derived from diamine having a PSQ skeleton.
  • T 1 is a group containing G 1 is derived by the reaction of tetracarboxylic acid-derivative having a PSQ skeleton with diamine.
  • This diamine may be diamine having a PSQ skeleton or diamine having no PSQ skeleton.
  • the structural unit in which T 1 is a group containing G 2 is derived by the reaction of diamine having a PSQ skeleton with polybasic acid-derivative.
  • the polybasic acid-derivative may be tetracarboxylic acid-derivative having a PSQ skeleton, or tricarboxylic acid-derivative or tetracarboxylic acid-derivative having no PSQ skeleton.
  • tetracarboxylic acid-derivative(s) is used as a general term including ester, acid anhydride and acid halide of tetracarboxylic acid in addition to tetracarboxylic acid, in the present invention.
  • Polybasic acid-derivative(s), tricarboxylic acid-derivative(s) and dicarboxylic acid-derivative(s) are terms defined in the same manner as described above.
  • the compound (1) can be produced by reacting a compound (1a) with dichlorosilane (1b) in the presence of a base such as triethylamine: In this scheme, Et 3 N is triethylamine, and the other codes have the same meanings as described above.
  • the compound (1a) can be produced by subjecting a silane compound R 1 SiA 3 to hydrolysis and condensation polymerization in the presence of monovalent alkaline metal hydroxide and water, in the presence or absence of an organic solvent.
  • A is a hydrolyzable group and is preferably chlorine and alkoxy having 1 to 4 carbon atoms.
  • the examples of the monovalent alkaline metal hydroxide are lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
  • sodium hydroxide and potassium hydroxide are preferred.
  • the amount of the monovalent alkaline metal hydroxide used is 0.3 to 1.5 in terms of a mole ratio based on the silane compound described above, and more preferred mole ratio is 0.4 to 0.8.
  • the amount of water added is 1.0 to 1.5 in terms of a mole ratio based on the silane compound, and more preferred mole ratio is 1.1 to 1.3.
  • the preferred examples of the organic solvent are linear, branched or cyclic monovalent alcohols. It is estimated that alcohol contributes to a control of the structure in a condensing step.
  • the compound (1a) is reacted with dichlorosilane (1c) to prepare a compound (1d), and then the compound (1d) may be reacted with a compound (1e) in the presence of a catalytic amount of a radical polymerization initiator (azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide and the like) or a transition metal compound (Pt, Rh, Pd, Ni and the like).
  • a radical polymerization initiator azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide and the like
  • a transition metal compound Pt, Rh, Pd, Ni and the like
  • G 2a is a group represented by Formula (5), and the other codes have the same meanings as described above.
  • l, m, n and p are independently 0, 1, 2 or 3
  • Z 6 is a single bond, —CH ⁇ CH—, ⁇ C—, —COO—, —OCO—, or alkylene having 1 to 18 carbon atoms.
  • optional —CH 2 — may be replaced by —O—, —S—, —NH—, —SiR 2 2 —, —SiR 2 2 O—, —OSiR 2 2 —, —OSi R 2 2 O—, —SiR 2 2 OSi R 2 2 ⁇ C—COO—, —OCO—, —CH ⁇ CH— or —C
  • MSG 1 and MSG 2 in the following scheme each are monovalent or divalent organic groups having at least one ring.
  • Plural MSG 1 (or MSG 2 ) in the scheme may be the same or different.
  • a compound (1A) to a compound (1H) correspond to the compound (I).
  • a boric acid derivative (6) and a halide (7) synthesized by a publicly known method are reacted in a carbonate aqueous solution in the presence of a catalyst such as tetrakis(triphenylphosphine)-palladium to synthesize a compound (1A).
  • This compound (1A) can be synthesized as well by first reacting n-butyllithium with a compound (8) synthesized by a publicly known method, then reacting zinc chloride and further reacting the compound (7) in the presence of a catalyst such as dichlorobis-(triphenylphosphine)palladium.
  • the boric acid derivative (6) can be produced by deriving the compound (8) into a Grignard reagent or a lithium reagent and reacting it with trialkylboric acid ester. (II) Formation of —COO— and —OCO—
  • the compound (8) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (9).
  • the carboxylic acid (9) is dehydrated with phenol (10) synthesized by a publicly known method, in the presence of DCC (1,3-dichlorohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to synthesize a compound (1B) having —COO—.
  • a compound having —OCO— can be synthesized as well by the method.
  • the compound (7) is treated with n-butyllithium and then reacted with formamide such as N,N-dimethyl-formamide to obtain aldehyde (11).
  • a phosphonium salt (12) synthesized by a publicly known method is treated with a base such as potassium t-butoxide to produce phosphorus ylid, and this is reacted with.
  • the aldehyde (11) to synthesize a compound (1C).
  • the cis compound is formed depending on the reaction conditions, and therefore the cis compound is isomerized, if necessary, to the trans compound by a publicly known method.
  • the compound (1C) is hydrogenated in the presence of a catalyst such as palladium carbon to thereby synthesize a compound.
  • a catalyst such as palladium carbon
  • a phosphonium salt (13) is used in place of the phosphonium salt (12) to obtain a compound having —(CH 2 ) 2 —CH ⁇ CH— according to the method described in the item (III). This is catalytically hydrogenated to synthesize a compound (1E).
  • the compound (8) is reacted with 2-methyl-3-butyne-2-ol in the presence of a catalyst of dichloropalladium and copper halide, and then the compound is deblocked on a basic condition to obtain a compound (14).
  • the compound (14) is reacted with the compound (7) in the presence of a catalyst of dichloropalladium and copper halide to synthesize a compound (1F).
  • VII Formation of —CH 2 O— or —OCH 2 —
  • the compound (11) is reduced by a reducing agent such as sodium boron hydride to obtain a compound (15). This is halogenated with hydrobromic acid to obtain a compound (16). The compound (16) is reacted with the compound (10) in the presence of potassium carbonate to synthesize a compound (1G). (VIII) Formation of —(CH 2 ) 3 O— or —O(CH 2 ) 3 —
  • a compound (17) is used in place of the compound (11) to synthesize a compound (1H) according to the method described in the item (VII).
  • the compound (1) can be produced by using freely synthetic methods in organic chemistry which are described in Houben-Wyle, Methods of Organic Chemistry, George Thieme Verlag, Stuttgart, Organic Syntheses, John Wiley & Sons Inc., Organic Reactions, John Wiley & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, and New Experimental Chemical Course (Maruzen).
  • the homopolymer is obtained by polymerizing only one compound (1).
  • a copolymer of the compound (1) is obtained by polymerizing a polymerizable composition containing at least two compounds (1).
  • the copolymer is obtained as well by polymerizing a polymerizable composition containing the compound (1) and other polymerizable compounds. All of these homopolymer and copolymers have almost the same structural unit as the structural unit represented by Formula (3).
  • a configuration of the structural unit in the copolymer may be any one of random, block, alternation and graft.
  • the polymer is obtained by subjecting the compound (1) or a polymerizable composition containing the compound (1) to addition polymerization or condensation polymerization. That is, when the functional group Y 1 in the compound (1) is an addition-polymerizable group, it is addition-polymerized by heat or light. When Y 1 is a condensation-polymerizable group, it is condensation-polymerized with a compound having at least two functional groups which can be reacted with Y 1 .
  • the polymerizable composition containing the compound (1) is preferably an addition-polymerizable composition or a condensation-polymerizable composition.
  • the addition-polymerizable composition is a composition containing the compound (1) having an addition-polymerizable group and further containing other addition-polymerizable compounds.
  • the other addition-polymerizable compound may be another compound (1) having an addition-polymerizable group or may be an addition-polymerizable compound which is not the compound (1). They may be blended all together.
  • the addition-polymerizable compound other than the compound (1) shall be referred to as the other polymerizable compound.
  • the condensation-polymerizable composition is a composition containing the compound (1) having a condensation-polymerizable group and further containing other condensation-polymerizable compounds having at least two functional groups which are reacted with the functional group.
  • the other condensation-polymerizable compound may be another compound (1) having a condensation-polymerizable group, or may be a compound other than the compound (1). They may be blended all together.
  • the condensation-polymerizable compound other than the compound (1) shall be referred to as the other reactive compound.
  • the reaction temperature is 0 to 300° C.
  • the reaction time is 1 to 100 hours.
  • a radical polymerization initiator is used.
  • the examples of the radical polymerization initiator are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxydiisobutylate, lauroyl peroxide, dimetyl 2,2′-azobisisobutyrate(MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN) and azobiscyclohexanecarbonitrile (ACN).
  • a radical photopolymerization initiator When the addition-polymerizable composition is polymerized by irradiation with light or an electron beam, a radical photopolymerization initiator may be used.
  • Darocure 1173 (2-hydroxy-2-methyl-1-phenylpropane-1-one), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimetoxy-1,2-diphenylethane-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocure 4265 and Irgacure 784, among the products of Ciba Specialty Chemicals Co., Ltd., can be given as the examples of the radical photopolymer
  • the other examples of the radical photopolymerization initiator are p-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, a mixture of benzophenone/Michler's ketone, a mixture of hexaarylbiimidazole/mercaptobenzimidazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyldimethylketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and a mixture of 2,4-diethylxanthone/methyl p-dimethylaminobenzoate.
  • Used for the condensation polymerization reaction are a method in which the raw materials are reacted in a solution state, a method in which the raw materials are reacted in a molten state, a method in which the raw materials are reacted in a vaporized state by heating under reduced pressure and a method in which they are reacted by giving energy such as light, supersonic wave and plasma from the outside to activate them.
  • a polymerization accelerator such as acid, alkali, metal compounds and the like is used for the purpose of accelerating the polymerization reaction.
  • polyester is produced by esterification or transesterification.
  • the examples of the polymerization accelerator in the reaction are simple substances such as alkaline metals, alkaline earth metals, tin, germanium, antimony, zinc, cobalt, nickel, titanium and aluminum, and compounds thereof.
  • the examples of the compounds are oxides, hydroxides, halides, carbonates, hydrogencarbonates and acetates. Inorganic acid salts, organic acid salts and complexes of the alkylated compounds thereof can be given.
  • the examples of the germanium compounds are germanium dioxide, germanium tetraethoxide and germanium tetra-n-butoxide.
  • the examples of the titanium compounds are tetraalkyl titanate (tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate and the like) and partially hydrolyzed products thereof, titanyl oxalate compounds (titanyl oxalate, ammonium titanyl oxalate, sodium titanyl oxalate, potassium titanyl oxalate, calcium titanyl oxalate, strontium titanyl oxalate and the like), titanium trimellitate, titanium sulfate and titanium chloride.
  • the examples of the antimony compounds are antimony trioxide, antimony acetate, antimony tartarate, potassium antimony tartarate, antimony oxychloride, antimony glycolate, antimony pentaoxide and triphenylantimony.
  • the examples of the aluminum compounds are aluminum carboxylate (aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate and the like), aluminum oxide, aluminum hydroxide, aluminum chloride, chloroaluminum hydroxide, aluminum carbonate, aluminum alkoxides (aluminum methoxide, aluminum ethoxide and the like), aluminum acetylacetonate or aluminum chelate compounds with aluminum acetylacetonate, organic aluminum compounds (trimethylaluminum, triethylaluminum and the like) and partially hydrolyzed products thereof.
  • a stabilizer can be used as well in addition to the polymerization accelerating agent.
  • the examples of the stabilizer are phosphoric acid esters (trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate and the like), phosphorous acid esters (triphenyl phosphite, trisdodecyl phosphite, trisnonylphenyl phosphite and the like) and phosphoric acid and polyphosphoric acid.
  • phosphoric acid esters trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, methyl acid phosphate, is
  • polyimide can be produced by subjecting diamine and tetracarboxylic dianhydride to condensation polymerization to prepare polyamic acid and then dehydrating it by a thermal imidation method or a chemical imidation method.
  • a reaction temperature in the thermal imidation method is 50 to 300° C.
  • a dehydrating agent or a basic catalyst having a hydrolyzing ability is used in the chemical imidation method.
  • the examples of the dehydrating agent are N,N-dialkylcarbodiimides, aliphatic carboxylic anhydrides (acetic anhydride, trifluoroacetic anhydride and the like), phosphoric acid derivatives (polyphosphoric acid, phosphorus pentaoxide and the like), acid anhydrides of phosphoric acid derivatives and acid chlorides (methanesulfonyl chloride, phosphorus pentachloride, thionyl chloride and the like).
  • the examples of the basic catalyst are organic bases, tertiary amines and inorganic bases.
  • the examples of the organic bases are N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, imidazole, N-methylcaprolactam, imidazole, N,N-dimethylaniline and N,N-diethylaniline.
  • the examples of the tertiary amines are pyridine, collidine, lutidine and triethylamine.
  • the examples of the inorganic bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
  • the epoxy resin is obtained from an epoxy composition containing at least one epoxy compound and a curing agent or a cationic photopolymerization initiator.
  • the epoxy composition may contain, if necessary, a solvent and/or a curing-accelerating agent.
  • the curing-accelerating agent accelerates the reaction of the epoxy compound with the curing agent.
  • the specific examples of the cationic photopolymerization initiator shall be shown below. Almost all of them are commercially available and can readily be obtained.
  • the examples of the cationic photopolymerization initiator are diaryliodonium salts (hereinafter abbreviated as DAS) and triarylphosphonium salts (hereinafter abbreviated as TAS).
  • DAS diaryliodonium salts
  • TAS triarylphosphonium salts
  • the examples of DAS are diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosfonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetra(pentafluorophenyl)borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-meth
  • DAS can be highly sensitized by adding a photosensitizer.
  • the examples of the photosensitizer are thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene and rubrene.
  • TAS triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarcenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetra(pentafluorophenyl)borate, 4-methoxyphenyl-diphenylsulfonium tetrafluoroborate, 4-methoxyphenyl-diphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarcenate, 4-methoxyphenyldiphenylsulfonium trifluoromethane-
  • Publicly known potential curing agents which are usually used as a curing agent for epoxy resins can be used as the curing agent.
  • the examples of the potential curing agents for epoxy resins are amine base curing agents, novolak resin base curing agents, imidazole base curing agents and acid anhydride base curing agents.
  • the examples of the amine base curing agents are aliphatic polyamines (diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine and the like), alicyclic polyamines (isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, Laromine and the like), aromatic polyamines (diaminodiphenylmethane, diaminodiphenyl ether, metaphenylenediamine, diaminodiphenylsulfone and the like), polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine mixtures and N-aminoethylpipe
  • the examples of the novolak resin base curing agents are phenol novolak resins, bisphenol novolak resins, poly(p-vinylphenol) and the like.
  • the examples of the imidazole base curing agents are 2-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium.trimellitate and 2-phenylimidazolium.isocyanurate.
  • the examples of the acid anhydride base curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenate methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexanetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerinbis(anhydrotrimellitate) monoacetate, dodecenylsuccinic anhydride, aliphatic dibasic polyanhydride and chlorendic anhydride.
  • the other curing agents include dicyandiamide, ketimine compounds and the like.
  • the examples of the curing-accelerating agent for accelerating the curing reaction of the epoxy compound with the curing agent are tertiary amines (benzyldimethylamine, tris(dimethylaminomethyl)phenol, dimethylcyclohexylamine and the like), imidazoles (1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and the like), organic phosphorus base compounds (triphenylphosphine, triphenyl phosphite and the like), quaternary phosphonium salts (tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide and the like), diazabicycloalkenes (1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof and the like), organic metal compounds (zinc octylate, tin o
  • a method for producing the epoxy resin shall not specifically be restricted, and it can be produced by a publicly known method, for example, by blending an epoxy compound, a curing agent, a curing-accelerating agent or a cationic photopolymerization initiator and, if necessary, additives and mixing them by a publicly known method.
  • the epoxy resin can be produced by preparing two liquids of an epoxy composition comprising an epoxy compound as a principal component and a curing agent composition comprising a curing agent and a curing-accelerating agent as principal components and mixing the epoxy composition with the curing agent composition prior to use. Further, the epoxy resin can be produced as well by blending all of an epoxy compound, a curing agent, a curing-accelerating agent or a cationic photopolymerization initiator and, if necessary, additives in the form of a single liquid.
  • the examples of the epoxy compound other than the compound (1) used for the epoxy composition are glycidyl ethers (bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether and the like), glycidyl esters (glycidyl hexahydrophthalate, dimer acid glycidyl ester and the like), glycidylamines (triglycidyl isocyanurate, tetraglycidyl-diaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N,N,N′,N′-tetraglycidyl-m-xylenediamine and the like) and alicyclic or aliphatic epoxides (3,4-epoxycyclohexylmethyl carboxy
  • a method for curing the epoxy composition shall not specifically be restricted, and capable of being used are publicly known curing apparatuses such as a closed type curing furnace and a tunnel furnace in which continuous curing can be carried out.
  • the heating source shall not specifically be restricted, and heating can be carried out by publicly known methods such as hot air circulating, infrared heating and high-frequency heating.
  • the curing temperature and the curing time fall preferably in the ranges of 80 to 250° C. and 30 seconds to 15 hours.
  • the polymer (3) can be produced as well by an anionic polymerization method, a coordinate polymerization method or a living polymerization method.
  • the examples of the preferred catalyst used in these polymerization methods are alkyl alkaline metals (n-butyllithium, sec-butyllithium, t-butyllithium, trialkylaluminum and the like), aluminum compound and transition metal compound.
  • a solvent may be used for the polymerization reaction.
  • the examples of the solvent are benzene, toluene, xylene, mesitylene, pentane, hexane, heptane, octane, nonane, decane, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, 1-3-dimethyl-2-imidazolidinone, imidazole, N-methylcaprolactam, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfoamide, cresol, phenol, xylenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol ldimethyl ether (triglyme), tetraglyme, di
  • the preferred examples of the other reactive compounds are glycols, dicarboxylic acids, diamines and tetracarboxylic dianhydrides, but they shall not be restricted thereto.
  • the preferred examples of the other polymerizable compounds are vinyl base monomers, fumaric acid diesters and maleimide derivatives, but they shall not be restricted thereto.
  • the glycols may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active.
  • the examples of the aliphatic glycol are aliphatic diols (ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, neopentyl glycol and the like) and polyether compounds (polyethylene glycol, polypropylene glycol, polybutylene glycol and the like).
  • the examples of the alicyclic glycol are 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, tetralindimethanol, norbornanedimethanol, tricyclodecanedimethanol and pentacyclododecanedimethanol.
  • the examples of the aromatic glycol are alkylene oxide adducts of bisphenols and alkylene oxide adducts of aromatic dihydroxy compounds.
  • the examples of the alkylene oxide adduct of bisphenol are 4,4′-(1-methylethylidene)bisphenol, methylenebisphenol (bisphenol F), 4,4′-cyclohexylidenebisphenol (bisphenol Z) and 4,4′-sulfonylbisphenol (bisphenol S).
  • the examples of the alkylene oxide adducts of aromatic dihydroxy compounds are hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxydiphenylbenzophenone.
  • the glycols described above include ones in which isomers are present, and they may be mixtures containing them. Two or more glycols may be used in combination. When two or more glycols are used, two or more glycols may be selected from the same kind of the glycols described above, or at least one glycol may be selected from each of the different kind of the glycols.
  • the glycols used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the dicarboxylic acids or the derivatives thereof may be belong to any one of groups of aliphatic type, alicyclic type, aromatic type and heterocyclic type, and they may contain a siloxane group and may be optically active.
  • the examples of the aliphatic dicarboxylic acid are malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.
  • the examples of the alicyclic dicarboxylic acid are 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxy
  • aromatic dicarboxylic acid examples include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalica acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene-dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene-dicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyl-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4′′-terphenyldicarboxylic acid, 4,4,-diphenylmethane
  • dicarboxylic acid containing heterocycles are 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furancarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridine-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid and 3,5-pyridinedicarboxylic acid.
  • the dicarboxylic acids described above may be monoesters, diesters, acid monohalides, acid dihalides or anhydrides. One of two carboxyl groups may be esterified, and the other may be acid halide. These compounds include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more dicarboxylic acids may be used in combination. When two or more dicarboxylic acids are used, two or more dicarboxylic acids may be selected from the same kind of the dicarboxylic acids described above, or at least one dicarboxylic acid may be selected from each of the different kind of the dicarboxylic acids.
  • the dicarboxylic acids used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the diamines may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active.
  • the examples of the aliphatic diamine are ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine.
  • the diamines may have a structure in which optional —CH 2 — may be replaced by —O—.
  • the examples of the alicyclic diamine are 1,4-diaminodicyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4′-diaminodicyclohexylmethane, bis(2-methyl-4-aminocyclohexyl)methane, isophoronediamine, 2,5-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,3-diaminobicyclo[2.2.1]heptane, 2,5-diaminobicyclo-[2.2.1]heptane, 2,6-diaminobicyclo[2.2.1]heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,3-diamino-7-azabicyclo[2.2.1]heptane,
  • aromatic diamine examples include 2,2-bis(4-aminophenyl)propane, 2,6-diaminopyridine, bis-(4-aminophenyl)diethylsilane, bis-(4-aminophenyl)-diphenylsilane, bis-(4-aminophenyl)ethylphosphine oxide, bis-(4-aminophenyl)-N-butylamine, N,N-bis-(4-aminophenyl)-N-methylamine, N-(3-aminophenyl)-4-aminobenzamide, 3,3′-diaminodiphenylmethane, 3,3′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 2,2-bis(3-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 3,3′-diamino
  • the diamines described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more diamines may be used in combination. When two or more diamines are used, two or more diamines may be selected from the same kind of the diamines described above, or at least one diamine may be selected from each of the different kind of the diamines.
  • the diamines used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the tetracarboxylic dianhydrides may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active.
  • the examples of the aliphatic tetracarboxylic dianhydride are ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride.
  • the examples of the alicyclic tetracarboxylic dianhydride are cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicycloheptanetetracarboxylic dianhydride, bicyclooctanetetracarboxylic dianhydride, bicyclo[2.2.2]-octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane-1,2,5,6-tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, 3,3′-bicyclohexyl-1,1′,2,2′-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl
  • aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, naphthalenic dianhydride (2,3,6,7-naphthalenic anhydride and the like), 3,3′-4,4′-diphenylmethanetetracarboxylic dianhydride, 3,3′-4,4′-diphenylethanetetracarboxylic dianhydride, 3,3′-4,4′-diphenylpropane-tetracarboxylic dianhydride, 3,3′-4,4′-diphenylsulfonetetracaroxylic dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 4,4′-bis(3,4-dicar)
  • the various tetracarboxylic dianhydrides described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more tetracarboxylic dianhydrides may be used in combination. When two or more tetracarboxylic dianhydrides are used, two or more tetracarboxylic dianhydrides may be selected from the same kind of the tetracarboxylic dianhydrides described above, or at least one tetracarboxylic dianhydride may be selected from each of the different kind of the tetracarboxylic dianhydrides.
  • the tetracarboxylic dianhydrides used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the tricarboxylic acids may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active.
  • the examples of the tricarboxylic acid are trimellitic acid, trimesic acid, hemimellitic acid, propanetricarboxylic acid and cyclohexane-tricarboxylic acid.
  • These tricarboxylic acids may be monoesters, diesters, triesters, acid monohalides, acid dihalides, acid trihalides or compounds in which two carboxyl groups are reduced to acid anhydrides.
  • They may be monoester acid dihalides, diester acid monohalides or compounds having a structure in which two carboxyl groups are reduced to acid anhydrides and remaining carboxyl group is esterified or is acid halide. These compounds include ones in which isomers are present, and they may be mixtures containing the isomers.
  • Two or more tricarboxylic acids may be used in combination. When two or more tricarboxylic acids are used, two or more tricarboxylic acids may be selected from the same kind of the tricarboxylic acids described above, or at least one tricarboxylic acid may be selected from each of the different kind of the tricarboxylic acids.
  • the tricarboxylic acid-derivatives used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids described above may be used in combination of two or three kinds thereof. That is, the examples of the combination are the combination consisting of at least one of each of dicarboxylic acids and tricarboxylic acids, the combination consisting of at least one of each of dicarboxylic acids and tetracarboxylic acids, the combination consisting of at least one of each of tricarboxylic acids and tetracarboxylic acids and the combination consisting of at least one of each of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids.
  • the vinyl base monomers are olefins, halogenated vinyls, vinyl esters, aromatic vinyl base monomers, styrene derivatives, vinyl ethers, alkyl vinyl ketones, dienes, (meth)acrylates, itaconates, ⁇ , ⁇ -vinylnaphthalene, N-vinylacetamide and the like. They may contain a siloxane group and may be optically active.
  • the examples of the olefin are ethylene, propylene and isobutene.
  • the examples of the halogenated vinyl are vinyl chloride and vinyl fluoride.
  • the examples of the vinyl ester are vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate and vinyl 2-ethyl-2-methylbutanoate.
  • the examples of the aromatic vinyl base monomer are vinyl p-t-butylbenzoate and vinyl N,N-dimethylaminobenzoate.
  • the examples of the styrene derivative are styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene and ⁇ -methylstyrene.
  • the examples of the vinyl ether are ethyl vinyl ether, hydroxybutyl vinyl ether, t-amyl vinyl ether and cyclohexanedimethanolmethyl vinyl ether.
  • the examples of the alkyl vinyl ketone are methyl vinyl ketone and isobutyl vinyl ketone.
  • the examples of the diene are butadiene and isoprene.
  • the examples of the (meth)acrylate are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and phenyl (meth)acrylate.
  • the examples of the itaconate are dimethyl itaconate, diethyl itaconate, dibutyl itaconate and diisopropyl itaconate.
  • (Meth)acrylate is a general term for acrylate and methacrylate.
  • the various vinyl base monomers described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination.
  • the vinyl base monomers used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the fumaric acid diesters may have a siloxane group and may be optically active.
  • the examples of the fumaric acid diester are diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclohexyl fumarate, di(1-phenyl-2-propyl) fumarate, di-sec-butyl fumarate, di-t-butyl fumarate, di-2-ethylhexyl fumarate, (isopropyl) (ethyl) fumarate, (isopropyl) (propyl) fumarate, (isopropyl) (butyl) fumarate, (isopropyl) (sec-butyl) fumarate, (isopropyl) (t-butyl) fumarate, (isopropyl) (isoamyl) fumarate, (isopropyl) (sec-amyl) fumarate, (isopropy
  • the fumaric acid diesters described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination.
  • the fumaric acid diesters used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • Multifunctional acrylates can be added in order to enhance more a coating film-forming ability of the polymer (3).
  • the multifunctional acrylates may have a siloxane group and may be optically active.
  • the preferred examples of the multifunctional acrylate are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO-added triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, bisphenol A EO-added diacrylate, bisphenol A glycidyl ether diacrylate and polyethylene glycol diacrylate.
  • the multifunctional acrylates described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination.
  • the multifunctional acrylates used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • the maleimide derivatives may have a siloxane group and may be optically active.
  • the examples of the maleimide derivative are N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-nonylmaleimide, N-decylmaleimide, N-undecylmaleimide, N-dodecylmaleimide, N-octadecylmaleimide, N-isopropylmaleimide, N-(sec-butyl)maleimide, N-(t-butyl)maleimide, N-(1-methylbutyl)maleimide, N-(2-methylbutyl)maleimide, N-(3-methylbutyl)maleimide, N-(sec-hexyl)
  • the maleimide derivatives described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination.
  • the maleimide derivatives used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • two or more compounds may be selected from the same kind of the addition-polymerizable compounds described above, or at least one compound may be selected from each of the different kind of the addition-polymerizable compounds.
  • the polymer (3) can be obtained by polymerizing the compound (1), the addition-polymerizable composition or the condensation-polymerizable composition described above.
  • the preferred example of the polymer obtained using the compound (1) is a polymer obtained using the compound (1) having —OM 1 , —CHO, —COOR 3 , —NHR 4 , —COX 1 , —OCOX 1 , —N ⁇ C ⁇ O, —CR 5 ⁇ CH 2 , oxiranyl, oxetanyl, 3,4-epoxycyclohexyl or any one of groups shown below:
  • polymer obtained using the compound (1) is a polymer obtained using the compound (1) having —OM 1 , —COOR 3 , —NHR 4 , —COX 1 , —N ⁇ C ⁇ O, —CR 5 ⁇ CH 2 , oxiranyl, oxetanyl or any one of groups shown below:
  • the representative examples of the polymer obtained using the compound (1) are polyimides, polyamic acids, polyesters, epoxy resins, polyacrylates and polymethacrylates.
  • the polyamic acid is obtained by the reaction of the compound (1), which is diamine, with tetracarboxylic dianhydride.
  • This tetracarboxylic dianhydride may be the compound (1), a tetracarboxylic dianhydride other than the compound (1), or a mixture of these tetracarboxylic dianhydrides.
  • Diamines other than the compound (1) may be added to the compound (1) which is diamine.
  • Another example of the polyamic acid is obtained by the reaction of the compound (1), which is tetracarboxylic dianhydride, with diamine.
  • This diamine may be the compound (1), a diamine other than the compound (1), or a mixture of these diamines.
  • Tetracarboxylic dianhydrides other than the compound (1) may be added to the compound (1) which is tetracarboxylic dianhydride.
  • the polyimides are obtained by subjecting the above polyamic acids to dehydration ring-closure.
  • the polyester is obtained by the reaction of the compound (1), which is diol, with a carboxylic acid derivative having at least two carboxyls, acid halide groups, acid anhydride groups or ester groups.
  • the carboxylic acid derivative may be the compound (1), a carboxylic acid derivative other than the compound (1), or a mixture of these carboxylic acid derivatives.
  • Diols other than the compound (1) may be added to the compound (1) which is diol.
  • Another example of the polyester is obtained by the reaction of the compound (1), which is the carboxylic acid derivative having at least two carboxyls, acid halide groups, acid anhydride groups or ester groups, with diol. This diol may be the compound (1), a diol other than the compound (1), or a mixture of these diols.
  • Carboxylic acid derivatives other than the compound (1) may be added to the compound (1) which is the carboxylic acid derivative.
  • the epoxy resin is obtained by the addition reaction of the compound (1), which is bisepoxide, with an active hydrogen compound having at least two of any one of amino group, carboxyl group, phenolic hydroxyl group and thiol group, the copolycondensation reaction of the compound (1), which is bisepoxide, with acid anhydride, or the self polymerization of the compound (1), which is bisepoxide, by a basic or acidic catalyst.
  • the active hydrogen compound may be the compound (1), an active hydrogen compound other than the compound (1), or a mixture of these active hydrogen compounds.
  • the acid anhydride may be the compound (1), which is tetracarboxylic dianhydride, a acid anhydride other than the compound (1) or a mixture of these compounds.
  • the basic or acidic catalyst is an anionic polymerization catalyst such as alkoxides of sodium or potassium, hydroxides, amides, hydrides and Na-naphthalene, a cationic polymerization catalyst including Lewis acids such as SnCl 4 , BF 3 and AlCl 3 , and protonic acids such as HCl, HBr and H 2 SO 4 , and a coordinate polymerization catalyst such as alkoxides of Ca and Ba, oxides, carbonates, amides, alkoxides of Al, Mg and Zn and Zn(C 2 H 5 ) 2 —H 2 O base and Al(C 2 H 5 ) 3 —H 2 O base catalysts.
  • anionic polymerization catalyst such as alkoxides of sodium or potassium, hydroxides, amides, hydrides and Na-naphthalene
  • a cationic polymerization catalyst including Lewis acids such as SnCl 4 , BF 3 and AlCl 3 , and protonic acids such as
  • bisepoxides other than the compound (1) may be added to the compound (1) which is bisepoxide.
  • the epoxy resin is an epoxy resin obtained by the reaction of the compound (1) having at least two of any one of amino group, carboxyl group, phenolic hydroxyl group and thiol group with bisepoxide, or the reaction of the compound (1), which is a tetracarboxylic dianhydride, with bisepoxide.
  • the bisepoxide may be the compound (1), a bisepoxide other than the compound (1), or a mixture of these bisepoxides.
  • Active hydrogen compounds other than the compound (1) may be added to the compound (1) which is an active hydrogen compound. Acid anhydrides compounds other than the compound (1) may be added to the compound (1) which is a tetracarboxylic dianhydride.
  • the examples of the polyacrylate are a homopolymer of the compound (1) having acryloyloxy, a copolymer obtained from at least two of the above compounds (1), a copolymer of at least one of the above compounds (1) and at least one of the compounds (1) having methacryloyloxy, a copolymer of at least one of the above compounds (1) and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1), and a copolymer of at least one of the above compounds (1), at least one of the compounds (1) having methacryloyloxy and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1).
  • the examples of the polymethacrylate are a homopolymer of the compound (1) having methacryloyloxy, a copolymer obtained from at least two of the above compounds (1), a copolymer of at least one of the above compounds (1) and at least one of the compounds (1) having acryloyloxy, a copolymer of at least one of the above compounds (1) and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1), and a copolymer of at least one of the above compounds (1), at least one of the compounds (1) having acryloyloxy and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1).
  • the compound (1) and the polymer (3) are characterized by that they are physically and chemically stable very much on conditions usually used and that they have a good compatibility with other polymers and compounds. Suited selection of rings, bonding groups or side chains constituting the compound (1) makes it possible to suitably select the structure of the polymer (3), and therefore capable of being produced is the polymer having optimum transparency, refractive index, mechanical strength, coating property, solubility, crystallinity, shrink property, water permeability, water absorbency, gas permeability, melting point, glass transition point, heat resistance, thermal expansion coefficient, water repellency, electrical insulating property, compatibility and chemical resistance.
  • the compound (1), the polymer (3) or the composition containing them can be molded into a thin film, a multilayer membrane, a film, a fiber, a powder, a paste and other molded articles by a method which is usually used for producing conventional molded articles of high molecular materials.
  • aliphatic polyols such as ethylene glycol and propylene glycol, aliphatic or aromatic carboxylic acid compounds, carbon dioxide gas-preventing agents such as phenol compounds, flexibility-providing agents such as polyalkylene glycols, antioxidants, plasticizers, lubricants, coupling agents such as silanes, surface treating agents for inorganic fillers, flame retardants, antistatic agents, colorants, leveling agents, ion trapping agents, slid-improving agents, various rubbers, impact-improving agents such as organic polymer beads, swing-providing agents, surfactants, surface tension-reducing agents, defoaming agents, precipitation preventives, light scattering agents, UV absorbers, heat stabilizers, antioxidants, mold releasing agents, fluorescent agents, conductive fillers, foaming agents and additives such as pigments.
  • carbon dioxide gas-preventing agents such as phenol compounds
  • flexibility-providing agents such as polyalkylene glycols, antioxidants, plasticizers, lubricants
  • the polymer (3) of the present invention is dissolved homogeneously in a solvent, and the resulting solution is cast on a substrate and heated to volatilize the solvent, whereby a uniform film of 1 to 100 ⁇ m can be obtained.
  • a polymer film, a glass plate, a silicon rubber plate and a metal plate can be given as the substrate used for molding a film by the above casting method.
  • the polymer is repeatedly cast and laminated so that the targeted film thickness is obtained, and then it is heated to volatilize the solvent, whereby the substrate having a prescribed thickness can be prepared. In this case, pressing can be carried out as well while heating and applying pressure.
  • a multilayer substrate can be obtained by laminating a metal conductive layer of gold, copper or aluminum between the films and/or on the outermost layer. Also in this case, a metal conductive film is superposed thereon and heated in the same manner as described above to volatilize the solvent, whereby the substrate having a good adhesive property with the metal conductive film can be obtained.
  • the metal conductive layer is obtained by forming a circuit by etching. Further, it can be formed as well by a vacuum deposition method and a screen printing method.
  • aromatic hydrocarbon base solvents such as benzene and toluene
  • ketone base solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, chloroform, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylacetamide dimethylacetal, dimethylsulfoxide, 1,4-dioxane, ethyl acetate, 2-n-butoxyethanol, ⁇ -butyrolactone, trifluoroacetic acid, ethyl trifluoroacetate and hexafluoro-2-propanol.
  • two or more solvents may be used in combination.
  • the solvents which can be used in the present invention shall not be restricted to the examples described above.
  • the present invention shall be explained below in more details with reference to examples, but the present invention shall not be restricted by these examples.
  • the structures of the compounds were confirmed by a nuclear magnetic resonance (NMR) spectrum, a mass (MS) spectrum and an infrared absorption (IR) spectrum.
  • NMR nuclear magnetic resonance
  • MS mass
  • IR infrared absorption
  • the polymer thin film formed on a glass plate was measured for a pencil hardness by means of a pencil hardness meter YOSHIMITSU SEIKI C-221 according to JIS “JIS-K-5600-5-4 scratch hardness (pencil method)”.
  • the polymer thin film formed on a glass plate was measured for a light transmittance by means of a micro color analyzer TC-1800M (manufactured by Tokyo Denshoku Technical Center.
  • the contact angles of purified water (specific resistance: 18 M ⁇ cm) and ethylene glycol which were dropped on the polymer thin film were measured at 25° C. by means of a contact angle meter CA-A (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) to calculate the surface free energy.
  • the polymer thin film formed on a glass plate was peeled to prepare a sample. It was heated from 30° C. to 800° C. at 10° C./minute in aerial atmosphere by means of SEIKO SSC5000 TG/DTA 300 to measure a weight change, and the respective temperatures were determined from the inflection points obtained.
  • Codes used in the examples have the following meanings:
  • Toluene (500 ml) was added to a compound (a) (50.0 g, 43.3 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 25 ⁇ l) was added thereto and heated to 90° C. Allyl p-nitrophenyl ether (16.3 g, 91 mmol) was dropwise added thereto in 5 minutes, and the solution was heated for 2 hours while refluxing. After standing to cool, toluene (100 ml) and water (300 ml) were added thereto, and extracting practic was carried out. The organic layer was washed with water and then dried on anhydrous magnesium sulfate.
  • a platinum-divinylsiloxane complex 3 wt % toluene solution, 25 ⁇ l
  • Compound (1-1-4) was produced via the following route:
  • Compound (1-1-1) was produced via the following route: First Stage: Production of Compound (d)
  • 3-Acetoxypropylmethyldichlorosilane (5.4 g, 25 mmol) was added to a mixture of a compound (c) (11.6 g, 10 mmol), triethylamine (2.5 g, 25 mmol) and THF (200 ml) under nitrogen atmosphere, and the solution was stirred at a room temperature for 3 hours.
  • Toluene (200 ml) and water (100 ml) were added thereto and stirred, and the organic layer was washed with water and then dried on anhydrous magnesium sulfate.
  • Toluene was distilled off under reduced pressure, and the residue thus obtained was washed with methanol and recrystallized from ethanol/ethyl acetate (100 ml) to obtain a compound (d) 6.51 g.
  • Compound (1-1-2) was produced via the following route: First Stage: Production of Trimethylsilyl 4-pentenoate
  • Toluene (1,000 ml) was added to the compound (a) (100.0 g, 86.7 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 50 ⁇ l) was added thereto and heated to 90° C. Trimethylsilyl 4-pentenoate (31.4 g, 182 mmol) was dropwise added thereto, and the solution was heated for 5 hours while refluxing. After standing to cool, toluene was distilled off under reduced pressure to obtain a crude compound (e) (92.9 g).
  • Compound (1-1-5) was produced via the following route:
  • Toluene (50 ml) was added to the compound (a) (5.0 g, 4.33 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 30 ⁇ l) was added thereto and heated to 90° C. Allyl glycidyl ether (1.04 g, 9.1 mmol) was dropwise added thereto, and the solution was heated for 3 hours while refluxing. After standing to cool, toluene (50 ml) and water (100 ml) were added thereto, and extracting practice was carried out. The organic layer was washed with water and then dried on anhydrous magnesium sulfate.
  • Compound (1-1-8) was produced via the following route:
  • Toluene (30 ml) was added to the compound (a) (3.0 g, 2.60 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 5 ⁇ l) was added thereto and heated to 90° C.
  • 4-Vinyl-1-cyclohexene 1,2-epoxide (0.68 g, 5.46 mmol) was dropwise added thereto, and the solution was heated for 5 hours while refluxing.
  • toluene (30 ml) and water (70 ml) were added thereto, and extracting practice was carried out. The organic layer was washed with water and then dried on anhydrous magnesium sulfate.
  • R 1 , Q 1 , Q 2 and Y 1 have the meanings described above. TABLE 1 No. R 1 Q 1 Q 2 Y 1 1-1-1 —CH 3 Q 2 -1-1 —OH 1-1-2 —CH 3 Q 2 -1-2 —COOH 1-1-3 —CH 3 Q 2 -1-1 —OCOCH ⁇ CH 2 1-1-4 —CH 3 Q 2 -1-1 1-1-5 —CH 3 Q 2 -1-3 1-1-6 —CH 3 Q 2 -1-3 1-1-7 —CH 3 Q 2 -1-4 —NH 2 1-1-8 —CH 3 Q 2 -1-5 1-2-1 Q 2 -2-1 —COOH 1-2-2 —CH 3 Q 2 -2-2 —OH 1-2-3 —C 2 H 5 Q 2 -2-3 —Cl 1-2-4 Q 2 -2-4 —CH ⁇ CHCOOCH(CH 3 ) 2 1-2-5 —OCH 3 Q 2 -2-5 —OCOC(CF 3
  • Q 2 -1-1 to Q 2 -89-2 described in the column of Q 2 have meanings shown in the following Formula (Q 2 -1-1) to Formula (Q 2 -89-2).
  • a code “ ⁇ ” shown at a left end in these formulas shows a bonding point to an Si atom.
  • a polyamic acid vanish (15 g) having a polymer concentration of 20% by weight was obtained in the same manner as in Comparative Example 1, except that pyromellitic dianhydride was changed to Compound (1-1-4) (1.49 g) and 4,4′-diaminodiphenyl ether was changed to Compound (1-3-7) (1.51 g) and that a use amount of NMP was changed to 12 g.
  • Polyamic acid contained in the above vanish is named PA acid 2.
  • a polyamic acid vanish (15 g) having a polymer concentration of 20% by weight was obtained in the same manner as in Example 5, except that Compound (1-1-4) was changed to pyromellitic dianhydride (0.39 g) and that a use amount of Compound (1-3-7) was changed to 2.61 g.
  • Polyamic acid contained in the above vanish is named PA acid 3.
  • a polyamic acid vanish (10 g) having a polymer concentration of 30% by weight was obtained in the same manner as in Example 5, except that a use amount of Compound (1-1-4) was changed to 2.63 g and Compound (1-3-7) was changed to 4,4′-diaminodiphenyl ether (0.38 g) and that a use amount of NMP was changed to 7 g.
  • Polyamic acid contained in the above vanish is named PA acid 4.
  • the respective vanishes of PA acid 1 to PA acid 4 were diluted to suitable concentrations by butyl cellosolve and coated on a glass substrate by means of a spinner. It was pre-baked at 80° C. for about 5 minutes and then subjected to heat treatment at 220° C. for 30 minutes and then at 300° C. for 60 minutes to form the respective polyimide thin films. These polyimide thin films are designated as PI-1, PI-2, PI-3 and PI-4. PI-1 to PI-4 were measured for physical properties, and the results thereof are shown in Table 29.
  • Example 11 A part of the polyester obtained in Example 11 was completely dissolved in NMP (9 g), and this solution was diluted to a suitable concentration by butyl cellosolve and coated on a glass substrate by means of a spinner. It was pre-dried at 80° C. for about 5 minutes and then subjected to heat treatment at 100° C. for one hour and then at 220° C. for 3 hours to obtain a polyester thin film PE-1. PE-1 was measured for physical properties, and the results thereof are shown in Table 29.
  • Example 11 The polyester (0.26 g) obtained in Example 11 was pressed by means of a pressing machine (upper face, lower face temperature: 260° C., press pressure: 19.6 MPa) to obtain a polyester substrate having an average thickness of 244 ⁇ m.
  • Bisphenol A glycidyl ether brand name: EPICLON 850S, manufactured by Dainippon Ink & Chemicals Inc.
  • NMP 1,3-bisphenol A glycidyl ether
  • This solution was coated on a copper foil, pre-baked at 80° C. for about 30 minutes and then subjected to heat treatment at 220° C. for 60 minutes and then at 220° C. for 60 minutes under reduced pressure, and it was subjected to etching treatment to obtain an epoxy resin film having a thickness of about 40 ⁇ m.
  • the above film had an average light transmittance of 65.2% in 400 to 800 nm, and a wavelength in which the light transmittance was less than 1% was 345 nm.
  • An epoxy compound solution having a compound concentration of 30% by weight was obtained in the same manner as in Comparative Example 2, except that EPICLON 850S was changed to Compound (1-1-5) (1.0 g) and a use amount of 4,4′-diaminodiphenyl ether was changed to 0.145 g and that a use amount of NMP was changed to 2.67 g.
  • the above solution was treated in the same manner as in Comparative Example 2 to obtain an epoxy resin film having a thickness of about 100 ⁇ m.
  • This film had an average light transmittance of 81.4% in 400 to 800 nm, and a wavelength in which the light transmittance was less than 1% was 260 nm. That is, it is apparent that a PSQ skeleton can be introduced into the epoxy resin without adding polysiloxane and that the resulting coating film is improved in transparency as compared with the coating film prepared in Comparative Example 2.
  • the compound of the present invention has a good compatibility with other compounds and polymers, and can readily provide a polymer of a high molecular weight having a silsesquioxane skeleton in a principal chain and/or side chains by homopolymerization or copolymerization.
  • the polymer is excellent in characteristics such as mechanical strength, coating property, compatibility, transparency, heat resistance, water repellency and electrical insulating property.
  • the polymer can be used for a coating agent, a plastic substrate and an optical material.

Abstract

The present invention relates to a compound represented by Formula (1) and a polymer obtained using the compound:
Figure US20050009982A1-20050113-C00001

wherein R1 is phenyl which may have substituents, Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms,
Figure US20050009982A1-20050113-C00002

and Q2 is a group represented by Formula (2) wherein the code < represents a bonding point with silicon, l, m, n and p are independently 0, 1, 2 or 3, A1 to A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene, Z0 to Z3 are independently a single bond, —CH═CR—, —C≡C—, —COO—, —OCO—, or alkylene having 1 to 20 carbon atoms, and Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene having 1 to 20 carbon atoms. And Y1 in Formula (1) is the group defined in Claim 1.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a compound having a silsesquioxane skeleton, a polymer obtained using the compound, and uses of the polymer.
  • BACKGROUND OF THE INVENTION
  • Polyorganosiloxane has excellent heat resistance, weatherability and surface-modifying function, and therefore it is used for semiconductor insulating protective films, flame retardants and coating material additives. For example, a coating agent prepared by blending an organic polymer with polyorganosiloxane can provide the surface of a material coated with the agent with functions such as water repellency. The representative examples of the organic polymer are acryl resins, polyurethanes and alkid resins. In general, however, these polymers do not have a good compatibility with polyorganosiloxane. Accordingly, there have been the problems that the coating agent is liable to become cloudy by blending polyorganosiloxane, and that a coating film obtained from the coating agent is liable to be whitened. That is, an addition amount of polyorganosiloxane has been restricted.
  • It has so far been known that an introduction of a polysiloxane structure into principal chain and/or side chain of an organic polymer makes it possible to improve the characteristics of the polymer such as heat resistance, water repellency and weatherability. Disclosed in, for example, the patent document 1 is a process in which a polysiloxane-containing polymer is radically copolymerized with other addition-polymerizable monomers to thereby produce a polysiloxane graft copolymer having a polysiloxane structure in a side chain. Polysilsesquioxane having a structure in which 1.5 oxygen atom is bonded to one silicon atom is disclosed in the patent document 2. It is described in the document that a polysilsesquioxane derivative having a polymerizable unsaturated bond and two or more functional groups such as hydroxyl group and alkoxy group is copolymerized with other addition-polymerizable monomers to thereby obtain a vinyl polymer into which a siloxane side chain is introduced. All of them are considered to be excellent in heat resistance, water repellency and weatherability as compared with the homopolymers of the other addition-polymerizable monomers.
  • It has so far been tried to enhance the content of a polyorganosiloxane structure in an organic polymer for the purpose of improving the characteristics as described above. However, in the foregoing organic polymer having a polyorganosiloxane structure, such a high improving effect as expected has not been provided to the characteristics such as heat resistance, water repellency, weatherability and electric insulating property. Accordingly, strongly desired is a polyorganosiloxane having a structure which further elevates characteristics such as heat resistance, water repellency and weatherability in the organic polymer.
      • Patent document 1: JP S60-231720 A/1985
      • Patent document 2: JP S62-275132 A/1987
  • An object of the present invention is to provide a useful polysilsesquioxane derivative in order to solve the problems described above, and another object is to provide a novel polymer obtained by using the derivative. Still another object is to provide a coating agent, a plastic substrate and an optical material each obtained by using the polymer.
  • SUMMARY OF THE INVENTION
  • First, terms and codes used in the present invention shall be explained. The term “optional” shows that not only the position but also the number are optional. For example, when “optional —CH2— in alkyl may be replaced by —O— or —CH═CH—” is expressed, plural —CH2— may be replaced by different groups respectively. Examples in such case are alkyl, alkoxy, alkoxyalkyl, alkoxyalkenyl and alkenyloxyalkyl. Alkyl and alkylene are used as groups including both of linear group and branched group unless otherwise described. The examples of halogen are fluorine, chlorine and bromine.
  • The present invention is constituted by the following items [1] to [40].
  • [1] A compound represented by Formula (1):
    Figure US20050009982A1-20050113-C00003

    wherein R1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; and Q2 is a group represented by Formula (2):
    Figure US20050009982A1-20050113-C00004

    wherein the code < represents a bonding point with silicon; l, m, n and p are independently 0, 1, 2 or 3; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in these rings, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional —CH═ may be replaced by —N═; optional hydrogen in all rings may be replaced by halogen, —CN, —NO2 or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is halogen, —OM1-, —SM1-, —CHO, —COOR3—, —CSOR3—, —CSSR3—, —NHR4—, —COX1—, —CSX1—, —OCOX1—, —OCOOR3—, —N═C═O, —CN, —C≡CH, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2, —SO2X1, —SiR2 2X1, —SiR2 2OR3, —SiR2 2OCOR7, —SiR2 2OC(CH3)═CH2, —SiR2 2ON═CR7R8, —SiR2 2NR7R8, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00005

    in these groups related to Y1, M1 is hydrogen or alkaline metal; R3 is hydrogen, alkaline metal, or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; R4 is hydrogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O— and optional hydrogen may be replaced by halogen, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by ≡O—, —CH═CH— or —C, and optional hydrogen may be replaced by halogen; X1 is halogen; R5, R6 and X2 are independently hydrogen, halogen, —CN, or alkyl in which the number of carbon atoms is 1 to 10 optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; R7 and R8 are independently alkyl having 1 to 10 carbon atoms; G1 is a trivalent organic group; R9 is hydrogen or alkyl having 1 to 5 carbon atoms; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
  • [2] The compound as described in the item [1], wherein in Formula (1), R1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; and Q2 is a group represented by Formula (2); in Formula (2), the code < represents a bonding point with silicon; l, m, n and p are independently 0, 1, 2 or 3; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in these rings, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional —CH═ may be replaced by —N═; in all rings, optional hydrogen may be replaced by halogen, —CN, —NO2, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is halogen, —OM1-, —SM1-, —CHO, —COOR3—, —CSOR3—, —CSSR3—, —NHR4—, —COX1—, —CSX1—, —OCOX1—, —OCOOR3—, —N═C═O, —CN, —C≡CH, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2, —SO2X1, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00006

    in the above groups related to Y1, M1 is hydrogen or alkaline metal; R3 is hydrogen, alkaline metal, or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; R4 is hydrogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen, or phenyl in which optional hydrogen may be replaced by halogen, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by ≡O—, —CH═CH— or —C, and optional hydrogen may be replaced by halogen; X1 is halogen; R5, R6 and X2 are independently hydrogen, halogen, —CN, or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; G1 is a trivalent organic group; R9 is hydrogen or alkyl having 1 to 5 carbon atoms; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
  • [3] The compound as described in the item [1] or [2], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine.
  • [4] The compound as described in the item [1] or [2], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • [5] The compound as described in the item [1] or [2], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in the above rings, optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the above alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene which has a carbon number of 1 to 20 and in which optional —CH2— may be replaced by —O—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; and Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—.
  • [6] The compound as described in the item [1] or [2], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in the above rings, optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the above alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is chlorine, bromine, —OM1-, —SM1-, —CHO, —COOR3—, —NHR4—, —COX1—, —OCOX1—, —N═C═O, —CN, —C≡CH, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2, —SO2X1, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00007

    in the above groups related to Y1, M1 is hydrogen or alkaline metal; R3 is hydrogen, alkaline metal, or alkyl having 1 to 5 carbon atoms; R4 is hydrogen, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; X1 is chlorine or bromine; R5, R6 and X2 are independently hydrogen, fluorine, chlorine, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
  • [7] The compound as described in the item [6], wherein R1 is phenyl.
  • [8] The compound as described in the item [6], wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • [9] The compound as described in the item [6], wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent for 1,4-phenylene, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; and Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—.
  • [10] The compound as described in the item [6], wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent for 1,4-phenylene, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is —OM1-, —CHO, —COOR3 —, —NHR4—, —COX1—, —OCOX1—, —N═C═O, —CR5═CH2, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00008

    in the above groups related to Y1, M1 is hydrogen, sodium or potassium; R3 is hydrogen, sodium, potassium, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; R4 is hydrogen, phenyl, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; X1 is chlorine or bromine; R5 and X2 are independently hydrogen, fluorine, chlorine, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
  • [11] The compound as described in the item [10], wherein Q1 is alkyl having 1 to 5 carbon atoms, or phenyl.
  • [12] The compound as described in the item [10], wherein Q1 is alkyl having 1 to 5 carbon atoms or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine or methyl; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
  • [13] The compound as described in the item [10], wherein Q1 is alkyl having 1 to 5 carbon atoms or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine or methyl; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and Y1 is —OM1-, —COOR3—, —NHR4—, —COX1—, —N═C═O, —CR5═CH2, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00009

    in the above groups related to Y1, M1 is hydrogen, sodium or potassium; R3 is hydrogen, sodium, potassium, methyl or ethyl; R4 is hydrogen, methyl or phenyl; X1 is chlorine or bromine; R5 and X2 are independently hydrogen, fluorine or alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
  • [14] The compound as described in the item [13], wherein Q1 is methyl or phenyl.
  • [15] The compound as described in the item [13], wherein Q1 is methyl or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene; and Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
  • [16] The compound as described in the item [13], wherein Q1 is methyl or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and Y1 is —OM1-, —COOR3—, —NHR4—, —COCl—, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00010

    in the above groups related to Y1, M1 is hydrogen, sodium or potassium; R3 is hydrogen, sodium, potassium, methyl or ethyl; R4 is hydrogen or methyl; X2 is hydrogen, fluorine or methyl; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
  • [17] The compound as described in the item [16], wherein Y1 is —OH, —COOR3, —NH2, —COCl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00011

    in the above groups related to Y1, R3 is hydrogen, methyl or ethyl; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
  • [18] A polymer having a structural unit represented by Formula (3):
    Figure US20050009982A1-20050113-C00012

    wherein R1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen; Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; and Q3 is a group represented by Formula (4):
    Figure US20050009982A1-20050113-C00013

    wherein a code < represents a bonding point with silicon; l, m, n and p are independently 0, 1, 2 or 3; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in these rings, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional —CH═ may be replaced by —N═; optional hydrogen in all rings may be replaced by halogen, —CN, —NO2 or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z5 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or a group represented by —W1-T1-; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and T1 is —O—, —S—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —CO—, —COO—, —OCO—, —CSO—, —OCS—, —CONR10—, —NR10CO—, —CONR10O—, —ONR10CO—, —OCONR10—, —NR10CONR10—, —NR10COO—, —OCOO—, —CH(OH)CH2—, —CH2CH(OH)—, —CH═CH—, —CH2CR5═CR6CH2—, —C≡C—, —SO2—, —SO2O—, —OSO2—, —SO2S—, —SSO2—, —SO2NR7—, —NR10SO2—, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00014

    in the groups related to T1, R2 is the same as described above; R10 is hydrogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by halogen, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C, and optional hydrogen may be replaced by halogen; R5, R6 and X2 are independently hydrogen, halogen, —CN or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen or alkyl having 1 to 5 carbon atoms; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
  • [19] The polymer as described in the item [18], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine.
  • [20] The polymer as described in the item [18], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; and in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • [21] The polymer as described in the item [18], wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or a condensed ring group having 6 to 10 carbon atoms which is a divalent group; in these rings, optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z5 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or a group represented by —W1-T1; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, —OCOO—, —CH(OH)CH2—, —CH2CH(OH)—, —CH═CH—, —C≡C—, —SO2—, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00015

    in these groups related to T1, R10 is hydrogen, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; X2 is hydrogen, fluorine, chlorine or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2—, which is not adjacent to each other, may be replaced by —O— and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen, methyl or ethyl; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
  • [22] The polymer as described in the item [21], wherein R1 is phenyl.
  • [23] The polymer as described in the item [21], wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; and in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
  • [24] The polymer as described in the item [21], wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl having 1 to 5 carbon atoms, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of 1,4-phenylene, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; Z5 is a single bond, —COO—, —OCO— or a group represented by —W1-T1; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00016

    in these groups related to T1, R10 is hydrogen, alkyl having 1 to 5 carbon atoms, or phenyl; X2 is hydrogen, fluorine or alkyl having 1 to 5 carbon atoms; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen, methyl or ethyl; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
  • [25] The polymer as described in the item [24], wherein Q1 is methyl or phenyl.
  • [26] The polymer as described in the item [24], wherein Q1 is methyl or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene; Z0, Z1, Z2 and Z3 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; Z5 is a single bond, —COO—, —OCO— or a group represented by —W1-T1; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00017

    in these groups related to T1, R10 is hydrogen or methyl; X2 is hydrogen or methyl; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen, methyl or ethyl; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
  • [27] The polymer as described in the item [26], wherein T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00018
  • [28] A composition comprising the compound as described in any one of the items [1] to [17].
  • [29] A polymer obtained by using at least one of the compounds as described in any one of the items [1] to [17].
  • [30] The polymer as described in the item [29], obtained by using only the compound as described in any one of the items [1] to [17].
  • [31] The polymer as described in the item [29], obtained by using at least one of the compounds as described in any one of the items [1] to [17] and at least one of compounds other than the compound as described in the item [1].
  • [32] The polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31], wherein the polymer is polyimide, polyamic acid, polyester, an epoxy resin, polyacrylate or polymethcylate.
  • [33] A composition comprising at least one of the polymers as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • [34] A coating agent comprising the polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • [35] A varnish composition comprising the polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • [36] A thin film formed by using the varnish composition as described in the item [35].
  • [37] A multilayer thin film formed by using the varnish composition as described in the item [35] and at least one of compositions of other polymers.
  • [38] A structural matter, wherein a part or the whole of a structural unit thereof is comprised with at least one of the polymer as described in any one of the items [18] to [27], or any one of the items [29] to [31].
  • [39] A plastic substrate having the thin film as described in the item [36].
  • [40] An optical material having the thin film as described in the item [36].
  • DETAILED DESCRIPTION OF THE INVENTION
  • In the following explanations, the compound represented by Formula (1) shall be designated as the compound (1), and the polymer having the structural unit represented by Formula (3) shall be designated as the polymer (3). Compounds and polymers represented by other formulas shall be designated by the same abbreviation. A silsesquioxane skeleton shall be designated as a PSQ skeleton.
  • First, the compound of the present invention shall be explained. The compound of the present invention has a silsesquioxane skeleton and is represented by Formula (1).
    Figure US20050009982A1-20050113-C00019
  • R1 in Formula (1) is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen. The preferred examples of R1 are phenyl and phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms. More preferred examples of R1 are phenyl and phenyl in which at least one hydrogen is replaced by alkyl having 1 to 5 carbon atoms. The most preferred example of R1 is phenyl.
  • Q1 in Formula (1) is hydrogen, halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl having 1 to 10 carbon atoms, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms. In both of the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C and optional hydrogen may be replaced by halogen.
  • The preferred examples of Q1 are hydrogen, halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl having 1 to 10 carbon atoms in which optional —CH2—, which is not adjacent to each other, may be replaced by —CH═CH—, and phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—. In both of the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional hydrogen may be replaced by halogen.
  • More preferred examples of Q1 are hydrogen, —F, —Cl, —CF3, —OCF3, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxymethyl, methoxypropyl, ethoxylpropyl, propoxypropyl, 2-fluoroethyl, 3-fluoropropyl, vinyl, 1-propenyl, 2-propenyl, allyl, 3-butenyl, 3-pentenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl.
  • Q2 in Formula (1) is a group represented by Formula (2).
    Figure US20050009982A1-20050113-C00020

    In Formula (2), a code < represents a bonding point with silicon. A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene. In these rings, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional —CH═ may be replaced by —N═. However, it is not preferred that two adjacent —CH2— are replaced in the form of —O—O—. The examples of 1,4-cyclohexylene in which —CH2— is replaced by —O—, are 1,3-dioxane-2,5-diyl and 1,4-dioxane-2,5-diyl. The examples of 1,4-phenylene in which —CH═ is replaced by —N═, are pyridine-2,5-diyl, pyrimidine-2,5-diyl and pyridazine-3,6-diyl. And, in all the rings described above which are the examples of A1 to A4, optional hydrogen may be replaced by halogen, —CN, —NO2 or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen.
  • The preferred examples of A1 to A4 are a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[3.1.0]hex-3,6-diyl, bicyclo[2.2.2]oct-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms, and 1,4-phenylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms.
  • More preferred examples of A1 to A4 are a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine or methyl, and 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine, methyl, ethyl or propyl.
  • Further more preferred examples of A1 to A4 are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 3-methyl-1,4-phenylene, 3-ethyl-1,4-phenylene and 3-propyl-1,4-phenylene.
  • Z0, Z1, Z2, and Z3 in Formula (2) are bonding groups. They are independently a single bond, —CH═CH—, —C COO—, —OCO—, or alkylene having 1 to 20 carbon atoms. Optional —CH2—, which is not adjacent to each other, in the alkylene may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSi R2 2—, —COO—, —OCO—, ≡CH═CH— or —C The alkylene may have asymmetric carbon and may be optically active.
  • R2 described above is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl having 1 to 10 carbon atoms, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen.
  • The preferred examples of Z0 to Z3 are a single bond, —(CH2)a—, —O(CH2)a—, —(CH2)aO—, —O(CH2)aO—, —(CH2)aO(CH2)b—, —O(CH 2)aO(CH2)b≡C—, —C
    Figure US20050009982A1-20050113-P00999
    H— and C—OCO—. The terms a and b are independently an integer of 1 to 18, and the preferred range thereof is 1 to 10. More preferred examples of Z0 to Z3 are a single bond, —(CH2)2—, —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH2)6—, —(CH2)7—, —(CH2)8—, —(CH2)9—, —(CH2)10—, —OCH2—, —O(CH2)2—, —O(CH2)3—, —O(CH2)4—, —O(CH2)5—, —O(CH2)6—, —O(CH2)7—, —O(CH2)8—, —O(CH2)9—, —O(CH2)10—, —CH2O—, —(CH2)2O—, —(CH2)3O—, —(CH2)4O—, —(CH2)5O—, —(CH2)6O—, —(CH2)7O—, —(CH2)8O—, —(CH2)9O—, —(CH2)10O—, —O(CH2)2O—, —O(CH2)3O—, —O(CH2)4O—, —O(CH2)5O—, —O(CH2)6O—, —O(CH2)7O—, —O(CH2)8O—, —O(CH2)9O—, —O(CH2)10O—, —CH2OCH2—, —(CH2)2OCH2—, —(CH2)3OCH2—, —(CH2)4OCH2—, —(CH2)5OCH2—, —(CH2)6OCH2—, —(CH2)7OCH2—, —(CH2)8OCH2—, —(CH2)9OCH2—, —(CH2)10OCH2—, —O(CH2)2OCH2—, —O(CH2)3OCH2—, —O(CH2)4OCH2—, —O(CH2)5OCH2—, —O(CH2)6OCH2—, —O(CH2)7OCH2—, —O(CH2)8OCH2—, —O(CH2)9OCH2—, —O(CH2)10OCH2— and —CH═CH—.
  • Z4 in Formula (2) is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or, alkylene having 1 to 20 carbon atoms. In the alkylene having 1 to 20 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—. The preferred example of Z4 is alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
  • When rings or bonding groups contained in the group represented by Formula (2) have plural steric configurations, the steric configurations may be any one of cis, trans and a mixture thereof. The bonds of R1, Q1 and Q2 to the PSQ skeleton are not restricted in terms of a steric configuration.
  • Y1 in Formula (1) is halogen, —OM1, —SM1, —CHO, —COOR3, —CSOR3, —CSSR3, —NHR4 1, —COX1, —CSX1, —OCOX1, —OCOOR3, —N═C═O, ≡CN, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2—, —SO2X1, —SiR2 2X1, —SiR2 2OR3, —SiR2 2OCOR7, —SiR2 2OC═CH2CH3, —SiR2 2ON═CR7R8, —SiR2 2NR7R8, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00021
  • Codes in these groups related to Y1 are defined as follows. M1 is hydrogen or alkaline metal. R3 is hydrogen, alkaline metal or alkyl having 1 to 10 carbon atoms. In the alkyl having 1 to 10 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen. R4 is hydrogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen, or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 10 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen. In the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH—
    Figure US20050009982A1-20050113-P00999
    C—C, and optional hydrogen may be replaced by halogen. X1 is halogen, and chlorine and bromine are preferred. R5, R6 and X2 are independently hydrogen, halogen, —CN, or alkyl having 1 to 10 carbon atoms. In the alkyl having 1 to 10 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen. The preferred examples of R5, R6 and X2 are hydrogen, methyl, —F, —CF3 and phenyl. R7 and R8 are independently alkyl having 1 to 10 carbon atoms. R9 is hydrogen or alkyl having 1 to 5 carbon atoms. The preferred examples of R9 are hydrogen, methyl and ethyl. G1 is a trivalent organic group. This is a part of a tetracarboxylic acid's residue when the compound having a PSQ skeleton is tetracarboxylic anhydride.
  • The preferred example of Y1 is —OM1, —CHO, —COOR3, —NHR4, —COX1, —OCOX1, —N═C═O, —CR5═CH2, 1,2-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00022
  • More preferred example of Y1 is —OM1, —COOR3, —NHR4, —COX1, —N═C═O, —CR5═CH2, 1,2-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00023
  • Further more preferred example of Y1 is —OH, —COOR3, —NH2, —COCl, oxiranyl, oxetanyl or a group shown below:
    Figure US20050009982A1-20050113-C00024
  • When Y1 is an addition-polymerizable group, it is preferred that an addition-polymerizable group is not contained in Q1 of Formula (1). It is preferred as well that an addition-polymerizable group is not contained in a substituent of a ring constituting Q2. When Y1 is a condensation-polymerizable group, it is preferrd that Q1 in Formula (1) is a group which do not react with Y1. It is preferred as well that a group which reacts with Y1 is not contained in a substituent of a ring constituting Q2 and a bonding group connecting rings.
  • Formula (2) can be specified to preferred formulas such as Formula (1-1) to Formula (1-86) shown below. Codes in these formulas mean the same as described above. Groups showing 1,4-cyclohexylene, 1,4-phenylene and pyridine-2,5-diyl each represent groups shown by the following formulas:
    Figure US20050009982A1-20050113-C00025
    Figure US20050009982A1-20050113-C00026
    Figure US20050009982A1-20050113-C00027
    Figure US20050009982A1-20050113-C00028
    Figure US20050009982A1-20050113-C00029
    Figure US20050009982A1-20050113-C00030
    Figure US20050009982A1-20050113-C00031
    Figure US20050009982A1-20050113-C00032
    Figure US20050009982A1-20050113-C00033
    Figure US20050009982A1-20050113-C00034
  • Among the above formulas, Formula (1-1) to Formula (1-80) are more preferred, and Formula (1-1) to Formula (1-58) are further more preferred.
  • Isotopes such as heavy hydrogen and 13C may be contained in the compound (1) in a larger proportion than those of naturally present ones. In such case, the compounds make little difference in physical properties.
  • Next, the polymer of the present invention shall be explained. The polymer of the present invention is a polymer having a PSQ skeleton and has a structural unit represented by Formula (3):
    Figure US20050009982A1-20050113-C00035
  • In Formula (3), R1 and Q1 are groups defined in the same manner as these codes in Formula (1), and the preferred examples of them are the same as in Formula (1). And, Q3 is a group represented by Formula (4):
    Figure US20050009982A1-20050113-C00036

    Codes in the formula are groups defined in the same manner as these codes in Formula (2) excluding Z5, and the preferred examples of them are the same as in Formula (2). Z5 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or a group represented by —W1-T1-. W1 is a single bond or alkylene having 1 to 20 carbon atoms. In the alkylene, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—. The preferred example of W1 is alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
  • T1 is —O—, —S—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —CO—, —COO—, —OCO—, —CSO—, —OCS—, —CONR10—, —NR10CO—, —CONR10O—, —ONR10CO—, —OCONR10—, —NR10CONR10—, —NR10COO—, —OCOO—, —CH(OH)CH2—, —CH2CH(OH)—, —CH═CH—, —CH2CR5═CR6CH2—, —SO2—, —SO2O—, —OSO2—, —SO2S—, —SSO2—, —SO2NR10—, —NR10SO2—, or any one of groups shown below:
    Figure US20050009982A1-20050113-C00037
  • In these groups related to T1, R2 is the same as described above. R10 is hydrogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 10 carbon atoms, optional hydrogen may be replaced by halogen. In the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by ≡O—, —CH═CH— or —C, and optional hydrogen may be replaced by halogen. The preferred examples of R10 are hydrogen, methyl, ethyl, propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and phenyl. R5, R6 and X2 have the same meanings as these codes in the definitions related to Y1, and the preferred examples thereof are the same as described above.
  • G1 is a trivalent organic group. This is a part of tetracarboxylic acid's residue when the structural unit having a PSQ skeleton is derived from tetracarboxylic acid-derivative having a PSQ skeleton. G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue. This shows a part of polybasic acid-derivative's rsidue which are the target of the reaction when the structural unit having a PSQ skeleton is derived from diamine having a PSQ skeleton. The structural unit in which T1 is a group containing G1 is derived by the reaction of tetracarboxylic acid-derivative having a PSQ skeleton with diamine. This diamine may be diamine having a PSQ skeleton or diamine having no PSQ skeleton. The structural unit in which T1 is a group containing G2 is derived by the reaction of diamine having a PSQ skeleton with polybasic acid-derivative. The polybasic acid-derivative may be tetracarboxylic acid-derivative having a PSQ skeleton, or tricarboxylic acid-derivative or tetracarboxylic acid-derivative having no PSQ skeleton. The term “tetracarboxylic acid-derivative(s)” is used as a general term including ester, acid anhydride and acid halide of tetracarboxylic acid in addition to tetracarboxylic acid, in the present invention. Polybasic acid-derivative(s), tricarboxylic acid-derivative(s) and dicarboxylic acid-derivative(s) are terms defined in the same manner as described above.
  • The compound (1) can be produced by reacting a compound (1a) with dichlorosilane (1b) in the presence of a base such as triethylamine:
    Figure US20050009982A1-20050113-C00038

    In this scheme, Et3N is triethylamine, and the other codes have the same meanings as described above. The compound (1a) can be produced by subjecting a silane compound R1SiA3 to hydrolysis and condensation polymerization in the presence of monovalent alkaline metal hydroxide and water, in the presence or absence of an organic solvent. A is a hydrolyzable group and is preferably chlorine and alkoxy having 1 to 4 carbon atoms. The examples of the monovalent alkaline metal hydroxide are lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide. Among them, sodium hydroxide and potassium hydroxide are preferred. The amount of the monovalent alkaline metal hydroxide used is 0.3 to 1.5 in terms of a mole ratio based on the silane compound described above, and more preferred mole ratio is 0.4 to 0.8. The amount of water added is 1.0 to 1.5 in terms of a mole ratio based on the silane compound, and more preferred mole ratio is 1.1 to 1.3. The preferred examples of the organic solvent are linear, branched or cyclic monovalent alcohols. It is estimated that alcohol contributes to a control of the structure in a condensing step.
  • The compound (1a) is reacted with dichlorosilane (1c) to prepare a compound (1d), and then the compound (1d) may be reacted with a compound (1e) in the presence of a catalytic amount of a radical polymerization initiator (azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide and the like) or a transition metal compound (Pt, Rh, Pd, Ni and the like). Thus, a compound (2a) is obtained.
    Figure US20050009982A1-20050113-C00039
  • In the scheme described above, G2a is a group represented by Formula (5), and the other codes have the same meanings as described above.
    Figure US20050009982A1-20050113-C00040

    In Formula (5), l, m, n and p are independently 0, 1, 2 or 3, and Z6 is a single bond, —CH═CH—, ≡C—, —COO—, —OCO—, or alkylene having 1 to 18 carbon atoms. In the alkylene, optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSi R2 2O—, —SiR2 2OSi R2 2≡C—COO—, —OCO—, —CH═CH— or —C
  • One example of a method for forming the bonding group Z1, Z2, Z3, Z4 or Z6 shall be explained by showing a scheme. MSG1 and MSG2 in the following scheme each are monovalent or divalent organic groups having at least one ring. Plural MSG1 (or MSG2) in the scheme may be the same or different. A compound (1A) to a compound (1H) correspond to the compound (I).
    (I) Formation of Single Bond
    Figure US20050009982A1-20050113-C00041
  • A boric acid derivative (6) and a halide (7) synthesized by a publicly known method are reacted in a carbonate aqueous solution in the presence of a catalyst such as tetrakis(triphenylphosphine)-palladium to synthesize a compound (1A). This compound (1A) can be synthesized as well by first reacting n-butyllithium with a compound (8) synthesized by a publicly known method, then reacting zinc chloride and further reacting the compound (7) in the presence of a catalyst such as dichlorobis-(triphenylphosphine)palladium. The boric acid derivative (6) can be produced by deriving the compound (8) into a Grignard reagent or a lithium reagent and reacting it with trialkylboric acid ester.
    (II) Formation of —COO— and —OCO—
    Figure US20050009982A1-20050113-C00042
  • The compound (8) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (9). The carboxylic acid (9) is dehydrated with phenol (10) synthesized by a publicly known method, in the presence of DCC (1,3-dichlorohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to synthesize a compound (1B) having —COO—. A compound having —OCO— can be synthesized as well by the method.
    (III) Formation of —CH═CH—
    Figure US20050009982A1-20050113-C00043
  • The compound (7) is treated with n-butyllithium and then reacted with formamide such as N,N-dimethyl-formamide to obtain aldehyde (11). A phosphonium salt (12) synthesized by a publicly known method is treated with a base such as potassium t-butoxide to produce phosphorus ylid, and this is reacted with. the aldehyde (11) to synthesize a compound (1C). The cis compound is formed depending on the reaction conditions, and therefore the cis compound is isomerized, if necessary, to the trans compound by a publicly known method.
    (IV) Formation of —(CH2)2
    Figure US20050009982A1-20050113-C00044
  • The compound (1C) is hydrogenated in the presence of a catalyst such as palladium carbon to thereby synthesize a compound. (1D).
    (V) Formation of —(CH2)4
    Figure US20050009982A1-20050113-C00045
  • A phosphonium salt (13) is used in place of the phosphonium salt (12) to obtain a compound having —(CH2)2—CH═CH— according to the method described in the item (III). This is catalytically hydrogenated to synthesize a compound (1E).
    (VI) Formation of ≡C—
    Figure US20050009982A1-20050113-C00046
  • The compound (8) is reacted with 2-methyl-3-butyne-2-ol in the presence of a catalyst of dichloropalladium and copper halide, and then the compound is deblocked on a basic condition to obtain a compound (14). The compound (14) is reacted with the compound (7) in the presence of a catalyst of dichloropalladium and copper halide to synthesize a compound (1F).
    (VII) Formation of —CH2O— or —OCH2
    Figure US20050009982A1-20050113-C00047
  • The compound (11) is reduced by a reducing agent such as sodium boron hydride to obtain a compound (15). This is halogenated with hydrobromic acid to obtain a compound (16). The compound (16) is reacted with the compound (10) in the presence of potassium carbonate to synthesize a compound (1G).
    (VIII) Formation of —(CH2)3O— or —O(CH2)3
    Figure US20050009982A1-20050113-C00048
  • A compound (17) is used in place of the compound (11) to synthesize a compound (1H) according to the method described in the item (VII).
  • In addition to the examples described above, the compound (1) can be produced by using freely synthetic methods in organic chemistry which are described in Houben-Wyle, Methods of Organic Chemistry, George Thieme Verlag, Stuttgart, Organic Syntheses, John Wiley & Sons Inc., Organic Reactions, John Wiley & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, and New Experimental Chemical Course (Maruzen).
  • Next, the polymer of the present invention shall be explained. The homopolymer is obtained by polymerizing only one compound (1). A copolymer of the compound (1) is obtained by polymerizing a polymerizable composition containing at least two compounds (1). The copolymer is obtained as well by polymerizing a polymerizable composition containing the compound (1) and other polymerizable compounds. All of these homopolymer and copolymers have almost the same structural unit as the structural unit represented by Formula (3). A configuration of the structural unit in the copolymer may be any one of random, block, alternation and graft.
  • The polymer is obtained by subjecting the compound (1) or a polymerizable composition containing the compound (1) to addition polymerization or condensation polymerization. That is, when the functional group Y1 in the compound (1) is an addition-polymerizable group, it is addition-polymerized by heat or light. When Y1 is a condensation-polymerizable group, it is condensation-polymerized with a compound having at least two functional groups which can be reacted with Y1. The polymerizable composition containing the compound (1) is preferably an addition-polymerizable composition or a condensation-polymerizable composition.
  • The addition-polymerizable composition is a composition containing the compound (1) having an addition-polymerizable group and further containing other addition-polymerizable compounds. The other addition-polymerizable compound may be another compound (1) having an addition-polymerizable group or may be an addition-polymerizable compound which is not the compound (1). They may be blended all together. In the following explanations, the addition-polymerizable compound other than the compound (1) shall be referred to as the other polymerizable compound. The condensation-polymerizable composition is a composition containing the compound (1) having a condensation-polymerizable group and further containing other condensation-polymerizable compounds having at least two functional groups which are reacted with the functional group. The other condensation-polymerizable compound may be another compound (1) having a condensation-polymerizable group, or may be a compound other than the compound (1). They may be blended all together. In the following explanations, the condensation-polymerizable compound other than the compound (1) shall be referred to as the other reactive compound.
  • When the addition-polymerizable composition is subjected to heat polymerization, the reaction temperature is 0 to 300° C., and the reaction time is 1 to 100 hours. Usually, a radical polymerization initiator is used. The examples of the radical polymerization initiator are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxydiisobutylate, lauroyl peroxide, dimetyl 2,2′-azobisisobutyrate(MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN) and azobiscyclohexanecarbonitrile (ACN).
  • When the addition-polymerizable composition is polymerized by irradiation with light or an electron beam, a radical photopolymerization initiator may be used. Darocure 1173 (2-hydroxy-2-methyl-1-phenylpropane-1-one), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimetoxy-1,2-diphenylethane-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocure 4265 and Irgacure 784, among the products of Ciba Specialty Chemicals Co., Ltd., can be given as the examples of the radical photopolymerization initiatorare.
  • The other examples of the radical photopolymerization initiator are p-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, a mixture of benzophenone/Michler's ketone, a mixture of hexaarylbiimidazole/mercaptobenzimidazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyldimethylketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and a mixture of 2,4-diethylxanthone/methyl p-dimethylaminobenzoate.
  • Used for the condensation polymerization reaction are a method in which the raw materials are reacted in a solution state, a method in which the raw materials are reacted in a molten state, a method in which the raw materials are reacted in a vaporized state by heating under reduced pressure and a method in which they are reacted by giving energy such as light, supersonic wave and plasma from the outside to activate them. Usually, a polymerization accelerator such as acid, alkali, metal compounds and the like is used for the purpose of accelerating the polymerization reaction. For example, polyester is produced by esterification or transesterification. The examples of the polymerization accelerator in the reaction are simple substances such as alkaline metals, alkaline earth metals, tin, germanium, antimony, zinc, cobalt, nickel, titanium and aluminum, and compounds thereof. The examples of the compounds are oxides, hydroxides, halides, carbonates, hydrogencarbonates and acetates. Inorganic acid salts, organic acid salts and complexes of the alkylated compounds thereof can be given.
  • The examples of the germanium compounds are germanium dioxide, germanium tetraethoxide and germanium tetra-n-butoxide. The examples of the titanium compounds are tetraalkyl titanate (tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate and the like) and partially hydrolyzed products thereof, titanyl oxalate compounds (titanyl oxalate, ammonium titanyl oxalate, sodium titanyl oxalate, potassium titanyl oxalate, calcium titanyl oxalate, strontium titanyl oxalate and the like), titanium trimellitate, titanium sulfate and titanium chloride. The examples of the antimony compounds are antimony trioxide, antimony acetate, antimony tartarate, potassium antimony tartarate, antimony oxychloride, antimony glycolate, antimony pentaoxide and triphenylantimony. The examples of the aluminum compounds are aluminum carboxylate (aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate and the like), aluminum oxide, aluminum hydroxide, aluminum chloride, chloroaluminum hydroxide, aluminum carbonate, aluminum alkoxides (aluminum methoxide, aluminum ethoxide and the like), aluminum acetylacetonate or aluminum chelate compounds with aluminum acetylacetonate, organic aluminum compounds (trimethylaluminum, triethylaluminum and the like) and partially hydrolyzed products thereof.
  • A stabilizer can be used as well in addition to the polymerization accelerating agent. The examples of the stabilizer are phosphoric acid esters (trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate and the like), phosphorous acid esters (triphenyl phosphite, trisdodecyl phosphite, trisnonylphenyl phosphite and the like) and phosphoric acid and polyphosphoric acid.
  • For example, polyimide can be produced by subjecting diamine and tetracarboxylic dianhydride to condensation polymerization to prepare polyamic acid and then dehydrating it by a thermal imidation method or a chemical imidation method. Usually, a reaction temperature in the thermal imidation method is 50 to 300° C. A dehydrating agent or a basic catalyst having a hydrolyzing ability is used in the chemical imidation method. The examples of the dehydrating agent are N,N-dialkylcarbodiimides, aliphatic carboxylic anhydrides (acetic anhydride, trifluoroacetic anhydride and the like), phosphoric acid derivatives (polyphosphoric acid, phosphorus pentaoxide and the like), acid anhydrides of phosphoric acid derivatives and acid chlorides (methanesulfonyl chloride, phosphorus pentachloride, thionyl chloride and the like). The examples of the basic catalyst are organic bases, tertiary amines and inorganic bases. The examples of the organic bases are N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, imidazole, N-methylcaprolactam, imidazole, N,N-dimethylaniline and N,N-diethylaniline. The examples of the tertiary amines are pyridine, collidine, lutidine and triethylamine. The examples of the inorganic bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
  • The epoxy resin is obtained from an epoxy composition containing at least one epoxy compound and a curing agent or a cationic photopolymerization initiator. The epoxy composition may contain, if necessary, a solvent and/or a curing-accelerating agent. The curing-accelerating agent accelerates the reaction of the epoxy compound with the curing agent. The specific examples of the cationic photopolymerization initiator shall be shown below. Almost all of them are commercially available and can readily be obtained.
  • The examples of the cationic photopolymerization initiator are diaryliodonium salts (hereinafter abbreviated as DAS) and triarylphosphonium salts (hereinafter abbreviated as TAS). The examples of DAS are diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosfonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetra(pentafluorophenyl)borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenato, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium p-toluenesulfonate, 4-methoxyphenylphenyliodonium diphenyliodonium tetra(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium diphenyliodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium diphenyliodonium hexafluoroarsenate, bis(4-tert-butylphenyl)iodonium diphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoroacetate, bis(tert-butylphenyl)iodonium p-toluenesulfonate and bis(4-tert-butylphenyl)iodonium diphenyliodonium tetra(pentafluorophenyl)borate.
  • DAS can be highly sensitized by adding a photosensitizer. The examples of the photosensitizer are thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene and rubrene.
  • The examples of TAS are triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarcenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetra(pentafluorophenyl)borate, 4-methoxyphenyl-diphenylsulfonium tetrafluoroborate, 4-methoxyphenyl-diphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarcenate, 4-methoxyphenyldiphenylsulfonium trifluoromethane-sulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra(pentafluorophenyl)borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluoro-phosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarcenate, 4-phenylthiophenyldiphenyl-sulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium p-toluenesulfonate and 4-phenylthiophenyldiphenylsulfonium tetra(pentafluorophenyl)borate.
  • Publicly known potential curing agents which are usually used as a curing agent for epoxy resins can be used as the curing agent. The examples of the potential curing agents for epoxy resins are amine base curing agents, novolak resin base curing agents, imidazole base curing agents and acid anhydride base curing agents. The examples of the amine base curing agents are aliphatic polyamines (diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine and the like), alicyclic polyamines (isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, Laromine and the like), aromatic polyamines (diaminodiphenylmethane, diaminodiphenyl ether, metaphenylenediamine, diaminodiphenylsulfone and the like), polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine mixtures and N-aminoethylpiperazine.
  • The examples of the novolak resin base curing agents are phenol novolak resins, bisphenol novolak resins, poly(p-vinylphenol) and the like. The examples of the imidazole base curing agents are 2-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium.trimellitate and 2-phenylimidazolium.isocyanurate.
  • The examples of the acid anhydride base curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenate methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexanetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerinbis(anhydrotrimellitate) monoacetate, dodecenylsuccinic anhydride, aliphatic dibasic polyanhydride and chlorendic anhydride. The other curing agents include dicyandiamide, ketimine compounds and the like.
  • The examples of the curing-accelerating agent for accelerating the curing reaction of the epoxy compound with the curing agent are tertiary amines (benzyldimethylamine, tris(dimethylaminomethyl)phenol, dimethylcyclohexylamine and the like), imidazoles (1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and the like), organic phosphorus base compounds (triphenylphosphine, triphenyl phosphite and the like), quaternary phosphonium salts (tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide and the like), diazabicycloalkenes (1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof and the like), organic metal compounds (zinc octylate, tin octylate and aluminum acetylacetone complexes thereof and the like), quaternary ammonium salts (tetraethylammonium bromide, tetrabutylammonium bromide and the like), boron compounds (boron trifluoride, triphenyl borate and the like) and metal halide compounds (zinc chloride, stannic chloride and the like). The curing-accelerating agents which can be used in the present invention shall not be restricted to the above examples. The above curing-accelerating agents can be used alone or in a mixture of two or more kinds thereof.
  • A method for producing the epoxy resin shall not specifically be restricted, and it can be produced by a publicly known method, for example, by blending an epoxy compound, a curing agent, a curing-accelerating agent or a cationic photopolymerization initiator and, if necessary, additives and mixing them by a publicly known method. Also, the epoxy resin can be produced by preparing two liquids of an epoxy composition comprising an epoxy compound as a principal component and a curing agent composition comprising a curing agent and a curing-accelerating agent as principal components and mixing the epoxy composition with the curing agent composition prior to use. Further, the epoxy resin can be produced as well by blending all of an epoxy compound, a curing agent, a curing-accelerating agent or a cationic photopolymerization initiator and, if necessary, additives in the form of a single liquid.
  • The examples of the epoxy compound other than the compound (1) used for the epoxy composition are glycidyl ethers (bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether and the like), glycidyl esters (glycidyl hexahydrophthalate, dimer acid glycidyl ester and the like), glycidylamines (triglycidyl isocyanurate, tetraglycidyl-diaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N,N,N′,N′-tetraglycidyl-m-xylenediamine and the like) and alicyclic or aliphatic epoxides (3,4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, epoxidized soy bean oil and the like).
  • A method for curing the epoxy composition shall not specifically be restricted, and capable of being used are publicly known curing apparatuses such as a closed type curing furnace and a tunnel furnace in which continuous curing can be carried out. The heating source shall not specifically be restricted, and heating can be carried out by publicly known methods such as hot air circulating, infrared heating and high-frequency heating. The curing temperature and the curing time fall preferably in the ranges of 80 to 250° C. and 30 seconds to 15 hours.
  • The polymer (3) can be produced as well by an anionic polymerization method, a coordinate polymerization method or a living polymerization method. The examples of the preferred catalyst used in these polymerization methods are alkyl alkaline metals (n-butyllithium, sec-butyllithium, t-butyllithium, trialkylaluminum and the like), aluminum compound and transition metal compound.
  • A solvent may be used for the polymerization reaction. The examples of the solvent are benzene, toluene, xylene, mesitylene, pentane, hexane, heptane, octane, nonane, decane, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, 1-3-dimethyl-2-imidazolidinone, imidazole, N-methylcaprolactam, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfoamide, cresol, phenol, xylenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol ldimethyl ether (triglyme), tetraglyme, dioxane, tetrahydrofuran and γ-buthyllactone. At least two of them may be used in a mixture.
  • Next, the other reactive compounds and the other polymerizable compounds used for copolymerizing with the compound (1) shall be explained. The preferred examples of the other reactive compounds are glycols, dicarboxylic acids, diamines and tetracarboxylic dianhydrides, but they shall not be restricted thereto. The preferred examples of the other polymerizable compounds are vinyl base monomers, fumaric acid diesters and maleimide derivatives, but they shall not be restricted thereto.
  • The glycols may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active. The examples of the aliphatic glycol are aliphatic diols (ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, neopentyl glycol and the like) and polyether compounds (polyethylene glycol, polypropylene glycol, polybutylene glycol and the like).
  • The examples of the alicyclic glycol are 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, tetralindimethanol, norbornanedimethanol, tricyclodecanedimethanol and pentacyclododecanedimethanol.
  • The examples of the aromatic glycol are alkylene oxide adducts of bisphenols and alkylene oxide adducts of aromatic dihydroxy compounds. The examples of the alkylene oxide adduct of bisphenol are 4,4′-(1-methylethylidene)bisphenol, methylenebisphenol (bisphenol F), 4,4′-cyclohexylidenebisphenol (bisphenol Z) and 4,4′-sulfonylbisphenol (bisphenol S). The examples of the alkylene oxide adducts of aromatic dihydroxy compounds are hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxydiphenylbenzophenone.
  • The glycols described above include ones in which isomers are present, and they may be mixtures containing them. Two or more glycols may be used in combination. When two or more glycols are used, two or more glycols may be selected from the same kind of the glycols described above, or at least one glycol may be selected from each of the different kind of the glycols. The glycols used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The dicarboxylic acids or the derivatives thereof may be belong to any one of groups of aliphatic type, alicyclic type, aromatic type and heterocyclic type, and they may contain a siloxane group and may be optically active. The examples of the aliphatic dicarboxylic acid are malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.
  • The examples of the alicyclic dicarboxylic acid are 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid and camphanic acid.
  • The examples of the aromatic dicarboxylic acid are o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalica acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene-dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene-dicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyl-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4″-terphenyldicarboxylic acid, 4,4,-diphenylmethane-dicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4-diphenylpropanedicarboxylic acid, 4,4′-diphenylhexafluoropropanedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-bibenzyl-dicarboxylic acid, 4,4′-stilbenedicarboxylic acid, 4,4′-trandicarboxylic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3′-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3′-(4,4′-(methylenedi-p-phenylene))dipropionic acid, 4,4′-(4,4′-(oxy-di-p-phenylene))dipropionic acid, 4,4′-(4,4′-(oxy-di-p-phenylene))dibutyric acid, (isopropylidenedi-p-phenylenedioxy)dibutyric acid and bis(p-carboxyphenyl)dimethyl silane.
  • The examples of the dicarboxylic acid containing heterocycles are 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furancarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridine-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid and 3,5-pyridinedicarboxylic acid.
  • The dicarboxylic acids described above may be monoesters, diesters, acid monohalides, acid dihalides or anhydrides. One of two carboxyl groups may be esterified, and the other may be acid halide. These compounds include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more dicarboxylic acids may be used in combination. When two or more dicarboxylic acids are used, two or more dicarboxylic acids may be selected from the same kind of the dicarboxylic acids described above, or at least one dicarboxylic acid may be selected from each of the different kind of the dicarboxylic acids. The dicarboxylic acids used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The diamines may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active. The examples of the aliphatic diamine are ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine. In these alkylenediamines, the diamines may have a structure in which optional —CH2— may be replaced by —O—.
  • The examples of the alicyclic diamine are 1,4-diaminodicyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4′-diaminodicyclohexylmethane, bis(2-methyl-4-aminocyclohexyl)methane, isophoronediamine, 2,5-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,3-diaminobicyclo[2.2.1]heptane, 2,5-diaminobicyclo-[2.2.1]heptane, 2,6-diaminobicyclo[2.2.1]heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,3-diamino-7-azabicyclo[2.2.1]heptane, 2,5-diamino-7-azabicyclo-[2.2.1]heptane, 2,6-diamino-7-azabicyclo-[2.2.1]heptane, 2,3-diamino-7-thiabicyclo-[2.2.1]heptane, 2,5-diamino-7-thiabicyclo-[2.2.1]heptane, 2,6-diamino-7-thiabicyclo-[2.2.1]heptane, 2,3-diaminobicyclo[2.2.2]octane, 2,5-diaminobicyclo[2.2.2]octane, 2,6-diaminobicyclo-[2.2.2]octane, 2,5-diaminobicyclo[2.2.2]octane-7-ene, 2,5-diamino-7-azabicyclo[2.2.2]octane, 2,5-diamino-7-oxabicyclo[2.2.2]octane, 2,5-diamino-7-thiabicyclo-[2.2.2]octane, 2,6-diaminobicyclo[3.2.1]octane, 2,6-diaminoazabicyclo[3.2.1]octane, 2,6-diaminooxabicyclo[3.2.1]octane, 2,6-diaminothiabicyclo[3.2.1]octane, 2,6-diaminobicyclo[3.2.2]nonane, 2,6-diaminobicyclo[3.2.2]nonane-8-ene, 2,6-diamino-8-azabicyclo[3.2.2]nonane, 2,6-diamino-8-oxabicyclo[3.2.2]nonane and 2,6-diamino-8-thiabicyclo[3.2.2]nonane.
  • The examples of the aromatic diamine are 2,2-bis(4-aminophenyl)propane, 2,6-diaminopyridine, bis-(4-aminophenyl)diethylsilane, bis-(4-aminophenyl)-diphenylsilane, bis-(4-aminophenyl)ethylphosphine oxide, bis-(4-aminophenyl)-N-butylamine, N,N-bis-(4-aminophenyl)-N-methylamine, N-(3-aminophenyl)-4-aminobenzamide, 3,3′-diaminodiphenylmethane, 3,3′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 2,2-bis(3-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 3,3′-diaminodiphenyl sulfide, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, p-xylenediamine, m-xylenediamine, p-xylenediamine, m-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,2-bis(3-diaminophenyl)ethane, 1,1-bis(3-diaminophenyl)ethane, 4,4′-diaminodiphenylhexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, bis(4-(4-aminophenoxy)phenyl)methane, 1,1-bis(4-(4-aminophenoxy)phenyl)ethane, 1,2-bis(4-(4-aminophenoxy)phenyl)ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-(4-aminophenoxy)phenyl]butane, 4,4′-bis(4-aminophenoxy)-diphenyl ketone, bis(4-(4-aminophenoxy)phenyl) sulfone, bis(4-(4-aminophenoxy)phenyl) sulfide, 1,3-bis(4-(4-aminophenoxy)phenyl)benzene, 1,4-bis(4-(4-aminophenoxy)phenyl)benzene, 4,4′-bis(4-(4-aminophenoxy)phenyl)biphenyl, 1,2-bis(4-(4-aminophenoxy)phenyl)cyclohexane, 1,3-bis(4-(4-aminophenoxy)phenyl)cyclohexane, 1,4-bis(4-(4-aminophenoxy)phenyl)cyclohexane, bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(2-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(3-carbamoyl-4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis-(3-sulfamoyl-4-aminophenyl)hexafluoropropane, 2,2-bis-(3-carboxy-4-aminophenyl)hexafluoropropane, 2,2-bis(4-(3-sulfamoyl-4-aminophenoxy)phenyl)-hexafluoropropane, 2,2-bis(4-(3-carboxy-4-aminophenoxy)phenyl)hexafluoropropane, 1,3-bis(2,2-{4-(4-aminophenoxy)phenyl}hexafluoroisopropyl)benzene, 2,4-bis(β-amino-t-butyl)toluene, bis(p-β-methyl-γ-aminopentyl)benzene, bis-p-(1,1-dimethyl-5-aminopentyl)benzene, bis(p-β-amino-t-butylphenyl) ether, bis(4-aminobenzoloxy)methane, bis(4-aminobenzoloxy)ethane, bis(4-aminobenzoloxy)propane, bis(4-aminobenzoloxy)cyclohexane, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminobiphenyl, 3,3′-dimethylbenzidine, 1,3-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-2-methylphenyl)-methane, 1,2-bis(4-amino-3-methylphenyl)ethane, 1,3-bis(4-amino-3-methylphenyl)propane, 1,2-bis(4-amino-2-methylphenyl)ethane, 1,3-bis(4-amino-2-methylphenyl)propane, 1,4-bis(4-aminophenyl)benzene, 1,4-bis((4-aminophenyl)methyl)benzene, 1,4-bis((3-aminophenyl)methyl)benzene, 1,4-bis((4-aminophenyl)-ethyl)benzene, 1,4-bis((3-aminophenyl)ethyl)benzene, 1,4-bis((4-amino-3-methyl-phenyl)methyl)benzene, 1,4-bis((4-amino-3-methyl-phenyl)ethyl)benzene, 4,4′-(4-aminophenyl)biphenyl, bis-((4-(4-aminophenylmethyl)-phenyl)methane, bis-((4-(4-aminophenylmethyl)-phenyl)ethane, bis-((4-(3-aminophenylmethyl)-phenyl)methane, bis((4-(3-aminophenylmethyl)-phenyl)ethane, 2,2-bis((4-(aminophenylmethyl)-phenyl)propane and 2,2-bis-((4-(3-aminophenylmethyl)phenyl)propane.
  • The diamines described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more diamines may be used in combination. When two or more diamines are used, two or more diamines may be selected from the same kind of the diamines described above, or at least one diamine may be selected from each of the different kind of the diamines. The diamines used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The tetracarboxylic dianhydrides may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active. Among them, the examples of the aliphatic tetracarboxylic dianhydride are ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride. The examples of the alicyclic tetracarboxylic dianhydride are cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicycloheptanetetracarboxylic dianhydride, bicyclooctanetetracarboxylic dianhydride, bicyclo[2.2.2]-octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane-1,2,5,6-tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, 3,3′-bicyclohexyl-1,1′,2,2′-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-franyl)-naphtho[1,2-c]-furan-1,3-dione, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride and tetracyclo[6.2.11,3.02,7]dodecane-4,5,9,10-tetracarboxylic dianhydride. Further, an acid anhydride having a structure represented by the following formula can be given. In these compounds, optional hydrogen may be replaced by lower alkyl such as methyl and ethyl:
    Figure US20050009982A1-20050113-C00049
  • The examples of the aromatic tetracarboxylic dianhydride are pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, naphthalenic dianhydride (2,3,6,7-naphthalenic anhydride and the like), 3,3′-4,4′-diphenylmethanetetracarboxylic dianhydride, 3,3′-4,4′-diphenylethanetetracarboxylic dianhydride, 3,3′-4,4′-diphenylpropane-tetracarboxylic dianhydride, 3,3′-4,4′-diphenylsulfonetetracaroxylic dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)-diphenylsulfonic dianhydride, 4,4′-bis(3,4-dicarboxyphenylmethyl)diphenylmethane dianhydride, 4,4′-bis(3,4-dicarboxyphenylmethyl)diphenylethane dianhydride, 4,4′-bis(3,4-dicarboxyphenylmethyl)-diphenylpropane dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylmethane dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylethane dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3′,4,4′-perfluoropropylidene-diphthalic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, bis(phthalic)-phenylsulfine oxide dianhydride, p-phenylene-bis(triphenyl phthalic) dianhydride, m-phenylene-bis(triphenylphthalic) dianhydride, bis(triphenyl-phthalic)-4,4′-diphenyl ether dianhydride and bis(triphenylphthalic)-4,4′-diphenylmethane dianhydride.
  • The various tetracarboxylic dianhydrides described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more tetracarboxylic dianhydrides may be used in combination. When two or more tetracarboxylic dianhydrides are used, two or more tetracarboxylic dianhydrides may be selected from the same kind of the tetracarboxylic dianhydrides described above, or at least one tetracarboxylic dianhydride may be selected from each of the different kind of the tetracarboxylic dianhydrides. The tetracarboxylic dianhydrides used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The tricarboxylic acids may be belong to any one of groups of aliphatic type, alicyclic type and aromatic type, and they may contain a siloxane group and may be optically active. The examples of the tricarboxylic acid are trimellitic acid, trimesic acid, hemimellitic acid, propanetricarboxylic acid and cyclohexane-tricarboxylic acid. These tricarboxylic acids may be monoesters, diesters, triesters, acid monohalides, acid dihalides, acid trihalides or compounds in which two carboxyl groups are reduced to acid anhydrides. They may be monoester acid dihalides, diester acid monohalides or compounds having a structure in which two carboxyl groups are reduced to acid anhydrides and remaining carboxyl group is esterified or is acid halide. These compounds include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more tricarboxylic acids may be used in combination. When two or more tricarboxylic acids are used, two or more tricarboxylic acids may be selected from the same kind of the tricarboxylic acids described above, or at least one tricarboxylic acid may be selected from each of the different kind of the tricarboxylic acids. The tricarboxylic acid-derivatives used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids described above may be used in combination of two or three kinds thereof. That is, the examples of the combination are the combination consisting of at least one of each of dicarboxylic acids and tricarboxylic acids, the combination consisting of at least one of each of dicarboxylic acids and tetracarboxylic acids, the combination consisting of at least one of each of tricarboxylic acids and tetracarboxylic acids and the combination consisting of at least one of each of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids.
  • Capable of being given as the vinyl base monomers are olefins, halogenated vinyls, vinyl esters, aromatic vinyl base monomers, styrene derivatives, vinyl ethers, alkyl vinyl ketones, dienes, (meth)acrylates, itaconates, α,β-vinylnaphthalene, N-vinylacetamide and the like. They may contain a siloxane group and may be optically active.
  • The examples of the olefin are ethylene, propylene and isobutene. The examples of the halogenated vinyl are vinyl chloride and vinyl fluoride. The examples of the vinyl ester are vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate and vinyl 2-ethyl-2-methylbutanoate. The examples of the aromatic vinyl base monomer are vinyl p-t-butylbenzoate and vinyl N,N-dimethylaminobenzoate. The examples of the styrene derivative are styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene and α-methylstyrene.
  • The examples of the vinyl ether are ethyl vinyl ether, hydroxybutyl vinyl ether, t-amyl vinyl ether and cyclohexanedimethanolmethyl vinyl ether. The examples of the alkyl vinyl ketone are methyl vinyl ketone and isobutyl vinyl ketone. The examples of the diene are butadiene and isoprene. The examples of the (meth)acrylate are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and phenyl (meth)acrylate. The examples of the itaconate are dimethyl itaconate, diethyl itaconate, dibutyl itaconate and diisopropyl itaconate. (Meth)acrylate is a general term for acrylate and methacrylate.
  • The various vinyl base monomers described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination. The vinyl base monomers used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The fumaric acid diesters may have a siloxane group and may be optically active. The examples of the fumaric acid diester are diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclohexyl fumarate, di(1-phenyl-2-propyl) fumarate, di-sec-butyl fumarate, di-t-butyl fumarate, di-2-ethylhexyl fumarate, (isopropyl) (ethyl) fumarate, (isopropyl) (propyl) fumarate, (isopropyl) (butyl) fumarate, (isopropyl) (sec-butyl) fumarate, (isopropyl) (t-butyl) fumarate, (isopropyl) (isoamyl) fumarate, (isopropyl) (sec-amyl) fumarate, (isopropyl) (sec-hexyl) fumarate, (isopropyl) (4-methyl-2-pentyl) fumarate, (isopropyl) (2-ethylhexyl) fumarate, (isopropyl) (octyl) fumarate, (isopropyl) (cyclohexyl) fumarate, (isopropyl) (nonyl) fumarate, (t-butyl) (sec-butyl) fumarate, (t-butyl) (cyclohexyl) fumarate, (t-butyl) (4-methyl-2-pentyl) fumarate, (t-butyl) (2-ethylhexyl) fumarate, (isopropyl) (cyclohexyl) fumarate, (isopropyl) (cyclopentyl) fumarate, (isopropyl) (2-phenyl-1-ethyl) fumarate, (isopropyl) (3-phenylpropyl) fumarate, (isopropyl) (1-phenyl-2-propyl) fumarate, (isopropyl) (1-phenyl-1-propyl) fumarate, (isopropyl) (trimethylsilylpropyl) fumarate, (t-butyl) (trimethylsilylpropyl)fumarate, (cyclohexyl) (trimethylsilylpropyl) fumarate, (isopropyl) (3-tris(trimethylsiloxy)silylpropyl) fumarate, (isopropyl) (3-(pentamethyldisiloxanyl)propyl) fumarate, (N,N-dimethylaminoethyl) (isopropyl) fumarate, (t-butyl) (1-butoxy-2-propyl) fumarate, (2-cyanoethyl) (isopropyl) fumarate, (2-hydroxyethyl) (isopropyl) fumarate, (glycidyl) (isopropyl) fumarate, (isopropyl) (diethylphosphomethyl) fumarate, (2-methylthioethyl) (isopropyl) fumarate, (isopropyl) (2-(hydroxyethylthioethyl)isopropyl) fumarate, (perfluorooctylethyl) (isopropyl) fumarate, (trifluoromethyl) (isopropyl) fumarate, (pentafluoroethyl) (isopropyl) fumarate and (hexafluoroisopropyl) (isopropyl) fumarate.
  • The fumaric acid diesters described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination. The fumaric acid diesters used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • Multifunctional acrylates can be added in order to enhance more a coating film-forming ability of the polymer (3). The multifunctional acrylates may have a siloxane group and may be optically active. The preferred examples of the multifunctional acrylate are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO-added triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, bisphenol A EO-added diacrylate, bisphenol A glycidyl ether diacrylate and polyethylene glycol diacrylate. Bisphenol A glycidyl ether diacrylate is commercially available as Biscoat 700 from Osaka Organic Chemical Co., Ltd.
  • The multifunctional acrylates described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination. The multifunctional acrylates used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • The maleimide derivatives may have a siloxane group and may be optically active. The examples of the maleimide derivative are N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-nonylmaleimide, N-decylmaleimide, N-undecylmaleimide, N-dodecylmaleimide, N-octadecylmaleimide, N-isopropylmaleimide, N-(sec-butyl)maleimide, N-(t-butyl)maleimide, N-(1-methylbutyl)maleimide, N-(2-methylbutyl)maleimide, N-(3-methylbutyl)maleimide, N-(sec-hexyl)maleimide, N-(4-methyl-2-pentyl)maleimide, N-(sec-heptyl)maleimide, N-(sec-octyl)maleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(2-ethylphenyl)maleimide, N-(2-isopropylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2,6-diisopropylphenyl)-maleimide, N-(2,4,6-trimethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-(3-methylphenyl)maleimide, N-(3-ethylphenyl)maleimide, N-(3-trifluoromethyl-phenyl)maleimide, N-(3,5-dimethylphenyl)maleimide, N-benzylmaleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(4-propylphenyl)maleimide, N-(4-isopropylphenyl)maleimide, N-(4-butylphenyl)-maleimide, N-(4-pentylphenyl)maleimide, N-trifluoromethylmaleimide, N-[1-(trifluoromethyl)-ethyl]maleimide, N-(3,3,3-trifluoropropyl)maleimide, N-hexafluoroisopropylmaleimide, N-perfluoroisopropyl-maleimide, N-perfluorobutylethylmaleimide, N-perfluorooctylethylmaleimide, N-(2-chloroethyl)-maleimide, N-(1-butoxy-2-propyl)maleimide, N-(methoxyethyl)maleimide, N-(trimethylsilyl)maleimide, N-(t-butyldimethylsilyl)maleimide, N-(dimethylmethoxysilyl)maleimide, N-(2-cyanoethyl)maleimide, N-(2-hydroxyethyl)maleimide, N-(3-hydroxypropyl)maleimide, N-(4-hydroxybutyl)-maleimide, N-(5-hydroxypentyl)maleimide, N-(6-hydroxyhexyl)maleimide, N-(7-hydroxyheptyl)maleimide, N-(8-hydroxyoctyl)maleimide, N-(9-hydroxynonyl)-maleimide and N-(10-hydroxydecyl)maleimide.
  • The maleimide derivatives described above include ones in which isomers are present, and they may be mixtures containing the isomers. Two or more kinds of the compounds may be used in combination. The maleimide derivatives used in the present invention shall not be restricted to the foregoing compounds given as the examples.
  • When two or more other polymerizable compounds are used for the addition-polymerizable composition, two or more compounds may be selected from the same kind of the addition-polymerizable compounds described above, or at least one compound may be selected from each of the different kind of the addition-polymerizable compounds.
  • The polymer (3) can be obtained by polymerizing the compound (1), the addition-polymerizable composition or the condensation-polymerizable composition described above. The preferred example of the polymer obtained using the compound (1) is a polymer obtained using the compound (1) having —OM1, —CHO, —COOR3, —NHR4, —COX1, —OCOX1, —N═C═O, —CR5═CH2, oxiranyl, oxetanyl, 3,4-epoxycyclohexyl or any one of groups shown below:
    Figure US20050009982A1-20050113-C00050
  • More preferred example of the polymer obtained using the compound (1) is a polymer obtained using the compound (1) having —OM1, —COOR3, —NHR4, —COX1, —N═C═O, —CR5═CH2, oxiranyl, oxetanyl or any one of groups shown below:
    Figure US20050009982A1-20050113-C00051
  • The representative examples of the polymer obtained using the compound (1) are polyimides, polyamic acids, polyesters, epoxy resins, polyacrylates and polymethacrylates. The polyamic acid is obtained by the reaction of the compound (1), which is diamine, with tetracarboxylic dianhydride. This tetracarboxylic dianhydride may be the compound (1), a tetracarboxylic dianhydride other than the compound (1), or a mixture of these tetracarboxylic dianhydrides. Diamines other than the compound (1) may be added to the compound (1) which is diamine. Another example of the polyamic acid is obtained by the reaction of the compound (1), which is tetracarboxylic dianhydride, with diamine. This diamine may be the compound (1), a diamine other than the compound (1), or a mixture of these diamines. Tetracarboxylic dianhydrides other than the compound (1) may be added to the compound (1) which is tetracarboxylic dianhydride. The polyimides are obtained by subjecting the above polyamic acids to dehydration ring-closure.
  • The polyester is obtained by the reaction of the compound (1), which is diol, with a carboxylic acid derivative having at least two carboxyls, acid halide groups, acid anhydride groups or ester groups. The carboxylic acid derivative may be the compound (1), a carboxylic acid derivative other than the compound (1), or a mixture of these carboxylic acid derivatives. Diols other than the compound (1) may be added to the compound (1) which is diol. Another example of the polyester is obtained by the reaction of the compound (1), which is the carboxylic acid derivative having at least two carboxyls, acid halide groups, acid anhydride groups or ester groups, with diol. This diol may be the compound (1), a diol other than the compound (1), or a mixture of these diols. Carboxylic acid derivatives other than the compound (1) may be added to the compound (1) which is the carboxylic acid derivative.
  • The epoxy resin is obtained by the addition reaction of the compound (1), which is bisepoxide, with an active hydrogen compound having at least two of any one of amino group, carboxyl group, phenolic hydroxyl group and thiol group, the copolycondensation reaction of the compound (1), which is bisepoxide, with acid anhydride, or the self polymerization of the compound (1), which is bisepoxide, by a basic or acidic catalyst. The active hydrogen compound may be the compound (1), an active hydrogen compound other than the compound (1), or a mixture of these active hydrogen compounds. Also, the acid anhydride may be the compound (1), which is tetracarboxylic dianhydride, a acid anhydride other than the compound (1) or a mixture of these compounds. The basic or acidic catalyst is an anionic polymerization catalyst such as alkoxides of sodium or potassium, hydroxides, amides, hydrides and Na-naphthalene, a cationic polymerization catalyst including Lewis acids such as SnCl4, BF3 and AlCl3, and protonic acids such as HCl, HBr and H2SO4, and a coordinate polymerization catalyst such as alkoxides of Ca and Ba, oxides, carbonates, amides, alkoxides of Al, Mg and Zn and Zn(C2H5)2—H2O base and Al(C2H5)3—H2O base catalysts. Also, bisepoxides other than the compound (1) may be added to the compound (1) which is bisepoxide. Another example of the epoxy resin is an epoxy resin obtained by the reaction of the compound (1) having at least two of any one of amino group, carboxyl group, phenolic hydroxyl group and thiol group with bisepoxide, or the reaction of the compound (1), which is a tetracarboxylic dianhydride, with bisepoxide. The bisepoxide may be the compound (1), a bisepoxide other than the compound (1), or a mixture of these bisepoxides. Active hydrogen compounds other than the compound (1) may be added to the compound (1) which is an active hydrogen compound. Acid anhydrides compounds other than the compound (1) may be added to the compound (1) which is a tetracarboxylic dianhydride.
  • The examples of the polyacrylate are a homopolymer of the compound (1) having acryloyloxy, a copolymer obtained from at least two of the above compounds (1), a copolymer of at least one of the above compounds (1) and at least one of the compounds (1) having methacryloyloxy, a copolymer of at least one of the above compounds (1) and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1), and a copolymer of at least one of the above compounds (1), at least one of the compounds (1) having methacryloyloxy and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1).
  • The examples of the polymethacrylate are a homopolymer of the compound (1) having methacryloyloxy, a copolymer obtained from at least two of the above compounds (1), a copolymer of at least one of the above compounds (1) and at least one of the compounds (1) having acryloyloxy, a copolymer of at least one of the above compounds (1) and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1), and a copolymer of at least one of the above compounds (1), at least one of the compounds (1) having acryloyloxy and at least one of compounds having acryloyloxy or methacryloyloxy other than the compound (1).
  • The compound (1) and the polymer (3) are characterized by that they are physically and chemically stable very much on conditions usually used and that they have a good compatibility with other polymers and compounds. Suited selection of rings, bonding groups or side chains constituting the compound (1) makes it possible to suitably select the structure of the polymer (3), and therefore capable of being produced is the polymer having optimum transparency, refractive index, mechanical strength, coating property, solubility, crystallinity, shrink property, water permeability, water absorbency, gas permeability, melting point, glass transition point, heat resistance, thermal expansion coefficient, water repellency, electrical insulating property, compatibility and chemical resistance.
  • The compound (1), the polymer (3) or the composition containing them can be molded into a thin film, a multilayer membrane, a film, a fiber, a powder, a paste and other molded articles by a method which is usually used for producing conventional molded articles of high molecular materials. In this case, capable of being blended, if necessary, are aliphatic polyols such as ethylene glycol and propylene glycol, aliphatic or aromatic carboxylic acid compounds, carbon dioxide gas-preventing agents such as phenol compounds, flexibility-providing agents such as polyalkylene glycols, antioxidants, plasticizers, lubricants, coupling agents such as silanes, surface treating agents for inorganic fillers, flame retardants, antistatic agents, colorants, leveling agents, ion trapping agents, slid-improving agents, various rubbers, impact-improving agents such as organic polymer beads, swing-providing agents, surfactants, surface tension-reducing agents, defoaming agents, precipitation preventives, light scattering agents, UV absorbers, heat stabilizers, antioxidants, mold releasing agents, fluorescent agents, conductive fillers, foaming agents and additives such as pigments.
  • For example, the polymer (3) of the present invention is dissolved homogeneously in a solvent, and the resulting solution is cast on a substrate and heated to volatilize the solvent, whereby a uniform film of 1 to 100 μm can be obtained. A polymer film, a glass plate, a silicon rubber plate and a metal plate can be given as the substrate used for molding a film by the above casting method. When a substrate having a prescribed thickness is obtained, the polymer is repeatedly cast and laminated so that the targeted film thickness is obtained, and then it is heated to volatilize the solvent, whereby the substrate having a prescribed thickness can be prepared. In this case, pressing can be carried out as well while heating and applying pressure.
  • Further, a multilayer substrate can be obtained by laminating a metal conductive layer of gold, copper or aluminum between the films and/or on the outermost layer. Also in this case, a metal conductive film is superposed thereon and heated in the same manner as described above to volatilize the solvent, whereby the substrate having a good adhesive property with the metal conductive film can be obtained. The metal conductive layer is obtained by forming a circuit by etching. Further, it can be formed as well by a vacuum deposition method and a screen printing method.
  • Capable of being given as the solvent which can be used in the casting method are aromatic hydrocarbon base solvents such as benzene and toluene, ketone base solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, chloroform, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylacetamide dimethylacetal, dimethylsulfoxide, 1,4-dioxane, ethyl acetate, 2-n-butoxyethanol, γ-butyrolactone, trifluoroacetic acid, ethyl trifluoroacetate and hexafluoro-2-propanol. Among the above solvents, two or more solvents may be used in combination. The solvents which can be used in the present invention shall not be restricted to the examples described above.
  • EXAMPLES
  • The present invention shall be explained below in more details with reference to examples, but the present invention shall not be restricted by these examples. The structures of the compounds were confirmed by a nuclear magnetic resonance (NMR) spectrum, a mass (MS) spectrum and an infrared absorption (IR) spectrum. The following apparatuses and methods were used for measuring the physical properties in the examples.
  • <Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)>
  • Used were a Shimadzu LC-9A type gel permeation chromatograph (GPC) manufactured by Shimadzu Mfg. Co., Ltd. and a column Shodex GF-7M HQ (developing solvent was DMF or THF, and a standard substance was polystyrene having a known molecular weight) manufactured by Showa Denko Co., Ltd.
  • <Pencil Hardness>
  • The polymer thin film formed on a glass plate was measured for a pencil hardness by means of a pencil hardness meter YOSHIMITSU SEIKI C-221 according to JIS “JIS-K-5600-5-4 scratch hardness (pencil method)”.
  • <Refractive Index>
  • The polymer thin film formed on a glass plate, on which chromium was deposited, was measured for a refractive index. It was measured at a measuring wavelength of 589.3 nm and 25° C. by a reflection system measuring method using a sulfur methylene iodide solution as an intermediate solution by means of an Abbe's refractometer ATAGO DR-M2.
  • <Light Transmittance>
  • The polymer thin film formed on a glass plate was measured for a light transmittance by means of a micro color analyzer TC-1800M (manufactured by Tokyo Denshoku Technical Center.
  • <Surface Free Energy>
  • The contact angles of purified water (specific resistance: 18 MΩ·cm) and ethylene glycol which were dropped on the polymer thin film were measured at 25° C. by means of a contact angle meter CA-A (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) to calculate the surface free energy.
  • <Thermal Cracking-Starting Temperature, 5% Weight-Reducing Temperature and 10% Weight-Reducing Temperature>
  • The polymer thin film formed on a glass plate was peeled to prepare a sample. It was heated from 30° C. to 800° C. at 10° C./minute in aerial atmosphere by means of SEIKO SSC5000 TG/DTA 300 to measure a weight change, and the respective temperatures were determined from the inflection points obtained. Codes used in the examples have the following meanings:
    • Ph: phenyl
    • Me: methyl
    • TMS: trtimethylsilyl group
    • HMDS: hexamethyldisilazane
    • THF: tetrahydrofuran
    • NMP: N-methyl-2-pyrrolidone
    Example 1
  • <Production of Compound (1-3-7)>
  • Compound (1-3-7) was produced via the following route:
    Figure US20050009982A1-20050113-C00052

    First Stage: Production of Allyl p-nitrophenyl Ether
  • Potassium carbonate (49.7 g, 0.36 mol) was added to an N,N-dimethylformamide (250 ml) solution of p-nitrophenol (25.0 g, 0.18 mol) under nitrogen atmosphere and suspended, and 3-bromopropene (21.7 g, 0.18 mol) was dropwise added thereto. After finishing dropwise adding, the solution was stirred at a room temperature for 5 hours, and then extracting practice with diethyl ether was carried out after adding water to the solution. The organic layer was washed with water and then dried on anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue thus obtained was refined by means of silica gel chromatography (eluent solvent: toluene). Toluene was distilled off under reduced pressure, and then the resulting residue was recrystallized from ethanol to obtain allyl p-nitrophenyl ether (25.7 g).
  • Second Stage: Production of Compound (b)
  • Toluene (500 ml) was added to a compound (a) (50.0 g, 43.3 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 25 μl) was added thereto and heated to 90° C. Allyl p-nitrophenyl ether (16.3 g, 91 mmol) was dropwise added thereto in 5 minutes, and the solution was heated for 2 hours while refluxing. After standing to cool, toluene (100 ml) and water (300 ml) were added thereto, and extracting practic was carried out. The organic layer was washed with water and then dried on anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue thus obtained was refined by means of silica gel chromatography (eluent solvent: toluene). Toluene was distilled off under reduced pressure, and then the resulting residue was recrystallized from ethanol/ethyl acetate to obtain a compound (b) 18.7 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.34 (s, 6H), 0.85-0.88 (t, 4H), 1.92-1.95 (m, 4H), 3.85-3.88 (t, 4H), 6.60-6.63 (d, 4H), 7.15-7.52 (m, 40H), 7.94-7.97 (d, 4H). 29Si-NMR (solvent: CDCl3) : δ (ppm) ; −17.8 (d, 2Si), −78.5 (s, 4Si), −79.4 (t, 4Si).
  • Third Stage: Production of Compound (1-3-7)
  • A mixture of the compound (b) (10.0 g, 6.61 mmol), Pd/C (1 g) and THF (100 ml) was stirred at a room temperature for 120 hours under hydrogen atmosphere. After filtering off Pd/C, THF was distilled off under reduced pressure. The resulting residue was refined by means of silica gel chromatography (eluent solvent: ethyl acetate). Ethyl acetate was distilled off under reduced pressure to obtain Compound (1-3-7) 6.3 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.31 (s, 6H), 0.83-0.87 (t, 4H), 1.82-1.87 (m, 4H), 3.71-3.74 (t, 4H), 6.51-6.57 (d, 8H), 7.14-7.95 (m, 40H). 29Si-NMR (solvent: CDCl3): δ (ppm); −17.5 (d, 2Si), −78.6 (s, 4Si), −79.6 (t, 4Si).
  • Example 2
  • <Production of Compound (1-1-4)>
  • Compound (1-1-4) was produced via the following route:
    Figure US20050009982A1-20050113-C00053
  • THF (150 ml) was added to the compound (a) (50.0 g, 43.3 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 320 μl) was added thereto and heated to 90° C. Allylsuccinic anhydride (14.5 g, 103.5 mmol) was dropwise added thereto in 5 minutes, and the solution was heated for 7 hours while refluxing. After standing to cool, the solvent was distilled off under reduced pressure, and then methanol (150 ml) was added to the resulting residue and stirred at a room temperature for 2 hours. The resulting solid matter was filtered and dissolved in THF (150 ml), and activated carbon (6 g) was added thereto, followed by stirring the mixture at a room temperature for 2 hours. After filtering off the activated carbon, THF was distilled off under reduced pressure to obtain Compound (1-1-4) 55.9 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.32 (s, 6H), 0.70-0.79 (t, 4H), 1.32-1.42 (m, 6H), 1.74-1.80 (m, 2H), 1.89-1.99 (m, 2H), 2.24-2.37 (m, 2H), 2.51-2.60 (m, 2H), 7.15-7.56 (m, 40H). 29Si-NMR (solvent: CDCl3): δ (ppm); −18.1 (d, 2Si), −78.5 (s, 4Si), −79.4-−79.8(t, 4Si).
  • Example 3
  • <Production of Compound (1-1-1)>
  • Compound (1-1-1) was produced via the following route:
    Figure US20050009982A1-20050113-C00054

    First Stage: Production of Compound (d)
  • 3-Acetoxypropylmethyldichlorosilane (5.4 g, 25 mmol) was added to a mixture of a compound (c) (11.6 g, 10 mmol), triethylamine (2.5 g, 25 mmol) and THF (200 ml) under nitrogen atmosphere, and the solution was stirred at a room temperature for 3 hours. Toluene (200 ml) and water (100 ml) were added thereto and stirred, and the organic layer was washed with water and then dried on anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue thus obtained was washed with methanol and recrystallized from ethanol/ethyl acetate (100 ml) to obtain a compound (d) 6.51 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.31 (s, 6H), 0.72-0.75 (t, 4H), 1.70-1.74 (m, 4H), 1.88 (s, 6H), 3.91-3.94 (t, 4H), 7.18-7.52 (m, 40H). 29Si-NMR (solvent: CDCl3): δ (ppm); −17.8 (d, 2Si), −78.4 (s, 4Si), −79.3 (t, 4Si).
  • Second Stage: Production of Compound (1-1-1)
  • Conc. sulfuric acid (3 ml) was added to a mixture of the compound (d) (9.0 g, 6.85 mmol) and methanol (1,500 ml), and the solution was heated for 3 hours while refluxing. After standing to cool, methanol was distilled off under reduced pressure, and chloroform (200 ml) and water (100 ml) were added to the resulting residue and stirred. The organic layer was washed with water and dried on anhydrous magnesium sulfate, and then chloroform was distilled off under reduced pressure. The resulting residue was washed with methanol to obtain a compound (1-1-1) 5.00 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.31 (s, 6H), 0.71-0.75 (t, 4H), 1.60-1.66 (m, 4H), 3.45-3.48 (t, 4H), 7.18-7.54 (m, 40H) 29Si-NMR (solvent: CDCl3): δ (ppm); −17.4 (d, 2Si), −78.5 (s, 4Si), −79.5 (t, 4Si).
  • Example 4
  • <Production of Compound (1-1-2)>
  • Compound (1-1-2) was produced via the following route:
    Figure US20050009982A1-20050113-C00055

    First Stage: Production of Trimethylsilyl 4-pentenoate
  • A mixture of HMDS (88.6 g, 0.55 mol) and THF (21.5 g) was heated at 80° C. under nitrogen atmosphere, and a toluene (50 g) solution of 4-pentenoic acid (100 g, 1 mol) was dropwise added thereto. After dropwise adding, the solution was stirred at 100° C. for 2 hours and distilled under reduced pressure to obtain trimethylsilyl 4-pentenoate (130.2 g). This compound had a boiling point of 83 to 84° C./77.1 hPa.
  • Second Stage: Production of Compound (e)
  • Toluene (1,000 ml) was added to the compound (a) (100.0 g, 86.7 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 50 μl) was added thereto and heated to 90° C. Trimethylsilyl 4-pentenoate (31.4 g, 182 mmol) was dropwise added thereto, and the solution was heated for 5 hours while refluxing. After standing to cool, toluene was distilled off under reduced pressure to obtain a crude compound (e) (92.9 g).
  • Third Stage: Production of Compound (1-1-2)
  • Methanol (1,000 ml) was added to the crude compound (e) (92.9 g, 61.8 mmol) and suspended, and the suspension was stirred at a room temperature for 3 hours. A solid matter filtered off from the suspension was dissolved in methanol/toluene, and activated carbon (2.7 g) was added thereto and stirred at a room temperature for 2 hours. The activated carbon was filtered off, and then the solvent was distilled off under reduced pressure. The residue was recrystallized from ethanol/ethyl acetate to obtain a compound (1-1-2) 75.0 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.28 (s, 6H), 0.72-0.75 (t, 4H), 1.40-1.43 (m, 4H), 1.53-1.56 (m, 4H), 2.08-2.11 (t, 4H), 7.18-7.53 (m, 40H). 29Si-NMR (solvent: CDCl3): δ (ppm); −17.7 (d, 2Si), −78.6 (s, 4Si), −79.6 (t, 4Si).
  • Example 5
  • <Production of Compound (1-1-5)>
  • Compound (1-1-5) was produced via the following route:
    Figure US20050009982A1-20050113-C00056
  • Toluene (50 ml) was added to the compound (a) (5.0 g, 4.33 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 30 μl) was added thereto and heated to 90° C. Allyl glycidyl ether (1.04 g, 9.1 mmol) was dropwise added thereto, and the solution was heated for 3 hours while refluxing. After standing to cool, toluene (50 ml) and water (100 ml) were added thereto, and extracting practice was carried out. The organic layer was washed with water and then dried on anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue thus obtained was refined by means of silica gel chromatography (eluent solvent: toluene/ethyl acetate). The solvent was distilled off under reduced pressure, and then the residue was recrystallized from ethanol/ethyl acetate to obtain a compound (1-1-5) 1.6 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.30 (s, 6H), 0.73-0.76 (t, 4H), 1.66-1.72 (m, 4H), 2.42-2.44 (m, 2H), 2.64-2.66 (m, 2H), 2.95-2.98 (m, 2H), 3.15-3.19 (m, 2H), 3.28-3.39 (m, 4H), 3.44-3.48 (m, 2H), 7.18-7.53 (m, 40H). 29Si-NMR (solvent: CDCl3): δ (ppm); −17.4 (d, 2Si), −78.6 (s, 4Si), −79.5-−79.6(t, 4Si).
  • Example 6
  • <Production of Compound (1-1-8)>
  • Compound (1-1-8) was produced via the following route:
    Figure US20050009982A1-20050113-C00057
  • Toluene (30 ml) was added to the compound (a) (3.0 g, 2.60 mmol) under nitrogen atmosphere and suspended, and a platinum-divinylsiloxane complex (3 wt % toluene solution, 5 μl) was added thereto and heated to 90° C. 4-Vinyl-1-cyclohexene 1,2-epoxide (0.68 g, 5.46 mmol) was dropwise added thereto, and the solution was heated for 5 hours while refluxing. After standing to cool, toluene (30 ml) and water (70 ml) were added thereto, and extracting practice was carried out. The organic layer was washed with water and then dried on anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue thus obtained was refined by means of silica gel chromatography (eluent solvent: toluene/ethyl acetate). The solvent was distilled off under reduced pressure, and then the residue was recrystallized from ethanol/ethyl acetate to obtain a compound (1-1-8) 0.77 g.
  • 1H-NMR (solvent: CDCl3): δ (ppm); 0.27 (s, 6H), 0.60-0.73 (m, 5H), 0.84-0.92 (m, 1H), 0.97-1.07 (m, 2H), 1.62-1.68 (m, 1H), 1.76-1.84 (m, 2H), 1.94-1.98 (m, 2H), 2.90-3.00 (m, 4H), 7.13-7.54 (m, 40H). 29Si-NMR (solvent: CDCl3): δ (ppm); −17.0-−17.1(d, 2Si), −78.7 (s, 4Si), −79.6(s, 4Si).
  • Compounds shown in the following Table 1 to Table 28 can be produced according to the methods described in Examples 1 to 6. R1, Q1, Q2 and Y1 have the meanings described above.
    TABLE 1
    No. R1 Q1 Q2 Y1
    1-1-1
    Figure US20050009982A1-20050113-C00058
    —CH3 Q2-1-1 —OH
    1-1-2
    Figure US20050009982A1-20050113-C00059
    —CH3 Q2-1-2 —COOH
    1-1-3
    Figure US20050009982A1-20050113-C00060
    —CH3 Q2-1-1 —OCOCH═CH2
    1-1-4
    Figure US20050009982A1-20050113-C00061
    —CH3 Q2-1-1
    Figure US20050009982A1-20050113-C00062
    1-1-5
    Figure US20050009982A1-20050113-C00063
    —CH3 Q2-1-3
    Figure US20050009982A1-20050113-C00064
    1-1-6
    Figure US20050009982A1-20050113-C00065
    —CH3 Q2-1-3
    Figure US20050009982A1-20050113-C00066
    1-1-7
    Figure US20050009982A1-20050113-C00067
    —CH3 Q2-1-4 —NH2
    1-1-8
    Figure US20050009982A1-20050113-C00068
    —CH3 Q2-1-5
    Figure US20050009982A1-20050113-C00069
    1-2-1
    Figure US20050009982A1-20050113-C00070
    Figure US20050009982A1-20050113-C00071
    Q2-2-1 —COOH
    1-2-2
    Figure US20050009982A1-20050113-C00072
    —CH3 Q2-2-2 —OH
    1-2-3
    Figure US20050009982A1-20050113-C00073
    —C2H5 Q2-2-3 —Cl
    1-2-4
    Figure US20050009982A1-20050113-C00074
    Figure US20050009982A1-20050113-C00075
    Q2-2-4 —CH═CHCOOCH(CH3)2
    1-2-5
    Figure US20050009982A1-20050113-C00076
    —OCH3 Q2-2-5 —OCOC(CF3)═CH2
    1-2-6
    Figure US20050009982A1-20050113-C00077
    —CH2CH═CH2 Q2-2-6 —CHO
    1-2-7
    Figure US20050009982A1-20050113-C00078
    —C2H5 Q2-2-7 —COOH
    1-2-8
    Figure US20050009982A1-20050113-C00079
    —OCH3 Q2-2-8
    Figure US20050009982A1-20050113-C00080
    1-2-9
    Figure US20050009982A1-20050113-C00081
    —CH(CH3)2 Q2-2-9
    Figure US20050009982A1-20050113-C00082
  • TABLE 2
    No. R1 Q1 Q2 Y1
    1-3-1
    Figure US20050009982A1-20050113-C00083
    —CH3 Q2-3-1 —OH
    1-3-2
    Figure US20050009982A1-20050113-C00084
    Figure US20050009982A1-20050113-C00085
    Q2-3-2 —NH2
    1-3-3
    Figure US20050009982A1-20050113-C00086
    —CH3 Q2-3-1 —COOH
    1-3-4
    Figure US20050009982A1-20050113-C00087
    —CH(CH3)2 Q2-3-2 —OCOC(CH)═CH2
    1-3-5
    Figure US20050009982A1-20050113-C00088
    Figure US20050009982A1-20050113-C00089
    Q2-3-4 —Br
    1-3-6
    Figure US20050009982A1-20050113-C00090
    —CH3 Q2-3-5
    Figure US20050009982A1-20050113-C00091
    1-3-7
    Figure US20050009982A1-20050113-C00092
    —CH3 Q2-3-2 —NH2
    1-3-8
    Figure US20050009982A1-20050113-C00093
    —CH3 Q2-3-6 —NH2
    1-3-9
    Figure US20050009982A1-20050113-C00094
    —CH3 Q2-3-7 —OH
    1-3-10
    Figure US20050009982A1-20050113-C00095
    —C2H5 Q2-3-8
    Figure US20050009982A1-20050113-C00096
    1-3-11
    Figure US20050009982A1-20050113-C00097
    —C3H7 Q2-3-8 —OCOCH═CH2
    1-3-12
    Figure US20050009982A1-20050113-C00098
    —CH(CH3)2 Q2-3-9 —OCOC(F)═CH2
    1-3-13
    Figure US20050009982A1-20050113-C00099
    Figure US20050009982A1-20050113-C00100
    Q2-3-9 —OCH═CH2
    1-3-14
    Figure US20050009982A1-20050113-C00101
    —OCH3 Q2-3-10 —Cl
    1-4-1
    Figure US20050009982A1-20050113-C00102
    —CH2CH═CH2 Q2-4-1 —CHO
    1-4-2
    Figure US20050009982A1-20050113-C00103
    —C2H5 Q2-4-1 —OH
    1-4-3
    Figure US20050009982A1-20050113-C00104
    —OCH3 Q2-4-1 —COOCH3
  • TABLE 3
    No. R1 Q1 Q2 Y1
    1-4-4
    Figure US20050009982A1-20050113-C00105
    —CH3 Q2-4-2 —OH
    1-4-5
    Figure US20050009982A1-20050113-C00106
    Figure US20050009982A1-20050113-C00107
    Q2-4-3 —COCH═CH2
    1-4-6
    Figure US20050009982A1-20050113-C00108
    —CH3 Q2-4- —OH
    1-4-7
    Figure US20050009982A1-20050113-C00109
    —CH(CH3)2 Q2-4-5 —Br
    1-5-1
    Figure US20050009982A1-20050113-C00110
    Figure US20050009982A1-20050113-C00111
    Q2-5-1 —OH
    1-5-2
    Figure US20050009982A1-20050113-C00112
    —CH3 Q2-5-1 —COOH
    1-5-3
    Figure US20050009982A1-20050113-C00113
    Figure US20050009982A1-20050113-C00114
    Q2-5-1 —NH2
    1-5-4
    Figure US20050009982A1-20050113-C00115
    Figure US20050009982A1-20050113-C00116
    Q2-5-2
    Figure US20050009982A1-20050113-C00117
    1-5-5
    Figure US20050009982A1-20050113-C00118
    —CH2CH═CH2 Q2-5-2 —OCH═CH2
    1-5-6
    Figure US20050009982A1-20050113-C00119
    —CH3 Q2-5-2
    Figure US20050009982A1-20050113-C00120
    1-5-7
    Figure US20050009982A1-20050113-C00121
    —C2H5 Q2-5-3 —COOH
    1-5-8
    Figure US20050009982A1-20050113-C00122
    —OCH3 Q2-5-3 —OH
    1-5-9
    Figure US20050009982A1-20050113-C00123
    —CH3 Q2-5-4
    Figure US20050009982A1-20050113-C00124
    1-5-10
    Figure US20050009982A1-20050113-C00125
    Figure US20050009982A1-20050113-C00126
    Q2-5-4
    Figure US20050009982A1-20050113-C00127
    1-5-11
    Figure US20050009982A1-20050113-C00128
    —C4H9 Q2-5-5 —Br
    1-5-12
    Figure US20050009982A1-20050113-C00129
    —CH(CH3)2 Q2-5-5 —OCOC(F)═CH2
    1-5-13
    Figure US20050009982A1-20050113-C00130
    —OCH3 Q2-5-5 —OH
  • TABLE 4
    No. R1 Q1 Q2 Y1
    1-6-1
    Figure US20050009982A1-20050113-C00131
    —CH(CH3)2 Q2-6-1 —OH
    1-6-2
    Figure US20050009982A1-20050113-C00132
    Figure US20050009982A1-20050113-C00133
    Q2-6-2 —COOH
    1-6-3
    Figure US20050009982A1-20050113-C00134
    —OCH3 Q2-6-2 —OH
    1-6-4
    Figure US20050009982A1-20050113-C00135
    —CH3 Q2-6-3 —OH
    1-6-5
    Figure US20050009982A1-20050113-C00136
    —CH2CH═CH2 Q2-6-3 —Br
    1-6-6
    Figure US20050009982A1-20050113-C00137
    —OCH3 Q2-6-4 —Cl
    1-6-7
    Figure US20050009982A1-20050113-C00138
    Figure US20050009982A1-20050113-C00139
    Q2-6-5
    Figure US20050009982A1-20050113-C00140
    1-7-1
    Figure US20050009982A1-20050113-C00141
    —CH3 Q2-7-1 —COOH
    1-7-2
    Figure US20050009982A1-20050113-C00142
    Figure US20050009982A1-20050113-C00143
    Q2-7-1 —NH2
    1-7-3
    Figure US20050009982A1-20050113-C00144
    Figure US20050009982A1-20050113-C00145
    Q2-7-2 —OCOC(CH)═CH2
    1-7-4
    Figure US20050009982A1-20050113-C00146
    —CH3 Q2-7-2
    Figure US20050009982A1-20050113-C00147
    1-7-5
    Figure US20050009982A1-20050113-C00148
    —C2H5 Q2-7-3 —OH
    1-7-6
    Figure US20050009982A1-20050113-C00149
    —C2H5 Q2-7-3
    Figure US20050009982A1-20050113-C00150
    1-7-7
    Figure US20050009982A1-20050113-C00151
    —C2H5 Q2-7-4 —COCl
    1-7-8
    Figure US20050009982A1-20050113-C00152
    Figure US20050009982A1-20050113-C00153
    Q2-7-5 —COOH
  • TABLE 5
    No. R1 Q1 Q2 Y1
    1-8-1
    Figure US20050009982A1-20050113-C00154
    —C2H5 Q2-8-1 —COOH
    1-8-2
    Figure US20050009982A1-20050113-C00155
    Figure US20050009982A1-20050113-C00156
    Q2-8-2 —OH
    1-8-3
    Figure US20050009982A1-20050113-C00157
    —CH3 Q2-8-3
    Figure US20050009982A1-20050113-C00158
    1-8-4
    Figure US20050009982A1-20050113-C00159
    —CH(CH3)2 Q2-8-4 —NH2
    1-8-5
    Figure US20050009982A1-20050113-C00160
    Figure US20050009982A1-20050113-C00161
    Q2-8-5 —OH
    1-9-1
    Figure US20050009982A1-20050113-C00162
    —CH3 Q2-9-1 —OH
    1-9-2
    Figure US20050009982A1-20050113-C00163
    Figure US20050009982A1-20050113-C00164
    Q2-9-2 —COOH
    1-9-3
    Figure US20050009982A1-20050113-C00165
    Figure US20050009982A1-20050113-C00166
    Q2-9-3
    Figure US20050009982A1-20050113-C00167
    1-9-4
    Figure US20050009982A1-20050113-C00168
    —CH3 Q2-9-4 —COOH
    1-9-5
    Figure US20050009982A1-20050113-C00169
    —C2H5 Q2-9-5 —Br
    1-10-1
    Figure US20050009982A1-20050113-C00170
    Figure US20050009982A1-20050113-C00171
    Q2-10-1 —COOH
    1-10-2
    Figure US20050009982A1-20050113-C00172
    —OCH3 Q2-10-2 —OH
    1-10-3
    Figure US20050009982A1-20050113-C00173
    Figure US20050009982A1-20050113-C00174
    Q2-10-3 —COOCH3
    1-10-4
    Figure US20050009982A1-20050113-C00175
    —C2H5 Q2-10-4 —COCH═CH2
    1-10-5
    Figure US20050009982A1-20050113-C00176
    —C2H5 Q2-10-5
    Figure US20050009982A1-20050113-C00177
  • TABLE 6
    No. R1 Q1 Q2 Y1
    1-11-1
    Figure US20050009982A1-20050113-C00178
    —CH3 Q2-11-1 —COOH
    1-11-2
    Figure US20050009982A1-20050113-C00179
    Figure US20050009982A1-20050113-C00180
    Q2-11-2 —OH
    1-11-3
    Figure US20050009982A1-20050113-C00181
    —C2H5 Q2-11-3 —COCl
    1-11-4
    Figure US20050009982A1-20050113-C00182
    —Cl Q2-11-4
    Figure US20050009982A1-20050113-C00183
    1-11-5
    Figure US20050009982A1-20050113-C00184
    Figure US20050009982A1-20050113-C00185
    Q2-11-5
    Figure US20050009982A1-20050113-C00186
    1-12-1
    Figure US20050009982A1-20050113-C00187
    —CH3 Q2-12-1 —OCOCH═CH2
    1-12-2
    Figure US20050009982A1-20050113-C00188
    Figure US20050009982A1-20050113-C00189
    Q2-12-2 —OH
    1-12-3
    Figure US20050009982A1-20050113-C00190
    —CH(CH3)2 Q2-12-3 —COOH
    1-12-4
    Figure US20050009982A1-20050113-C00191
    Figure US20050009982A1-20050113-C00192
    Q2-12-4 —OH
    1-12-5
    Figure US20050009982A1-20050113-C00193
    Figure US20050009982A1-20050113-C00194
    Q2-12-5 —COCl
    1-13-1
    Figure US20050009982A1-20050113-C00195
    —CH3 Q2-13-1 —COOH
    1-13-2
    Figure US20050009982A1-20050113-C00196
    —CH═CH2 Q2-13-2 —OH
    1-13-3
    Figure US20050009982A1-20050113-C00197
    —C3H7 Q2-13-3
    Figure US20050009982A1-20050113-C00198
    1-13-4
    Figure US20050009982A1-20050113-C00199
    —C2H5 Q2-13-4 —OCH═CH2
    1-13-5
    Figure US20050009982A1-20050113-C00200
    Figure US20050009982A1-20050113-C00201
    Q2-13-5
    Figure US20050009982A1-20050113-C00202
  • TABLE 7
    No. R1 Q1 Q2 Y1
    1-14-1
    Figure US20050009982A1-20050113-C00203
    —CH3 Q2-14-1 —COOH
    1-14-2
    Figure US20050009982A1-20050113-C00204
    —CH3 Q2-14-2 —OH
    1-14-3
    Figure US20050009982A1-20050113-C00205
    —C3H7 Q2-14-3
    Figure US20050009982A1-20050113-C00206
    1-14-4
    Figure US20050009982A1-20050113-C00207
    —H Q2-14-4 —COOH
    1-14-5
    Figure US20050009982A1-20050113-C00208
    Figure US20050009982A1-20050113-C00209
    Q2-14-5 —OH
    1-15-1
    Figure US20050009982A1-20050113-C00210
    —CH3 Q2-15-1 —COOH
    1-15-2
    Figure US20050009982A1-20050113-C00211
    Figure US20050009982A1-20050113-C00212
    Q2-15-2
    Figure US20050009982A1-20050113-C00213
    1-15-3
    Figure US20050009982A1-20050113-C00214
    —C2H5 Q2-15-3
    Figure US20050009982A1-20050113-C00215
    1-15-4
    Figure US20050009982A1-20050113-C00216
    Figure US20050009982A1-20050113-C00217
    Q2-15-4 —OCOCH═CH2
    1-15-5
    Figure US20050009982A1-20050113-C00218
    —CH(CH3)2 Q2-15-5 —NH2
    1-16-1
    Figure US20050009982A1-20050113-C00219
    —CH3 Q2-16-1 —COOH
    1-16-2
    Figure US20050009982A1-20050113-C00220
    —C4H9 Q2-16-2 —OH
    1-16-3
    Figure US20050009982A1-20050113-C00221
    Figure US20050009982A1-20050113-C00222
    Q2-16-3 —OH
    1-16-4
    Figure US20050009982A1-20050113-C00223
    —C2H5 Q2-16-4 —NH2
    1-16-5
    Figure US20050009982A1-20050113-C00224
    —CH3 Q2-16-5 —CN
  • TABLE 8
    No. R1 Q1 Q2 Y1
    1-17-1
    Figure US20050009982A1-20050113-C00225
    —C2H5 Q2-17-1 —COOH
    1-17-2
    Figure US20050009982A1-20050113-C00226
    —CH3 Q2-17-2 —OH
    1-17-3
    Figure US20050009982A1-20050113-C00227
    —CH3 Q2-17-3 —COCl
    1-17-4
    Figure US20050009982A1-20050113-C00228
    Figure US20050009982A1-20050113-C00229
    Q217-4 —OH
    1-17-5
    Figure US20050009982A1-20050113-C00230
    Figure US20050009982A1-20050113-C00231
    Q2-17-5 —NH2
    1-18-1
    Figure US20050009982A1-20050113-C00232
    —C3H7 Q2-18-1 —CH═CHCH═CH2
    1-18-2
    Figure US20050009982A1-20050113-C00233
    Figure US20050009982A1-20050113-C00234
    Q2-18-2
    Figure US20050009982A1-20050113-C00235
    1-18-3
    Figure US20050009982A1-20050113-C00236
    —CH(CH3)2 Q2-18-3 —OH
    1-18-4
    Figure US20050009982A1-20050113-C00237
    Figure US20050009982A1-20050113-C00238
    Q2-18-4
    Figure US20050009982A1-20050113-C00239
    1-18-5
    Figure US20050009982A1-20050113-C00240
    —CH(CH3)2 Q2-18-5 —NH2
    1-19-1
    Figure US20050009982A1-20050113-C00241
    Figure US20050009982A1-20050113-C00242
    Q2-19-1
    Figure US20050009982A1-20050113-C00243
    1-19-2
    Figure US20050009982A1-20050113-C00244
    Figure US20050009982A1-20050113-C00245
    Q2-19-2 —OH
    1-19-3
    Figure US20050009982A1-20050113-C00246
    —CH3 Q2-19-3 —COOH
    1-19-4
    Figure US20050009982A1-20050113-C00247
    —CH3 Q2-19-4 —CH═CH2
    1-19-5
    Figure US20050009982A1-20050113-C00248
    Figure US20050009982A1-20050113-C00249
    Q2-19-5
    Figure US20050009982A1-20050113-C00250
  • TABLE 9
    No. R1 Q1 Q2 Y1
    1-20-1
    Figure US20050009982A1-20050113-C00251
    Figure US20050009982A1-20050113-C00252
    Q2-20-1 —OH
    1-20-2
    Figure US20050009982A1-20050113-C00253
    —CH═CH2 Q2-20-2 —COOH
    1-20-3
    Figure US20050009982A1-20050113-C00254
    —CH3 Q2-20-3
    Figure US20050009982A1-20050113-C00255
    1-20-4
    Figure US20050009982A1-20050113-C00256
    Figure US20050009982A1-20050113-C00257
    Q2-20-4 —CHO
    1-20-5
    Figure US20050009982A1-20050113-C00258
    —C3H7 Q2-20-5 —OH
    1-21-1
    Figure US20050009982A1-20050113-C00259
    —C3H7 Q2-21-1 —COOH
    1-21-2
    Figure US20050009982A1-20050113-C00260
    Figure US20050009982A1-20050113-C00261
    Q2-21-2
    Figure US20050009982A1-20050113-C00262
    1-21-3
    Figure US20050009982A1-20050113-C00263
    —C2H5 Q2-21-3 —Br
    1-21-4
    Figure US20050009982A1-20050113-C00264
    Figure US20050009982A1-20050113-C00265
    Q2-21-4 —OCOCH═CH2
    1-21-5
    Figure US20050009982A1-20050113-C00266
    —CH3 Q2-21-5
    Figure US20050009982A1-20050113-C00267
    1-22-1
    Figure US20050009982A1-20050113-C00268
    Figure US20050009982A1-20050113-C00269
    Q2-22-1 —COOH
    1-22-2
    Figure US20050009982A1-20050113-C00270
    —OCH3 Q2-22-2 —OCOC(CF3)═CH2
    1-22-3
    Figure US20050009982A1-20050113-C00271
    Figure US20050009982A1-20050113-C00272
    Q2-22-3 —COOH
    1-22-4
    Figure US20050009982A1-20050113-C00273
    —CH3 Q2-22-4 —OH
    1-22-5
    Figure US20050009982A1-20050113-C00274
    —CH(CH3)2 Q2-22-5 —NH2
  • TABLE 10
    No. R1 Q1 Q2 Y1
    1-23-1
    Figure US20050009982A1-20050113-C00275
    Figure US20050009982A1-20050113-C00276
    Q2-23-1 —COOH
    1-23-2
    Figure US20050009982A1-20050113-C00277
    —CH3 Q2-23-2
    Figure US20050009982A1-20050113-C00278
    1-23-3
    Figure US20050009982A1-20050113-C00279
    —CH3 Q2-23-3 —OCH═CH2
    1-23-4
    Figure US20050009982A1-20050113-C00280
    Figure US20050009982A1-20050113-C00281
    Q2-23-4 —OH
    1-23-5
    Figure US20050009982A1-20050113-C00282
    —CH3 Q2-23-5 —NH2
    1-24-1
    Figure US20050009982A1-20050113-C00283
    Figure US20050009982A1-20050113-C00284
    Q2-24-1
    Figure US20050009982A1-20050113-C00285
    1-24-2
    Figure US20050009982A1-20050113-C00286
    —C2H5 Q2-24-2 —COCl
    1-24-3
    Figure US20050009982A1-20050113-C00287
    —CH(CH3)2 Q2-24-3 —NH2
    1-24-4
    Figure US20050009982A1-20050113-C00288
    Figure US20050009982A1-20050113-C00289
    Q2-24-4 —COOH
    1-24-5
    Figure US20050009982A1-20050113-C00290
    —CH3 Q2-24-5 —OCOCH═CH2
    1-25-1
    Figure US20050009982A1-20050113-C00291
    —OCH3 Q2-25-1 —COOH
    1-25-2
    Figure US20050009982A1-20050113-C00292
    —C3H7 Q2-25-2
    Figure US20050009982A1-20050113-C00293
    1-25-3
    Figure US20050009982A1-20050113-C00294
    —CH(CH3)2 Q2-25-3 —COOH
    1-25-4
    Figure US20050009982A1-20050113-C00295
    —CH3 Q2-25-4 —NH2
    1-25-5
    Figure US20050009982A1-20050113-C00296
    —OCH3 Q2-25-5 —OH
  • TABLE 11
    No. R1 Q1 Q2 Y1
    1-26-1
    Figure US20050009982A1-20050113-C00297
    Figure US20050009982A1-20050113-C00298
    Q2-26-1 —COOH
    1-26-2
    Figure US20050009982A1-20050113-C00299
    —CH3 Q2-26-2 —OH
    1-26-3
    Figure US20050009982A1-20050113-C00300
    —CH3 Q2-26-3
    Figure US20050009982A1-20050113-C00301
    1-26-4
    Figure US20050009982A1-20050113-C00302
    Figure US20050009982A1-20050113-C00303
    Q2-26-4
    Figure US20050009982A1-20050113-C00304
    1-26-5
    Figure US20050009982A1-20050113-C00305
    —C3H7 Q2-26-5 —COOH
    1-27-1
    Figure US20050009982A1-20050113-C00306
    Figure US20050009982A1-20050113-C00307
    Q2-27-1 —COOH
    1-27-2
    Figure US20050009982A1-20050113-C00308
    —C4H9 Q2-27-2
    Figure US20050009982A1-20050113-C00309
    1-27-3
    Figure US20050009982A1-20050113-C00310
    —CH3 Q2-27-3 —NH2
    1-27-4
    Figure US20050009982A1-20050113-C00311
    Figure US20050009982A1-20050113-C00312
    Q2-27-4
    Figure US20050009982A1-20050113-C00313
    1-27-5
    Figure US20050009982A1-20050113-C00314
    —CH3 Q2-27-5
    Figure US20050009982A1-20050113-C00315
    1-28-1
    Figure US20050009982A1-20050113-C00316
    —C2H5 Q2-28-1 —COOH
    1-28-2
    Figure US20050009982A1-20050113-C00317
    —CH3 Q2-28-2 —OH
    1-28-3
    Figure US20050009982A1-20050113-C00318
    Figure US20050009982A1-20050113-C00319
    Q2-28-3 —COOH
    1-28-4
    Figure US20050009982A1-20050113-C00320
    —OCH3 Q2-28-4
    Figure US20050009982A1-20050113-C00321
    1-28-5
    Figure US20050009982A1-20050113-C00322
    Figure US20050009982A1-20050113-C00323
    Q2-28-5 —NH2
  • TABLE 12
    No. R1 Q1 Q2 Y1
    1-29-1
    Figure US20050009982A1-20050113-C00324
    —OCH3 Q2-29-1 —COOH
    1-29-2
    Figure US20050009982A1-20050113-C00325
    —CH3 Q2-29-2 —OH
    1-29-3
    Figure US20050009982A1-20050113-C00326
    Figure US20050009982A1-20050113-C00327
    Q2-29-3 —OCOC(CF3)═CH2
    1-29-4
    Figure US20050009982A1-20050113-C00328
    Figure US20050009982A1-20050113-C00329
    Q2-29-4 —NH2
    1-29-5
    Figure US20050009982A1-20050113-C00330
    —CH(CH3)2 Q2-29-5 —COOH
    1-30-1
    Figure US20050009982A1-20050113-C00331
    —C2H5 Q230-1 —OH
    1-30-2
    Figure US20050009982A1-20050113-C00332
    —CH3 Q230-2 —OCOCH═CH2
    1-30-3
    Figure US20050009982A1-20050113-C00333
    Figure US20050009982A1-20050113-C00334
    Q2-30-3 —COCl
    1-30-4
    Figure US20050009982A1-20050113-C00335
    Figure US20050009982A1-20050113-C00336
    Q2-30-4
    Figure US20050009982A1-20050113-C00337
    1-30-5
    Figure US20050009982A1-20050113-C00338
    —CH3 Q2-30-5 —COOH
    1-31-1
    Figure US20050009982A1-20050113-C00339
    —CH3 Q231-1
    Figure US20050009982A1-20050113-C00340
    1-31-2
    Figure US20050009982A1-20050113-C00341
    Figure US20050009982A1-20050113-C00342
    Q231-2 —OH
    1-31-3
    Figure US20050009982A1-20050113-C00343
    Figure US20050009982A1-20050113-C00344
    Q231-3 —COOH
    1-31-4
    Figure US20050009982A1-20050113-C00345
    —OCH3 Q2-31-4 —OCH═CH2
    1-31-5
    Figure US20050009982A1-20050113-C00346
    Figure US20050009982A1-20050113-C00347
    Q231-5 —OH
  • TABLE 13
    No. R1 Q1 Q2 Y1
    1-32-1
    Figure US20050009982A1-20050113-C00348
    —C3H7 Q2-32-1 —OCH═CH2
    1-32-2
    Figure US20050009982A1-20050113-C00349
    Figure US20050009982A1-20050113-C00350
    Q2-32-2 —COOH
    1-32-3
    Figure US20050009982A1-20050113-C00351
    Figure US20050009982A1-20050113-C00352
    Q2-32-3 —NH2
    1-32-4
    Figure US20050009982A1-20050113-C00353
    Figure US20050009982A1-20050113-C00354
    Q2-32-4 —OH
    1-32-5
    Figure US20050009982A1-20050113-C00355
    —C2H5 Q2-32-5 —OCOC(CH3)═CH2
    1-33-1
    Figure US20050009982A1-20050113-C00356
    Figure US20050009982A1-20050113-C00357
    Q2-33-1 —CN
    1-33-2
    Figure US20050009982A1-20050113-C00358
    —CH3 Q2-33-2 —COOH
    1-33-3
    Figure US20050009982A1-20050113-C00359
    —CH(CH3)2 Q2-33-3
    Figure US20050009982A1-20050113-C00360
    1-33-4
    Figure US20050009982A1-20050113-C00361
    Figure US20050009982A1-20050113-C00362
    Q233-4 —COOH
    1-33-5
    Figure US20050009982A1-20050113-C00363
    —CH3 Q2-33-5
    Figure US20050009982A1-20050113-C00364
    1-34-1
    Figure US20050009982A1-20050113-C00365
    Figure US20050009982A1-20050113-C00366
    Q2-34-1 —OH
    1-34-2
    Figure US20050009982A1-20050113-C00367
    Figure US20050009982A1-20050113-C00368
    Q2-34-2
    Figure US20050009982A1-20050113-C00369
    1-34-3
    Figure US20050009982A1-20050113-C00370
    —CH3 Q2-34-3 —NH2
    1-34-4
    Figure US20050009982A1-20050113-C00371
    —OCH3 Q2-34-4 —C≡CH
    1-34-5
    Figure US20050009982A1-20050113-C00372
    Figure US20050009982A1-20050113-C00373
    Q2-34-5 —OH
  • TABLE 14
    No. R1 Q1 Q2 Y1
    1-35-1
    Figure US20050009982A1-20050113-C00374
    Figure US20050009982A1-20050113-C00375
    Q2-35-1 —OH
    1-35-2
    Figure US20050009982A1-20050113-C00376
    Figure US20050009982A1-20050113-C00377
    Q2-35-2 —COOH
    1-35-3
    Figure US20050009982A1-20050113-C00378
    —CH3 Q2-35-3
    Figure US20050009982A1-20050113-C00379
    1-35-4
    Figure US20050009982A1-20050113-C00380
    Figure US20050009982A1-20050113-C00381
    Q2-35-4 —NH2
    1-35-5
    Figure US20050009982A1-20050113-C00382
    —CH(CH3)2 Q2-35-5
    Figure US20050009982A1-20050113-C00383
    1-36-1
    Figure US20050009982A1-20050113-C00384
    Figure US20050009982A1-20050113-C00385
    Q2-36-1 —CH═CHCH═CH2
    1-36-2
    Figure US20050009982A1-20050113-C00386
    —C3H7 Q2-36-2 —OH
    1-36-3
    Figure US20050009982A1-20050113-C00387
    —C2H5 Q2-36-3 —Br
    1-36-4
    Figure US20050009982A1-20050113-C00388
    Figure US20050009982A1-20050113-C00389
    Q2-36-4
    Figure US20050009982A1-20050113-C00390
    1-36-5
    Figure US20050009982A1-20050113-C00391
    —CH3 Q2-36-5 —COOH
    1-37-1
    Figure US20050009982A1-20050113-C00392
    —OC2H5 Q2-37-1
    Figure US20050009982A1-20050113-C00393
    1-37-2
    Figure US20050009982A1-20050113-C00394
    Figure US20050009982A1-20050113-C00395
    Q2-37-2 —OH
    1-37-3
    Figure US20050009982A1-20050113-C00396
    Figure US20050009982A1-20050113-C00397
    Q237-3 —CHO
    1-37-4
    Figure US20050009982A1-20050113-C00398
    —OCH3 Q2-37-4 —OH
    1-37-5
    Figure US20050009982A1-20050113-C00399
    Figure US20050009982A1-20050113-C00400
    Q2-37-5
    Figure US20050009982A1-20050113-C00401
  • TABLE 15
    No. R1 Q1 Q2 Y1
    1-38-1
    Figure US20050009982A1-20050113-C00402
    Figure US20050009982A1-20050113-C00403
    Q2-38-1 NH2
    1-38-2
    Figure US20050009982A1-20050113-C00404
    Figure US20050009982A1-20050113-C00405
    Q2-38-2 —OCOCH═CH2
    1-38-3
    Figure US20050009982A1-20050113-C00406
    —C3H7 Q2-38-3 —OCH═CH2
    1-38-4
    Figure US20050009982A1-20050113-C00407
    Figure US20050009982A1-20050113-C00408
    Q2-38-4 —OH
    1-38-5
    Figure US20050009982A1-20050113-C00409
    —CH3 Q2-38-5 —OCH═CH2
    1-39-1
    Figure US20050009982A1-20050113-C00410
    Figure US20050009982A1-20050113-C00411
    Q2-39-1
    Figure US20050009982A1-20050113-C00412
    1-39-2
    Figure US20050009982A1-20050113-C00413
    —CH(CH3)2 Q2-39-2 —OH
    1-39-3
    Figure US20050009982A1-20050113-C00414
    —CH3 Q2-39-3
    Figure US20050009982A1-20050113-C00415
    1-39-4
    Figure US20050009982A1-20050113-C00416
    Figure US20050009982A1-20050113-C00417
    Q2-39-4 —COOH
    1-39-5
    Figure US20050009982A1-20050113-C00418
    Figure US20050009982A1-20050113-C00419
    Q2-39-5
    Figure US20050009982A1-20050113-C00420
    1-40-1
    Figure US20050009982A1-20050113-C00421
    —OCH3 Q2-40-1 —OH
    1-40-2
    Figure US20050009982A1-20050113-C00422
    Figure US20050009982A1-20050113-C00423
    Q2-40-2 —NH2
    1-40-3
    Figure US20050009982A1-20050113-C00424
    —CH(CH3)2 Q2-40-3 —OH
    1-40-4
    Figure US20050009982A1-20050113-C00425
    —C2H5 Q2-40-4 —OCCH═CH2
    1-40-5
    Figure US20050009982A1-20050113-C00426
    Figure US20050009982A1-20050113-C00427
    Q2-40-5 —COOH
  • TABLE 16
    No. R1 Q1 Q2 Y1
    1-41-1
    Figure US20050009982A1-20050113-C00428
    —CH3 Q2-41-1 —COOH
    1-41-2
    Figure US20050009982A1-20050113-C00429
    Figure US20050009982A1-20050113-C00430
    Q2-41-2 —NH2
    1-41-3
    Figure US20050009982A1-20050113-C00431
    —OC2H5 Q2-41-3 —OCOC(CH)═CH2
    1-41-4
    Figure US20050009982A1-20050113-C00432
    Figure US20050009982A1-20050113-C00433
    Q2-41-4 —NH2
    1-41-5
    Figure US20050009982A1-20050113-C00434
    —C4H9 Q2-41-5
    Figure US20050009982A1-20050113-C00435
    1-42-1
    Figure US20050009982A1-20050113-C00436
    Figure US20050009982A1-20050113-C00437
    Q2-42-1 —OH
    1-42-2
    Figure US20050009982A1-20050113-C00438
    —CH(CH3)2 Q2-42-2 —NH2
    1-42-3
    Figure US20050009982A1-20050113-C00439
    —CH3 Q2-42-3 —COOH
    1-42-4
    Figure US20050009982A1-20050113-C00440
    Figure US20050009982A1-20050113-C00441
    Q2-42-4
    Figure US20050009982A1-20050113-C00442
    1-42-5
    Figure US20050009982A1-20050113-C00443
    Figure US20050009982A1-20050113-C00444
    Q2-42-5
    Figure US20050009982A1-20050113-C00445
    1-43-1
    Figure US20050009982A1-20050113-C00446
    —C2H5 Q2-43-1
    Figure US20050009982A1-20050113-C00447
    1-43-2
    Figure US20050009982A1-20050113-C00448
    Figure US20050009982A1-20050113-C00449
    Q2-43-2 —CH═CH2
    1-43-3
    Figure US20050009982A1-20050113-C00450
    —CH(CH3)2 Q2-43-3 —COOH
    1-43-4
    Figure US20050009982A1-20050113-C00451
    —CH3 Q2-43-4 —OCOCH═CH2
    1-43-5
    Figure US20050009982A1-20050113-C00452
    Figure US20050009982A1-20050113-C00453
    Q2-43-5
    Figure US20050009982A1-20050113-C00454
  • TABLE 17
    No. R1 Q1 Q2 Y1
    1-44-1
    Figure US20050009982A1-20050113-C00455
    Figure US20050009982A1-20050113-C00456
    Q2-44-1 —COOH
    1-44-2
    Figure US20050009982A1-20050113-C00457
    —CH3 Q2-44-2 —OCH═CH2
    1-44-3
    Figure US20050009982A1-20050113-C00458
    —CH(CH3)2 Q2-44-3
    Figure US20050009982A1-20050113-C00459
    1-44-4
    Figure US20050009982A1-20050113-C00460
    —OCH3 Q2-44-4 —OH
    1-44-5
    Figure US20050009982A1-20050113-C00461
    —C3H7 Q2-44-5 —COOH
    1-45-1
    Figure US20050009982A1-20050113-C00462
    Figure US20050009982A1-20050113-C00463
    Q2-45-1
    Figure US20050009982A1-20050113-C00464
    1-45-2
    Figure US20050009982A1-20050113-C00465
    —CH═CH2 Q2-45-2 —NH2
    1-45-3
    Figure US20050009982A1-20050113-C00466
    —CH3 Q2-45-3 —COOH
    1-45-4
    Figure US20050009982A1-20050113-C00467
    Figure US20050009982A1-20050113-C00468
    Q2-45-4 —NH2
    1-46-1
    Figure US20050009982A1-20050113-C00469
    Figure US20050009982A1-20050113-C00470
    Q2-45-5
    Figure US20050009982A1-20050113-C00471
    1-46-2
    Figure US20050009982A1-20050113-C00472
    —CH3 Q2-46-1 —OH
    1-46-2
    Figure US20050009982A1-20050113-C00473
    Figure US20050009982A1-20050113-C00474
    Q2-46-2 —CN
    1-46-3
    Figure US20050009982A1-20050113-C00475
    —C3H7 Q2-46-3
    Figure US20050009982A1-20050113-C00476
    1-46-4
    Figure US20050009982A1-20050113-C00477
    Figure US20050009982A1-20050113-C00478
    Q2-46-4 —COOH
    1-46-5
    Figure US20050009982A1-20050113-C00479
    Figure US20050009982A1-20050113-C00480
    Q2-46-5 —OCOC(CF3)═CH2
  • TABLE 18
    No. R1 Q1 Q2 Y1
    1-47-1
    Figure US20050009982A1-20050113-C00481
    Figure US20050009982A1-20050113-C00482
    Q2-47-1 —COOH
    1-47-2
    Figure US20050009982A1-20050113-C00483
    —C4H9 Q2-47-2
    Figure US20050009982A1-20050113-C00484
    1-47-3
    Figure US20050009982A1-20050113-C00485
    Figure US20050009982A1-20050113-C00486
    Q2-47-3
    Figure US20050009982A1-20050113-C00487
    1-47-4
    Figure US20050009982A1-20050113-C00488
    —OCH(CH3)2 Q2-47-4 —OH
    1-47-5
    Figure US20050009982A1-20050113-C00489
    —CH3 Q2-47-5
    Figure US20050009982A1-20050113-C00490
    1-48-1
    Figure US20050009982A1-20050113-C00491
    Figure US20050009982A1-20050113-C00492
    Q248-1 —COOH
    1-48-2
    Figure US20050009982A1-20050113-C00493
    —CH3 Q2-48-2 —NH2
    1-48-3
    Figure US20050009982A1-20050113-C00494
    —CH3 Q2-48-3
    Figure US20050009982A1-20050113-C00495
    1-48-4
    Figure US20050009982A1-20050113-C00496
    Figure US20050009982A1-20050113-C00497
    Q2-48-4 —OH
    1-48-5
    Figure US20050009982A1-20050113-C00498
    Figure US20050009982A1-20050113-C00499
    Q2-48-5 —OCOCH═CH2
    1-49-1
    Figure US20050009982A1-20050113-C00500
    —CH(CH3)2 Q2-49-1
    Figure US20050009982A1-20050113-C00501
    1-49-2
    Figure US20050009982A1-20050113-C00502
    Figure US20050009982A1-20050113-C00503
    Q2-49-2 —COCl
    1-49-3
    Figure US20050009982A1-20050113-C00504
    —C3H7 Q2-49-3 —OCH═CH2
    1-49-4
    Figure US20050009982A1-20050113-C00505
    Figure US20050009982A1-20050113-C00506
    Q2-49-4 —NH2
    1-49-5
    Figure US20050009982A1-20050113-C00507
    Figure US20050009982A1-20050113-C00508
    Q2-49-5
    Figure US20050009982A1-20050113-C00509
  • TABLE 19
    No. R1 Q1 Q2 Y1
    1-50-1
    Figure US20050009982A1-20050113-C00510
    —CH(CH3)2 Q2-50-1 —NH2
    1-50-2
    Figure US20050009982A1-20050113-C00511
    Figure US20050009982A1-20050113-C00512
    Q2-50-2
    Figure US20050009982A1-20050113-C00513
    1-50-3
    Figure US20050009982A1-20050113-C00514
    —OCH3 Q2-50-3 —OH
    1-50-4
    Figure US20050009982A1-20050113-C00515
    —CH3 Q2-50-4
    Figure US20050009982A1-20050113-C00516
    1-50-5
    Figure US20050009982A1-20050113-C00517
    —CH2CH═CH2 Q2-50-5 —OCOC(CH3)═CH2
    1-51-1
    Figure US20050009982A1-20050113-C00518
    —OCH3 Q2-51-1 —COOH
    1-51-2
    Figure US20050009982A1-20050113-C00519
    Figure US20050009982A1-20050113-C00520
    Q2-51-2 —NH2
    1-51-3
    Figure US20050009982A1-20050113-C00521
    —CH3 Q2-51-3
    Figure US20050009982A1-20050113-C00522
    1-51-4
    Figure US20050009982A1-20050113-C00523
    Figure US20050009982A1-20050113-C00524
    Q2-51-4 —NH2
    1-51-5
    Figure US20050009982A1-20050113-C00525
    Figure US20050009982A1-20050113-C00526
    Q2-51-5 —COCH═CH2
    1-52-1
    Figure US20050009982A1-20050113-C00527
    —CH3 Q2-52-1 —OH
    1-52-2
    Figure US20050009982A1-20050113-C00528
    —C2H5 Q2-52-2 —COOH
    1-52-3
    Figure US20050009982A1-20050113-C00529
    —C2H5 Q2-52-3
    Figure US20050009982A1-20050113-C00530
    1-52-4
    Figure US20050009982A1-20050113-C00531
    —C2H5 Q2-52-4 —OCOCH═CH2
    1-52-5
    Figure US20050009982A1-20050113-C00532
    Figure US20050009982A1-20050113-C00533
    Q2-52-5 —COOH
  • TABLE 20
    No. R1 Q1 Q2 Y1
    1-53-1
    Figure US20050009982A1-20050113-C00534
    —C2H5 Q2-53-1 —NH2
    1-53-2
    Figure US20050009982A1-20050113-C00535
    Figure US20050009982A1-20050113-C00536
    Q2-53-2
    Figure US20050009982A1-20050113-C00537
    1-53-3
    Figure US20050009982A1-20050113-C00538
    —CH3 Q2-53-3 —NH2
    1-53-4
    Figure US20050009982A1-20050113-C00539
    —CH(CH3)2 Q2-53-4 —OH
    1-53-5
    Figure US20050009982A1-20050113-C00540
    Figure US20050009982A1-20050113-C00541
    Q2-53-5
    Figure US20050009982A1-20050113-C00542
    1-54-1
    Figure US20050009982A1-20050113-C00543
    —CH3 Q2-54-1 —COOH
    1-54-2
    Figure US20050009982A1-20050113-C00544
    Figure US20050009982A1-20050113-C00545
    Q2-54-2
    Figure US20050009982A1-20050113-C00546
    1-54-3
    Figure US20050009982A1-20050113-C00547
    Figure US20050009982A1-20050113-C00548
    Q2-54-3 —OH
    1-54-4
    Figure US20050009982A1-20050113-C00549
    —CH3 Q2-54-4 —NH2
    1-54-5
    Figure US20050009982A1-20050113-C00550
    —C2H5 Q2-54-5 —COCH═CH2
    1-55-1
    Figure US20050009982A1-20050113-C00551
    Figure US20050009982A1-20050113-C00552
    Q2-55-1 —COOH
    1-55-2
    Figure US20050009982A1-20050113-C00553
    —OCH3 Q2-55-2
    Figure US20050009982A1-20050113-C00554
    1-55-3
    Figure US20050009982A1-20050113-C00555
    Figure US20050009982A1-20050113-C00556
    Q2-55-3 —CH═CH2
    1-55-4
    Figure US20050009982A1-20050113-C00557
    —C2H5 Q2-55-4
    Figure US20050009982A1-20050113-C00558
    1-55-5
    Figure US20050009982A1-20050113-C00559
    —C2H5 Q2-55-5 —OH
  • TABLE 21
    No. R1 Q1 Q2 Y1
    1-56-1
    Figure US20050009982A1-20050113-C00560
    —CH3 Q2-56-1 —COOH
    1-56-2
    Figure US20050009982A1-20050113-C00561
    Figure US20050009982A1-20050113-C00562
    Q2-56-2 —OCOC(CH3)═CH2
    1-56-3
    Figure US20050009982A1-20050113-C00563
    —C2H5 Q2-56-3 —OCH═CH2
    1-56-4
    Figure US20050009982A1-20050113-C00564
    —Cl Q2-56-4 —OH
    1-56-5
    Figure US20050009982A1-20050113-C00565
    Figure US20050009982A1-20050113-C00566
    Q2-56-5
    Figure US20050009982A1-20050113-C00567
    1-57-1
    Figure US20050009982A1-20050113-C00568
    —CH3 Q2-57-1 —NH2
    1-57-2
    Figure US20050009982A1-20050113-C00569
    Figure US20050009982A1-20050113-C00570
    Q2-57-2 —COOH
    1-57-3
    Figure US20050009982A1-20050113-C00571
    —CH(CH3)2 Q2-57-3
    Figure US20050009982A1-20050113-C00572
    1-57-4
    Figure US20050009982A1-20050113-C00573
    Figure US20050009982A1-20050113-C00574
    Q2-57-4
    Figure US20050009982A1-20050113-C00575
    1-57-5
    Figure US20050009982A1-20050113-C00576
    Figure US20050009982A1-20050113-C00577
    Q2-57-5 —OH
    1-58-1
    Figure US20050009982A1-20050113-C00578
    —CH3 Q2-58-1 —COOH
    1-58-2
    Figure US20050009982A1-20050113-C00579
    —CH═CH2 Q2-58-2 —NH2
    1-58-3
    Figure US20050009982A1-20050113-C00580
    —C3H7 Q2-58-3 —OCOCH═CH2
    1-58-4
    Figure US20050009982A1-20050113-C00581
    —C2H5 Q2-58-4
    Figure US20050009982A1-20050113-C00582
    1-58-5
    Figure US20050009982A1-20050113-C00583
    Figure US20050009982A1-20050113-C00584
    Q2-58-5
    Figure US20050009982A1-20050113-C00585
  • TABLE 22
    No. R1 Q1 Q2 Y1
    1-59-1
    Figure US20050009982A1-20050113-C00586
    —CH3 Q2-59-1 —OH
    1-59-2
    Figure US20050009982A1-20050113-C00587
    —CH3 Q2-59-2
    Figure US20050009982A1-20050113-C00588
    1-59-3
    Figure US20050009982A1-20050113-C00589
    —C3H7 Q2-59-3 —OCOCH═CH2
    1-59-4
    Figure US20050009982A1-20050113-C00590
    —H Q2-59-4 —COOH
    1-59-5
    Figure US20050009982A1-20050113-C00591
    Figure US20050009982A1-20050113-C00592
    Q2-59-5 —OH
    1-60-1
    Figure US20050009982A1-20050113-C00593
    —CH3 Q2-60-1 —NH2
    1-60-2
    Figure US20050009982A1-20050113-C00594
    Figure US20050009982A1-20050113-C00595
    Q2-60-2 —OCH═CH2
    1-60-3
    Figure US20050009982A1-20050113-C00596
    —C2H5 Q2-60-3
    Figure US20050009982A1-20050113-C00597
    1-60-4
    Figure US20050009982A1-20050113-C00598
    Figure US20050009982A1-20050113-C00599
    Q2-60-4 —NH2
    1-60-5
    Figure US20050009982A1-20050113-C00600
    —CH(CH3)2 Q2-60-5
    Figure US20050009982A1-20050113-C00601
    1-61-1
    Figure US20050009982A1-20050113-C00602
    —CH3 Q2-61-1 —COOH
    1-61-2
    Figure US20050009982A1-20050113-C00603
    —C4H9 Q2-61-2 —OH
    1-61-3
    Figure US20050009982A1-20050113-C00604
    Figure US20050009982A1-20050113-C00605
    Q2-61-3 —NH2
    1-61-4
    Figure US20050009982A1-20050113-C00606
    —C2H5 Q2-61-4 —CH═CH2
    1-61-5
    Figure US20050009982A1-20050113-C00607
    —CH3 Q2-61-5
    Figure US20050009982A1-20050113-C00608
  • TABLE 23
    No. R1 Q1 Q2 Y1
    1-62-1
    Figure US20050009982A1-20050113-C00609
    —C2H5 Q2-62-1 —OH
    1-62-2
    Figure US20050009982A1-20050113-C00610
    —CH3 Q2-62-2 —NH2
    1-62-3
    Figure US20050009982A1-20050113-C00611
    —CH3 Q2-62-3 —COOH
    1-63-1
    Figure US20050009982A1-20050113-C00612
    Figure US20050009982A1-20050113-C00613
    Q2-63-1
    Figure US20050009982A1-20050113-C00614
    1-63-2
    Figure US20050009982A1-20050113-C00615
    Figure US20050009982A1-20050113-C00616
    Q2-63-2 —COCH═CH2
    1-63-3
    Figure US20050009982A1-20050113-C00617
    —C3H7 Q2-63-3
    Figure US20050009982A1-20050113-C00618
    1-64-1
    Figure US20050009982A1-20050113-C00619
    Figure US20050009982A1-20050113-C00620
    Q2-64-1
    Figure US20050009982A1-20050113-C00621
    1-64-2
    Figure US20050009982A1-20050113-C00622
    —CH(CH3)2 Q2-64-2 —OCOCH═CH2
    1-64-3
    Figure US20050009982A1-20050113-C00623
    Figure US20050009982A1-20050113-C00624
    Q2-64-3 —COOH
    1-65-1
    Figure US20050009982A1-20050113-C00625
    —CH(CH3)2 Q2-65-1
    Figure US20050009982A1-20050113-C00626
    1-65-2
    Figure US20050009982A1-20050113-C00627
    Figure US20050009982A1-20050113-C00628
    Q2-65-2 —NH2
    1-65-3
    Figure US20050009982A1-20050113-C00629
    Figure US20050009982A1-20050113-C00630
    Q2-65-3 —COOH
    1-66-1
    Figure US20050009982A1-20050113-C00631
    —CH3 Q2-66-1 —NH2
    1-66-2
    Figure US20050009982A1-20050113-C00632
    —CH3 Q2-66-2 —OH
    1-66-3
    Figure US20050009982A1-20050113-C00633
    Figure US20050009982A1-20050113-C00634
    Q2-66-3
    Figure US20050009982A1-20050113-C00635
  • TABLE 24
    No. R1 Q1 Q2 Y1
    1-67-1
    Figure US20050009982A1-20050113-C00636
    Figure US20050009982A1-20050113-C00637
    Q2-67-1 —OH
    1-67-2
    Figure US20050009982A1-20050113-C00638
    —CH═CH2 Q2-67-2
    Figure US20050009982A1-20050113-C00639
    1-67-3
    Figure US20050009982A1-20050113-C00640
    —CH3 Q2-67-3 —COOH
    1-68-1
    Figure US20050009982A1-20050113-C00641
    Figure US20050009982A1-20050113-C00642
    Q2-68-1 —OCOC(CF3)═CH2
    1-68-2
    Figure US20050009982A1-20050113-C00643
    —C3H7 Q2-68-2 —Br
    1-68-3
    Figure US20050009982A1-20050113-C00644
    —C3H7 Q2-68-3 —COOH
    1-69-1
    Figure US20050009982A1-20050113-C00645
    Figure US20050009982A1-20050113-C00646
    Q2-69-1 —OH
    1-69-2
    Figure US20050009982A1-20050113-C00647
    —C2H5 Q2-69-2
    Figure US20050009982A1-20050113-C00648
    1-69-3
    Figure US20050009982A1-20050113-C00649
    Figure US20050009982A1-20050113-C00650
    Q2-69-3 —CH═CH2
    1-70-1
    Figure US20050009982A1-20050113-C00651
    —CH3 Q2-70-1 —COOH
    1-70-2
    Figure US20050009982A1-20050113-C00652
    Figure US20050009982A1-20050113-C00653
    Q2-70-2
    Figure US20050009982A1-20050113-C00654
    1-70-3
    Figure US20050009982A1-20050113-C00655
    —OCH3 Q2-70-3 —COCl
    1-71-1
    Figure US20050009982A1-20050113-C00656
    Figure US20050009982A1-20050113-C00657
    Q2-71-1 —NH2
    1-71-2
    Figure US20050009982A1-20050113-C00658
    —CH3 Q2-71-2 —OH
    1-71-3
    Figure US20050009982A1-20050113-C00659
    —CH(CH3)2 Q2-71-3 —OCH═CH2
  • TABLE 25
    No. R1 Q1 Q2 Y1
    1-72-1
    Figure US20050009982A1-20050113-C00660
    Figure US20050009982A1-20050113-C00661
    Q2-72-1 —COOH
    1-72-2
    Figure US20050009982A1-20050113-C00662
    —CH3 Q2-72-2 —OH
    1-72-3
    Figure US20050009982A1-20050113-C00663
    —CH3 Q2-72-3 —OCH═CH2
    1-73-1
    Figure US20050009982A1-20050113-C00664
    Figure US20050009982A1-20050113-C00665
    Q2-73-1 —NH2
    1-73-2
    Figure US20050009982A1-20050113-C00666
    —CH3 Q2-73-2 —OH
    1-73-3
    Figure US20050009982A1-20050113-C00667
    Figure US20050009982A1-20050113-C00668
    Q2-73-3
    Figure US20050009982A1-20050113-C00669
    1-74-1
    Figure US20050009982A1-20050113-C00670
    —C2H5 Q2-74-1 —OH
    1-74-2
    Figure US20050009982A1-20050113-C00671
    —CH(CH3)2 Q2-74-2 —COOH
    1-74-3
    Figure US20050009982A1-20050113-C00672
    Figure US20050009982A1-20050113-C00673
    Q2-74-3
    Figure US20050009982A1-20050113-C00674
    1-75-1
    Figure US20050009982A1-20050113-C00675
    —CH3 Q2-75-1
    Figure US20050009982A1-20050113-C00676
    1-75-2
    Figure US20050009982A1-20050113-C00677
    —OCH3 Q2-75-2 —COOH
    1-75-3
    Figure US20050009982A1-20050113-C00678
    —C3H7 Q2-75-3 —OH
    1-76-1
    Figure US20050009982A1-20050113-C00679
    —CH(CH3)2 Q2-76-1 —OH
    1-76-2
    Figure US20050009982A1-20050113-C00680
    —CH3 Q2-76-2 —OCOCH═CH2
    1-76-3
    Figure US20050009982A1-20050113-C00681
    —OCH3 Q2-76-3
    Figure US20050009982A1-20050113-C00682
  • TABLE 26
    No. R1 Q1 Q2 Y2
    1-77-1
    Figure US20050009982A1-20050113-C00683
    Figure US20050009982A1-20050113-C00684
    Q2-77-1 —COOH
    1-77-2
    Figure US20050009982A1-20050113-C00685
    —CH3 Q2-77-2 —OH
    1-77-3
    Figure US20050009982A1-20050113-C00686
    —CH3 Q2-77-3 —CH═CH2
    1-78-1
    Figure US20050009982A1-20050113-C00687
    Figure US20050009982A1-20050113-C00688
    Q2-78-1 —OH
    1-78-2
    Figure US20050009982A1-20050113-C00689
    —C3H7 Q2-78-2 —OCH═CH2
    1-78-3
    Figure US20050009982A1-20050113-C00690
    Figure US20050009982A1-20050113-C00691
    Q2-78-3
    Figure US20050009982A1-20050113-C00692
    1-79-1
    Figure US20050009982A1-20050113-C00693
    —C4H9 Q2-79-1 —OH
    1-79-2
    Figure US20050009982A1-20050113-C00694
    —CH3 Q2-79-2 —NH2
    1-79-3
    Figure US20050009982A1-20050113-C00695
    Figure US20050009982A1-20050113-C00696
    Q2-79-3 —COOH
    1-80-1
    Figure US20050009982A1-20050113-C00697
    —CH3 Q2-80-1 —NH2
    1-80-2
    Figure US20050009982A1-20050113-C00698
    —C2H5 Q2-80-2 —CN
    1-80-3
    Figure US20050009982A1-20050113-C00699
    —CH3 Q2-80-3 —COOH
    1-81-1
    Figure US20050009982A1-20050113-C00700
    Figure US20050009982A1-20050113-C00701
    Q2-81-1 —OH
    1-81-2
    Figure US20050009982A1-20050113-C00702
    —OCH3 Q2-81-2
    Figure US20050009982A1-20050113-C00703
    1-81-3
    Figure US20050009982A1-20050113-C00704
    Figure US20050009982A1-20050113-C00705
    Q2-81-3
    Figure US20050009982A1-20050113-C00706
  • TABLE 27
    No. R1 Q1 Q2 Y1
    1-82-1
    Figure US20050009982A1-20050113-C00707
    —OCH3 Q2-82-1 —COOH
    1-82-2
    Figure US20050009982A1-20050113-C00708
    —CH3 Q2-82-2 —OH
    1-82-3
    Figure US20050009982A1-20050113-C00709
    Figure US20050009982A1-20050113-C00710
    Q2-82-3 —NH2
    1-83-1
    Figure US20050009982A1-20050113-C00711
    Figure US20050009982A1-20050113-C00712
    Q2-83-1 —CH═CH2
    1-83-2
    Figure US20050009982A1-20050113-C00713
    —CH(CH3)2 Q2-83-2 —NH2
    1-84-1
    Figure US20050009982A1-20050113-C00714
    —C2H5 Q2-84-1 —OH
    1-84-2
    Figure US20050009982A1-20050113-C00715
    —CH3 Q2-84-2
    Figure US20050009982A1-20050113-C00716
    1-85-1
    Figure US20050009982A1-20050113-C00717
    Figure US20050009982A1-20050113-C00718
    Q2-85-1 —COCl
    1-85-2
    Figure US20050009982A1-20050113-C00719
    Figure US20050009982A1-20050113-C00720
    Q2-85-2
    Figure US20050009982A1-20050113-C00721
    1-86-1
    Figure US20050009982A1-20050113-C00722
    —CH3 Q2-86-1 —OH
    1-86-2
    Figure US20050009982A1-20050113-C00723
    —CH3 Q2-86-2 —COOH
    1-86-3
    Figure US20050009982A1-20050113-C00724
    Figure US20050009982A1-20050113-C00725
    Q2-86-3 —OH
    1-87-1
    Figure US20050009982A1-20050113-C00726
    Figure US20050009982A1-20050113-C00727
    Q2-87-1 —CHO
    1-87-2
    Figure US20050009982A1-20050113-C00728
    —OCH3 Q2-87-2
    Figure US20050009982A1-20050113-C00729
  • TABLE 28
    No. R1 Q1 Q2 Y1
    1-88-1
    Figure US20050009982A1-20050113-C00730
    Figure US20050009982A1-20050113-C00731
    Q2-88-1 —COOH
    1-88-2
    Figure US20050009982A1-20050113-C00732
    —CH(CH3)2 Q2-88-2
    Figure US20050009982A1-20050113-C00733
    1-89-1
    Figure US20050009982A1-20050113-C00734
    Figure US20050009982A1-20050113-C00735
    Q2-89-1 —OH
    1-89-2
    Figure US20050009982A1-20050113-C00736
    Figure US20050009982A1-20050113-C00737
    Q2-89-2 —NH2
  • In the tables described above, Q2-1-1 to Q2-89-2 described in the column of Q2 have meanings shown in the following Formula (Q2-1-1) to Formula (Q2-89-2). A code “<” shown at a left end in these formulas shows a bonding point to an Si atom.
    Figure US20050009982A1-20050113-C00738
    Figure US20050009982A1-20050113-C00739
    Figure US20050009982A1-20050113-C00740
    Figure US20050009982A1-20050113-C00741
    Figure US20050009982A1-20050113-C00742
    Figure US20050009982A1-20050113-C00743
    Figure US20050009982A1-20050113-C00744
    Figure US20050009982A1-20050113-C00745
    Figure US20050009982A1-20050113-C00746
    Figure US20050009982A1-20050113-C00747
    Figure US20050009982A1-20050113-C00748
    Figure US20050009982A1-20050113-C00749
    Figure US20050009982A1-20050113-C00750
    Figure US20050009982A1-20050113-C00751
    Figure US20050009982A1-20050113-C00752
    Figure US20050009982A1-20050113-C00753
    Figure US20050009982A1-20050113-C00754
    Figure US20050009982A1-20050113-C00755
    Figure US20050009982A1-20050113-C00756
    Figure US20050009982A1-20050113-C00757
    Figure US20050009982A1-20050113-C00758
    Figure US20050009982A1-20050113-C00759
    Figure US20050009982A1-20050113-C00760
    Figure US20050009982A1-20050113-C00761
    Figure US20050009982A1-20050113-C00762
    Figure US20050009982A1-20050113-C00763
    Figure US20050009982A1-20050113-C00764
    Figure US20050009982A1-20050113-C00765
    Figure US20050009982A1-20050113-C00766
    Figure US20050009982A1-20050113-C00767
    Figure US20050009982A1-20050113-C00768
    Figure US20050009982A1-20050113-C00769
    Figure US20050009982A1-20050113-C00770
    Figure US20050009982A1-20050113-C00771
    Figure US20050009982A1-20050113-C00772
    Figure US20050009982A1-20050113-C00773
  • Comparative Example 1
  • <Production 1 of Polyamic Acid>
  • An NMP (45 g) solution of 4,4′-diaminodiphenyl ether (2.39 g) was cooled under nitrogen atmosphere. Pyromellitic dianhydride (2.61 g) was added to the above solution while maintaining the temperature of the reaction system in a range of 5 to 70° C. Then, the solution was stirred for 20 hours to obtain a polyamic acid vanish (50 g) having a polymer concentration of 10% by weight. Polyamic acid contained in the above vanish is named PA acid 1.
  • Example 7
  • <Production 2 of Polyamic Acid>
  • A polyamic acid vanish (15 g) having a polymer concentration of 20% by weight was obtained in the same manner as in Comparative Example 1, except that pyromellitic dianhydride was changed to Compound (1-1-4) (1.49 g) and 4,4′-diaminodiphenyl ether was changed to Compound (1-3-7) (1.51 g) and that a use amount of NMP was changed to 12 g. Polyamic acid contained in the above vanish is named PA acid 2.
  • Example 8
  • <Production 3 of Polyamic Acid>
  • A polyamic acid vanish (15 g) having a polymer concentration of 20% by weight was obtained in the same manner as in Example 5, except that Compound (1-1-4) was changed to pyromellitic dianhydride (0.39 g) and that a use amount of Compound (1-3-7) was changed to 2.61 g. Polyamic acid contained in the above vanish is named PA acid 3.
  • Example 9
  • <Production 4 of Polyamic Acid>
  • A polyamic acid vanish (10 g) having a polymer concentration of 30% by weight was obtained in the same manner as in Example 5, except that a use amount of Compound (1-1-4) was changed to 2.63 g and Compound (1-3-7) was changed to 4,4′-diaminodiphenyl ether (0.38 g) and that a use amount of NMP was changed to 7 g. Polyamic acid contained in the above vanish is named PA acid 4.
  • Example 10
  • The respective vanishes of PA acid 1 to PA acid 4 were diluted to suitable concentrations by butyl cellosolve and coated on a glass substrate by means of a spinner. It was pre-baked at 80° C. for about 5 minutes and then subjected to heat treatment at 220° C. for 30 minutes and then at 300° C. for 60 minutes to form the respective polyimide thin films. These polyimide thin films are designated as PI-1, PI-2, PI-3 and PI-4. PI-1 to PI-4 were measured for physical properties, and the results thereof are shown in Table 29.
  • Example 11
  • <Production of Polyester>
  • Two drops of titanium triisopropoxide were added to a mixture of Compound (1-1-2) (3.12 g, 2.25 mmol) and butanediol (0.40 g, 4.44 mmol) under nitrogen atmosphere, and the solution was heated and stirred at 220° C. for one hour. After cooling, the content was taken out to obtain 1.91 g of a polyester.
  • Example 12
  • A part of the polyester obtained in Example 11 was completely dissolved in NMP (9 g), and this solution was diluted to a suitable concentration by butyl cellosolve and coated on a glass substrate by means of a spinner. It was pre-dried at 80° C. for about 5 minutes and then subjected to heat treatment at 100° C. for one hour and then at 220° C. for 3 hours to obtain a polyester thin film PE-1. PE-1 was measured for physical properties, and the results thereof are shown in Table 29.
    TABLE 29
    PI-1 PI-2 PI-3 PI-4 PE-1
    Pencil hardness 3 H 2 H 2 H 2 H HB
    Refractive index >1.710 1.599 1.601 1.556 1.58
    Light transmittance 49 91.2 87.5 95.8 99.6
    (%)
    Surface free energy 40.4 31.7 31.9 29.8 31.6
    Thermal cracking- 182 375 360 377 366
    starting temperature
    (° C.)
     5% weight-reducing 199 438 460 448 387
    temperature (° C.)
    10% weight-reducing 231 502 518 496 413
    temperature (° C.)
    • (Remark 1): the light transmittance is a value measured at 400 nm.
    • (Remark 2): the unit of the surface free energy is erg/cm2.
    Example 13
  • The polyester (0.26 g) obtained in Example 11 was pressed by means of a pressing machine (upper face, lower face temperature: 260° C., press pressure: 19.6 MPa) to obtain a polyester substrate having an average thickness of 244 μm.
  • Comparative Example 2
  • <Production 1 of Epoxy Resin>
  • Bisphenol A glycidyl ether (brand name: EPICLON 850S, manufactured by Dainippon Ink & Chemicals Inc.) (0.3 g) and 4,4′-diaminodiphenyl ether (0.176 g) were dissolved in NMP (1.11 g) to obtain an epoxy compound solution having a compound concentration of 30% by weight. This solution was coated on a copper foil, pre-baked at 80° C. for about 30 minutes and then subjected to heat treatment at 220° C. for 60 minutes and then at 220° C. for 60 minutes under reduced pressure, and it was subjected to etching treatment to obtain an epoxy resin film having a thickness of about 40 μm. The above film had an average light transmittance of 65.2% in 400 to 800 nm, and a wavelength in which the light transmittance was less than 1% was 345 nm.
  • Example 14
  • <Production 2 of Epoxy Resin>
  • An epoxy compound solution having a compound concentration of 30% by weight was obtained in the same manner as in Comparative Example 2, except that EPICLON 850S was changed to Compound (1-1-5) (1.0 g) and a use amount of 4,4′-diaminodiphenyl ether was changed to 0.145 g and that a use amount of NMP was changed to 2.67 g. The above solution was treated in the same manner as in Comparative Example 2 to obtain an epoxy resin film having a thickness of about 100 μm. This film had an average light transmittance of 81.4% in 400 to 800 nm, and a wavelength in which the light transmittance was less than 1% was 260 nm. That is, it is apparent that a PSQ skeleton can be introduced into the epoxy resin without adding polysiloxane and that the resulting coating film is improved in transparency as compared with the coating film prepared in Comparative Example 2.
  • INDUSTRIAL APPLICABILITY
  • The compound of the present invention has a good compatibility with other compounds and polymers, and can readily provide a polymer of a high molecular weight having a silsesquioxane skeleton in a principal chain and/or side chains by homopolymerization or copolymerization. The polymer is excellent in characteristics such as mechanical strength, coating property, compatibility, transparency, heat resistance, water repellency and electrical insulating property. The polymer can be used for a coating agent, a plastic substrate and an optical material.

Claims (40)

1. a compound represented by formula (1):
Figure US20050009982A1-20050113-C00774
wherein R1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; and Q2 is a group represented by Formula (2):
Figure US20050009982A1-20050113-C00775
wherein the code < represents a bonding point with silicon; l, m, n and p are independently 0, 1, 2 or 3; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in these rings, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional —CH═ may be replaced by —N═; optional hydrogen in all rings may be replaced by halogen, —CN, —NO2 or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is halogen, —OM1-, —SM1-, —CHO, —COOR3—, —CSOR3—, —CSSR3—, —NHR4—, —COX1—, —CSX1—, —OCOX1—, —OCOOR3—, —N═C═O, —CN, —C≡CH, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2, —SO2X1, —SiR2 2X1, —SiR2 2OR3, —SiR2 2OCOR7, —SiR2 2OC(CH3)═CH2, —SiR2 2ON═CR7R8, —SiR2 2NR7R8, or any one of groups shown below:
Figure US20050009982A1-20050113-C00776
in these groups related to Y1, M1 is hydrogen or alkaline metal; R3 is hydrogen, alkaline metal, or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; R4 is hydrogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O— and optional hydrogen may be replaced by halogen, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; X1 is halogen; R5, R6 and X2 are independently hydrogen, halogen, —CN, or alkyl in which the number of carbon atoms is 1 to 10 optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; R7 and R8 are independently alkyl having 1 to 10 carbon atoms; G1 is a trivalent organic group; R9 is hydrogen or alkyl having 1 to 5 carbon atoms; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
2. The compound according to claim 1, wherein in Formula (1), R1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; and Q2 is a group represented by Formula (2);
in Formula (2), the code < represents a bonding point with silicon; l, m, n and p are independently 0, 1, 2 or 3; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in these rings, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional —CH═ may be replaced by —N═; in all rings, optional hydrogen may be replaced by halogen, —CN, —NO2, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is halogen, —OM1-, —SM1-, —CHO, —COOR3—, —CSOR3—, —CSSR3—, —NHR4—, —COX1—, —CSX1—, —OCOX1—, —OCOOR3—, —N═C═O, —CN, —C≡CH, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2, —S0 2X1, or any one of groups shown below:
Figure US20050009982A1-20050113-C00777
in the above groups related to Y1, M1 is hydrogen or alkaline metal; R3 is hydrogen, alkaline metal, or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; R4 is hydrogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen, or phenyl in which optional hydrogen may be replaced by halogen, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; X1 is halogen; R5, R6 and X2 are independently hydrogen, halogen, —CN, or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by halogen; G1 is a trivalent organic group; R9 is hydrogen or alkyl having 1 to 5 carbon atoms; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
3. The compound according to claim 1, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine.
4. The compound according to claim 1, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
5. The compound according to claim 1, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in the above rings, optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the above alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene which has a carbon number of 1 to 20 and in which optional —CH2— may be replaced by —O—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; and Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—.
6. The compound according to claim 1, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in the above rings, optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the above alkyl having 1 to 5 carbon atoms, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z4 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is chlorine, bromine, —OM1-, —SM1-, —CHO, —COOR3—, —NHR4—, —COX1—, —OCOX1—, —N═C═O, —CN, —C≡CH, —CR5═CH2, —CR5═CR6COOR3, —CH═CR5CR6═CH2, —SO2X1, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
Figure US20050009982A1-20050113-C00778
in the above groups related to Y1, M1 is hydrogen or alkaline metal; R3 is hydrogen, alkaline metal, or alkyl having 1 to 5 carbon atoms; R4 is hydrogen, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine, or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; X1 is chlorine or bromine; R5, R6 and X2 are independently hydrogen, fluorine, chlorine, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
7. The compound according to claim 6, wherein R1 is phenyl.
8. The compound according to claim 6, wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
9. The compound according to claim 6, wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent for 1,4-phenylene, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; and Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO—, or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—.
10. The compound according to claim 6, wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5, and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent for 1,4-phenylene, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20, and optional —CH2— which is not adjacent to each other may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and Y1 is —OM1-, —CHO, —COOR3—, —NHR4—, —COX1—, —OCOX1—, —N═C═O, —CR5═CH2, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
Figure US20050009982A1-20050113-C00779
in the above groups related to Y1, M1 is hydrogen, sodium or potassium; R3 is hydrogen, sodium, potassium, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; R4 is hydrogen, phenyl, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; X1 is chlorine or bromine; R5 and X2 are independently hydrogen, fluorine, chlorine, or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2— which is not adjacent to each other may be replaced by —O—, and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
11. The compound according to claim 10, wherein Q1 is alkyl having 1 to 5 carbon atoms, or phenyl.
12. The compound according to claim 10, wherein Q1 is alkyl having 1 to 5 carbon atoms or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine or methyl; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
13. The compound according to claim 10, wherein Q1 is alkyl having 1 to 5 carbon atoms or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine or methyl; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and Y1 is —OM1-, —COOR3—, —NHR4—, —COX1—, —N═C═O, —CR5═CH2, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
Figure US20050009982A1-20050113-C00780
in the above groups related to Y1, M1 is hydrogen, sodium or potassium; R3 is hydrogen, sodium, potassium, methyl or ethyl; R4 is hydrogen, methyl or phenyl; X1 is chlorine or bromine; R5 and X2 are independently hydrogen, fluorine or alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
14. The compound according to claim 13, wherein Q1 is methyl or phenyl.
15. The compound according to claim 13, wherein Q1 is methyl or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene; and Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—.
16. The compound according to claim 13, wherein Q1 is methyl or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene; Z0, Z1, Z2, Z3 and Z4 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and Y1 is —OM1-, —COOR3—, —NHR4—, —COCl—, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
Figure US20050009982A1-20050113-C00781
in the above groups related to Y1, M1 is hydrogen, sodium or potassium; R3 is hydrogen, sodium, potassium, methyl or ethyl; R4 is hydrogen or methyl; X2 is hydrogen, fluorine or methyl; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
17. The compound according to claim 16, wherein Y1 is —OH, —COOR3, —NH2, —COCl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, or any one of groups shown below:
Figure US20050009982A1-20050113-C00782
in the above groups related to Y1, R3 is hydrogen, methyl or ethyl; G1 is a trivalent organic group; R9 is hydrogen, methyl or ethyl; and q is 1 or 0.
18. A polymer having a structural unit represented by Formula (3):
Figure US20050009982A1-20050113-C00783
wherein R1 is phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen; Q1 is hydrogen, halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; and Q3 is a group represented by Formula (4):
Figure US20050009982A1-20050113-C00784
wherein a code < represents a bonding point with silicon; l, m, n and p are independently 0, 1, 2 or 3; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, a condensed ring group having 6 to 10 carbon atoms which is a divalent group, or 1,4-phenylene; in these rings, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional —CH═ may be replaced by —N═; optional hydrogen in all rings may be replaced by halogen, —CN, —NO2 or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2— may be replaced by —O—, —S—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 10 carbon atoms and alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH— or —C≡C—, and optional hydrogen may be replaced by halogen; Z5 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or a group represented by —W1-T1-; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and T1 is —O—, —S—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —OSiR2 2O—, —SiR2 2OSiR2 2—, —CO—, —COO—, —OCO—, —CSO—, —OCS—, —CONR10—, —NR10CO—, —CONR10O—, —ONR10CO—, —OCONR10—, —NR10CONR10—, —NR10COO—, —OCOO—, —CH(OH)CH2—, —CH2CH(OH)—, —CH═CH—, —CH2CR5═CR6CH2—, —C≡C—, —SO2—, —SO2O—, —OSO2—, —SO2S—, —SSO2—, —SO2NR7—, —NR10SO2—, or any one of groups shown below:
Figure US20050009982A1-20050113-C00785
in the groups related to T1, R2 is the same as described above; R10 is hydrogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, alkyl in which the number of carbon atoms is 1 to 10, and optional hydrogen may be replaced by halogen, or phenyl in which optional hydrogen may be replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —CH═CH—or —C≡C—, and optional hydrogen may be replaced by halogen; R5, R6 and X2 are independently hydrogen, halogen, —CN or alkyl in which the number of carbon atoms is 1 to 10, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by halogen; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen or alkyl having 1 to 5 carbon atoms; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
19. The polymer according to claim 18, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine.
20. The polymer according to claim 18, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; and in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
21. The polymer according to claim 18, wherein R1 is phenyl in which optional hydrogen may be replaced by fluorine or chlorine; Q1 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or a condensed ring group having 6 to 10 carbon atoms which is a divalent group; in these rings, optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —NH—, —SiR2 2—, —SiR2 2O—, —OSiR2 2—, —SiR2 2OSiR2 2—, —COO—, —OCO—, —CH═CH— or —C≡C—; R2 is halogen, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 10 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z5 is a single bond, —CH═CH—, —C≡C—, —COO—, —OCO— or a group represented by —W1-T1; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; and T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, —OCOO—, —CH(OH)CH2—, —CH2CH(OH)—, —CH═CH—, —C≡C—, —SO2—, or any one of groups shown below:
Figure US20050009982A1-20050113-C00786
in these groups related to T1, R10 is hydrogen, cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; X2 is hydrogen, fluorine, chlorine or alkyl in which the number of carbon atoms is 1 to 5, optional —CH2—, which is not adjacent to each other, may be replaced by —O— and optional hydrogen may be replaced by fluorine; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen, methyl or ethyl; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
22. The polymer according to claim 21, wherein R1 is phenyl.
23. The polymer according to claim 21, wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl in which the number of carbon atoms is 1 to 5 and optional hydrogen may be replaced by fluorine, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; and in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine.
24. The polymer according to claim 21, wherein R1 is phenyl; Q1 is cyclopentyl, cyclohexyl, alkyl having 1 to 5 carbon atoms, or phenyl in which optional hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene in which optional hydrogen may be replaced by fluorine, chlorine or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms which is a substituent of 1,4-phenylene, optional —CH2—, which is not adjacent to each other, may be replaced by —O—, and optional hydrogen may be replaced by fluorine; Z0, Z1, Z2 and Z3 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; Z5 is a single bond, —COO—, —OCO— or a group represented by —W1-T1; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, or any one of groups shown below:
Figure US20050009982A1-20050113-C00787
in these groups related to T1, R10 is hydrogen, alkyl having 1 to 5 carbon atoms, or phenyl; X2 is hydrogen, fluorine or alkyl having 1 to 5 carbon atoms; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen, methyl or ethyl; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
25. The polymer according to claim 24, wherein Q1 is methyl or phenyl.
26. The polymer according to claim 24, wherein Q1 is methyl or phenyl; A1, A2, A3 and A4 are independently a single bond or 1,4-phenylene; Z0, Z1, Z2 and Z3 are independently a single bond, —COO—, —OCO— or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; Z5 is a single bond, —COO—, —OCO— or a group represented by —W1-T1; W1 is a single bond or alkylene in which the number of carbon atoms is 1 to 20 and optional —CH2—, which is not adjacent to each other, may be replaced by —O—, —COO— or —OCO—; and T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, or any one of groups shown below:
Figure US20050009982A1-20050113-C00788
in these groups related to T1, R10 is hydrogen or methyl; X2 is hydrogen or methyl; G1 is a trivalent organic group; G2 is a part of tricarboxylic acid-derivative's residue or a part of tetracarboxylic acid-derivative's residue; R9 is hydrogen, methyl or ethyl; q is 1 or 0; r is an integer of 0 to 5; and t is an integer of 1 to 5.
27. The polymer according to claim 26, wherein T1 is —O—, —COO—, —OCO—, —CONR10—, —NR10CO—, or any one of groups shown below:
Figure US20050009982A1-20050113-C00789
28. A composition comprising the compound as described in claim 1.
29. A polymer obtained by using at least one of the compounds as described in claim 1.
30. A polymer obtained by using only the compound as described in claim 1.
31. A polymer obtained by using at least one of the compounds as described in claim 1 and at least one of compounds other than the compound as described in claim 1.
32. The polymer according to claim 29, wherein the polymer is polyimide, polyamic acid, polyester, an epoxy resin, polyacrylate or polymethcylate.
33. A composition comprising at least one of the polymers as described in claim 29.
34. A coating agent comprising the polymer as described in claim 29.
35. A varnish composition comprising the polymer as described in claim 29.
36. A thin film formed by using the varnish composition according to claim 35.
37. A multilayer thin film formed by using the varnish composition as described in claim 35 and at least one of compositions of other polymers.
38. A structural matter, wherein a part or the whole of a structural unit thereof is comprised with at least one of the polymer as described in claim 29.
39. A plastic substrate having the thin film as described in claim 36.
40. An optical material having the thin film as described in claim 36.
US10/798,872 2003-03-13 2004-03-12 Compound having silsesquioxane skeleton and its polymer Abandoned US20050009982A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US11/704,253 US7705105B2 (en) 2003-03-13 2007-02-09 Compound having silsequioxane skeleton and its polymer
US12/659,478 US8236917B2 (en) 2003-03-13 2010-03-10 Compound having silsesquioxane skeleton and its polymer
US13/423,548 US8420764B2 (en) 2003-03-13 2012-03-19 Compound having silsesquioxane skeleton and its polymer

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2003-067768 2003-03-13
JP2003067768 2003-03-13
JP2003114221 2003-04-18
JP2003-114221 2003-04-18
JP2004-53219 2004-02-27
JP2004053219A JP4483344B2 (en) 2003-03-13 2004-02-27 Compound having silsesquioxane skeleton and polymer thereof

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/704,253 Continuation US7705105B2 (en) 2003-03-13 2007-02-09 Compound having silsequioxane skeleton and its polymer

Publications (1)

Publication Number Publication Date
US20050009982A1 true US20050009982A1 (en) 2005-01-13

Family

ID=33514532

Family Applications (4)

Application Number Title Priority Date Filing Date
US10/798,872 Abandoned US20050009982A1 (en) 2003-03-13 2004-03-12 Compound having silsesquioxane skeleton and its polymer
US11/704,253 Active 2025-12-17 US7705105B2 (en) 2003-03-13 2007-02-09 Compound having silsequioxane skeleton and its polymer
US12/659,478 Expired - Lifetime US8236917B2 (en) 2003-03-13 2010-03-10 Compound having silsesquioxane skeleton and its polymer
US13/423,548 Expired - Lifetime US8420764B2 (en) 2003-03-13 2012-03-19 Compound having silsesquioxane skeleton and its polymer

Family Applications After (3)

Application Number Title Priority Date Filing Date
US11/704,253 Active 2025-12-17 US7705105B2 (en) 2003-03-13 2007-02-09 Compound having silsequioxane skeleton and its polymer
US12/659,478 Expired - Lifetime US8236917B2 (en) 2003-03-13 2010-03-10 Compound having silsesquioxane skeleton and its polymer
US13/423,548 Expired - Lifetime US8420764B2 (en) 2003-03-13 2012-03-19 Compound having silsesquioxane skeleton and its polymer

Country Status (2)

Country Link
US (4) US20050009982A1 (en)
JP (1) JP4483344B2 (en)

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060175684A1 (en) * 2004-12-28 2006-08-10 Hisao Oikawa Organosilicon compound
US20060194068A1 (en) * 2005-02-28 2006-08-31 Takashi Katoh Organosilicon compound and polymer having a cage-type silicon skeleton
US20060202288A1 (en) * 2005-03-11 2006-09-14 Seiko Epson Corporation Insulator composition, organic semiconductor device, electronic device, and electronic apparatus
US20060204680A1 (en) * 2005-02-28 2006-09-14 Takayuki Hattori Varnish for forming liquid crystal alignment layer and liquid crystal display element using the same
US20060275694A1 (en) * 2005-06-07 2006-12-07 International Business Machines Corporation High resolution silicon-containing resist
US20080051487A1 (en) * 2004-02-25 2008-02-28 Lintec Corporation Process for Producing Polysilsesquioxane Graft Polymer, Pressure-Sensitive Adhesive, and Pressure-Sensitive Adhesive Sheet
US20080071017A1 (en) * 2004-09-10 2008-03-20 Gordon Glenn V Anhydride-Functional Silsesquioxane Resins
US20080103280A1 (en) * 2006-10-26 2008-05-01 Chisso Corporation Ink-jet ink and cured film obtained from same
US20080249271A1 (en) * 2007-03-02 2008-10-09 Lintec Corporation Adhesive containing ladder-type polysilsesquioxane and adhesive sheet
US20090165913A1 (en) * 2007-12-31 2009-07-02 Hergenrother William L Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US20090171014A1 (en) * 2007-12-27 2009-07-02 Hergenrother William L Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US20090326255A1 (en) * 2007-05-23 2009-12-31 Hergenrother William L Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes
US20100071818A1 (en) * 2007-12-31 2010-03-25 Hergenrother William L Amino alkoxy-modified silsesquioxanes in silica-filled rubber with low volatile organic chemical evolution
US20110076501A1 (en) * 2009-09-30 2011-03-31 Federal-Mogul Corporation Substrate and rubber composition and method of making the composition
US20110144235A1 (en) * 2007-05-23 2011-06-16 Hergenrother William L Method For Making Alkoxy-Modified Silsesquioxanes
US20110177252A1 (en) * 2006-01-30 2011-07-21 Ashland Licensing And Intellectual Property Llc Coating compositions for producing transparent super-hydrophobic surfaces
US20110180195A1 (en) * 2005-03-24 2011-07-28 Bridgestone Corporation Compounding silica-reinforced rubber with low volatile organic compound (voc) emission
CN103204872A (en) * 2013-04-14 2013-07-17 吉林大学 Dyhydroxyl cage-type silsesquioxane monomer and preparation method thereof
US8642691B2 (en) 2009-12-28 2014-02-04 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
EP2692776A1 (en) * 2011-03-30 2014-02-05 Asahi Kasei Chemicals Corporation Organopolysiloxane, method for producing same, and curable resin composition containing organopolysiloxane
WO2014128303A1 (en) * 2013-02-25 2014-08-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photoresist having positive resist characteristics, process for photochemical structuring thereof, process for preparing silanes and silica (hetero)poly(co)condensates having positive resist characteristics and silica (hetero)poly(co)condensates
WO2014144986A1 (en) * 2013-03-15 2014-09-18 Olive Medical Corporation Scope sensing in a light controlled environment
US8952108B2 (en) 2009-06-02 2015-02-10 Jnc Corporation Organic silicon compound, thermosetting composition containing said organic silicon compound, and sealing material for optical semiconductor
US8981140B1 (en) * 2010-08-18 2015-03-17 The United States Of America As Represented By The Secretary Of The Air Force Peripherally aromatic silsesquioxanes featuring reactive functionality: synthesis and applications thereof
US9012673B1 (en) 2011-09-21 2015-04-21 The United States Of America As Represented By The Secretary Of The Air Force Synthesis and applications of peripherally asymmetric aryl POSS compounds
CN104804033A (en) * 2015-03-30 2015-07-29 兰州大学 Difluoro POSS (polyhedral oligomeric silsesquioxane) monomer, polymers derived from same as well as preparation method of monomer
US9150596B2 (en) 2014-03-10 2015-10-06 Adam Mickiewicz University Functionalized unsaturated double-decker derivatives of divinylsilsesquioxanes
US9217064B2 (en) 2013-01-24 2015-12-22 The United States Of America, As Represented By The Secretary Of The Air Force Thermosetting resins with enhanced cure characteristics containing organofunctional silane moieties
WO2016001154A1 (en) * 2014-07-01 2016-01-07 Wacker Chemie Ag Method for producing siloxanes from alkali salts of silanols
US9249313B2 (en) 2011-09-21 2016-02-02 The United States Of America As Represented By The Secretary Of The Air Force Synthesis of functional fluorinated polyhedral oligomeric silsesquioxane (F-POSS)
US9394408B2 (en) 2013-08-29 2016-07-19 The United States Of America As Represented By The Secretary Of The Air Force Controlled polymerization of functional fluorinated polyhedral oligomeric silsesquioxane monomers
US9516239B2 (en) 2012-07-26 2016-12-06 DePuy Synthes Products, Inc. YCBCR pulsed illumination scheme in a light deficient environment
CN106279246A (en) * 2015-05-21 2017-01-04 北京化工大学 Furan functionalization double tower type polyhedral oligomeric silsesquioxane and preparation method thereof
CN106279247A (en) * 2015-05-21 2017-01-04 北京化工大学 A kind of furan functionalization cage modle polyhedral oligomeric silsesquioxane and preparation method thereof
US9641815B2 (en) 2013-03-15 2017-05-02 DePuy Synthes Products, Inc. Super resolution and color motion artifact correction in a pulsed color imaging system
US9777913B2 (en) 2013-03-15 2017-10-03 DePuy Synthes Products, Inc. Controlling the integral light energy of a laser pulse
US10075626B2 (en) 2012-07-26 2018-09-11 DePuy Synthes Products, Inc. Camera system with minimal area monolithic CMOS image sensor
US10084944B2 (en) 2014-03-21 2018-09-25 DePuy Synthes Products, Inc. Card edge connector for an imaging sensor
CN110191889A (en) * 2017-01-10 2019-08-30 捷恩智株式会社 Silsesquioxane derivative, its composition and low cure shrinkage cured film with free-radical polymerised functional group
US10517471B2 (en) 2011-05-12 2019-12-31 DePuy Synthes Products, Inc. Pixel array area optimization using stacking scheme for hybrid image sensor with minimal vertical interconnects
US10568496B2 (en) 2012-07-26 2020-02-25 DePuy Synthes Products, Inc. Continuous video in a light deficient environment
US10881272B2 (en) 2013-03-15 2021-01-05 DePuy Synthes Products, Inc. Minimize image sensor I/O and conductor counts in endoscope applications
US10980406B2 (en) 2013-03-15 2021-04-20 DePuy Synthes Products, Inc. Image sensor synchronization without input clock and data transmission clock
US11401440B2 (en) 2014-12-31 2022-08-02 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for adhering steel alloy to rubber

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4306317B2 (en) * 2003-04-24 2009-07-29 チッソ株式会社 Liquid crystal alignment film forming varnish, liquid crystal alignment film, and liquid crystal display element
JP4396139B2 (en) * 2003-05-27 2010-01-13 チッソ株式会社 Polymer having silsesquioxane skeleton and method for forming thin film thereof
JP4742216B2 (en) * 2004-07-08 2011-08-10 Jnc株式会社 Silicon compounds
JP5082258B2 (en) * 2005-02-28 2012-11-28 Jnc株式会社 Organosilicon compound and polymer compound having cage silicon skeleton
JP4775033B2 (en) * 2005-02-28 2011-09-21 Jnc株式会社 Liquid crystal alignment film forming varnish and liquid crystal display element using the same
JP4682644B2 (en) * 2005-02-28 2011-05-11 チッソ株式会社 Varnish for silicone resin molding and silicone resin molding
JP4929687B2 (en) * 2005-11-16 2012-05-09 Jnc株式会社 Photosensitive compound, additive compound, positive photosensitive composition containing these, and display element having film of this positive photosensitive composition
JP2007326988A (en) * 2006-06-09 2007-12-20 Chisso Corp Epoxy resin composition
JP5408597B2 (en) * 2006-06-13 2014-02-05 学校法人 関西大学 Thermosetting polymer composition and cured product thereof
JP5013127B2 (en) * 2007-12-19 2012-08-29 Jnc株式会社 Thermosetting resin composition and use thereof
US20090163652A1 (en) * 2007-12-19 2009-06-25 Chisso Corporation Thermosetting resin composition and use thereof
US8633292B2 (en) * 2009-03-26 2014-01-21 Signet Armorlite Polyurethane-based photochromic optical materials
JP5707607B2 (en) 2009-04-24 2015-04-30 Jnc株式会社 Organosilicon compound and thermosetting resin composition containing the same
JP5773585B2 (en) * 2009-06-29 2015-09-02 日東電工株式会社 Luminescent triaryl
KR101836962B1 (en) 2010-05-18 2018-03-09 제이엔씨 주식회사 New organosilicon compound, thermosetting resin composition containing the organosilicon compound, hardening resin and encapsulation material for optical semiconductor
JP5857039B2 (en) * 2011-03-30 2016-02-10 旭化成ケミカルズ株式会社 Organopolysiloxane, process for producing the same, and curable resin composition containing organopolysiloxane
JP5387638B2 (en) * 2011-09-12 2014-01-15 Jnc株式会社 Epoxy resin composition
CN104447850A (en) * 2014-11-04 2015-03-25 烟台大学 Preparation method for double-splint type divinyl oligomeric silsesquioxane
CN108699340A (en) 2016-03-02 2018-10-23 捷恩智株式会社 The manufacturing method of heat release component composition, heat release component, e-machine and heat release component
WO2023218889A1 (en) * 2022-05-13 2023-11-16 Agc株式会社 Composition, compound, surface treatment agent, article and method for producing article

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6750308B2 (en) * 2001-11-05 2004-06-15 Nippon Steel Chemical Co., Ltd. Silicone resin compositions and molded products of silicone resins
US20040249103A1 (en) * 2001-09-18 2004-12-09 Yoshitaka Morimoto Silsesquioxane derivatives and process for production thereof
US6927270B2 (en) * 2001-06-27 2005-08-09 Hybrid Plastics Llp Process for the functionalization of polyhedral oligomeric silsesquioxanes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6770724B1 (en) * 1998-03-03 2004-08-03 The United States Of America As Represented By The Secretary Of The Air Force Altering of poss rings
US6767930B1 (en) * 2001-09-07 2004-07-27 Steven A. Svejda Polyhedral oligomeric silsesquioxane polyimide composites
JP4259148B2 (en) * 2002-03-28 2009-04-30 チッソ株式会社 Sealing material for LCD panels
JP4479160B2 (en) * 2003-03-11 2010-06-09 チッソ株式会社 Polymers obtained using silsesquioxane derivatives
TWI278473B (en) * 2003-03-12 2007-04-11 Chisso Corp Polymer with the silsesquioxane skeleton in its main chain, method of forming the same, and coating film and membrane of preventing metal ion elution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6927270B2 (en) * 2001-06-27 2005-08-09 Hybrid Plastics Llp Process for the functionalization of polyhedral oligomeric silsesquioxanes
US20040249103A1 (en) * 2001-09-18 2004-12-09 Yoshitaka Morimoto Silsesquioxane derivatives and process for production thereof
US6750308B2 (en) * 2001-11-05 2004-06-15 Nippon Steel Chemical Co., Ltd. Silicone resin compositions and molded products of silicone resins

Cited By (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080051487A1 (en) * 2004-02-25 2008-02-28 Lintec Corporation Process for Producing Polysilsesquioxane Graft Polymer, Pressure-Sensitive Adhesive, and Pressure-Sensitive Adhesive Sheet
US7759406B2 (en) * 2004-02-25 2010-07-20 Lintec Corporation Process for producing polysilsesquioxane graft polymer, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet
US20080071017A1 (en) * 2004-09-10 2008-03-20 Gordon Glenn V Anhydride-Functional Silsesquioxane Resins
EP1849788A1 (en) * 2004-12-28 2007-10-31 Chisso Corporation Organosilicon compound
EP1849787A1 (en) * 2004-12-28 2007-10-31 Chisso Corporation Organosilicon compound
US20060175684A1 (en) * 2004-12-28 2006-08-10 Hisao Oikawa Organosilicon compound
US7375170B2 (en) 2004-12-28 2008-05-20 Chisso Corporation Organosilicon compound
EP1686133A3 (en) * 2004-12-28 2006-08-16 Chisso Corporation Organosilicon compound
US20060204680A1 (en) * 2005-02-28 2006-09-14 Takayuki Hattori Varnish for forming liquid crystal alignment layer and liquid crystal display element using the same
US20060194068A1 (en) * 2005-02-28 2006-08-31 Takashi Katoh Organosilicon compound and polymer having a cage-type silicon skeleton
US7507450B2 (en) * 2005-02-28 2009-03-24 Chisso Corporation Varnish for forming liquid crystal alignment layer and liquid crystal display element using the same
US20060202288A1 (en) * 2005-03-11 2006-09-14 Seiko Epson Corporation Insulator composition, organic semiconductor device, electronic device, and electronic apparatus
US20110180195A1 (en) * 2005-03-24 2011-07-28 Bridgestone Corporation Compounding silica-reinforced rubber with low volatile organic compound (voc) emission
US8288474B2 (en) 2005-03-24 2012-10-16 Bridgestone Corporation Compounding silica-reinforced rubber with low volatile organic compound (VOC) emission
US9403969B2 (en) 2005-03-24 2016-08-02 Bridgestone Corporation Compounding silica-reinforced rubber with low volatile organic compound (VOC) emission
US20060275694A1 (en) * 2005-06-07 2006-12-07 International Business Machines Corporation High resolution silicon-containing resist
US7659050B2 (en) * 2005-06-07 2010-02-09 International Business Machines Corporation High resolution silicon-containing resist
US8338351B2 (en) 2006-01-30 2012-12-25 Ashland Licensing And Intellectual Property, Llc Coating compositions for producing transparent super-hydrophobic surfaces
US20110177252A1 (en) * 2006-01-30 2011-07-21 Ashland Licensing And Intellectual Property Llc Coating compositions for producing transparent super-hydrophobic surfaces
US20080103280A1 (en) * 2006-10-26 2008-05-01 Chisso Corporation Ink-jet ink and cured film obtained from same
US8080604B2 (en) * 2007-03-02 2011-12-20 Lintec Corporation Adhesive containing ladder-type polysilsesquioxane and adhesive sheet
US20080249271A1 (en) * 2007-03-02 2008-10-09 Lintec Corporation Adhesive containing ladder-type polysilsesquioxane and adhesive sheet
US20110144235A1 (en) * 2007-05-23 2011-06-16 Hergenrother William L Method For Making Alkoxy-Modified Silsesquioxanes
US8501895B2 (en) 2007-05-23 2013-08-06 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes
US20090326255A1 (en) * 2007-05-23 2009-12-31 Hergenrother William L Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes
US8822620B2 (en) 2007-05-23 2014-09-02 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes
US8962746B2 (en) * 2007-12-27 2015-02-24 Bridgestone Corporation Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US20090171014A1 (en) * 2007-12-27 2009-07-02 Hergenrother William L Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US9447244B2 (en) 2007-12-27 2016-09-20 Bridgestone Corporation Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US8097674B2 (en) 2007-12-31 2012-01-17 Bridgestone Corporation Amino alkoxy-modified silsesquioxanes in silica-filled rubber with low volatile organic chemical evolution
US8513371B2 (en) 2007-12-31 2013-08-20 Bridgestone Corporation Amino alkoxy-modified silsesquioxanes and method of preparation
US20090165913A1 (en) * 2007-12-31 2009-07-02 Hergenrother William L Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US8794282B2 (en) 2007-12-31 2014-08-05 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US8809481B2 (en) 2007-12-31 2014-08-19 Bridgestone Corporation Amino alkoxy-modified silsesquioxanes and method of preparation
US20100071818A1 (en) * 2007-12-31 2010-03-25 Hergenrother William L Amino alkoxy-modified silsesquioxanes in silica-filled rubber with low volatile organic chemical evolution
US9365700B2 (en) 2007-12-31 2016-06-14 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US8952108B2 (en) 2009-06-02 2015-02-10 Jnc Corporation Organic silicon compound, thermosetting composition containing said organic silicon compound, and sealing material for optical semiconductor
US9382451B2 (en) 2009-09-30 2016-07-05 Federal-Mogul Corporation Substrate and rubber composition and method of making the composition
US8182646B2 (en) * 2009-09-30 2012-05-22 Federal-Mogul Corporation Substrate and rubber composition and method of making the composition
US20110076501A1 (en) * 2009-09-30 2011-03-31 Federal-Mogul Corporation Substrate and rubber composition and method of making the composition
US8642691B2 (en) 2009-12-28 2014-02-04 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US8981140B1 (en) * 2010-08-18 2015-03-17 The United States Of America As Represented By The Secretary Of The Air Force Peripherally aromatic silsesquioxanes featuring reactive functionality: synthesis and applications thereof
EP2692776A4 (en) * 2011-03-30 2014-08-20 Asahi Kasei Chemicals Corp Organopolysiloxane, method for producing same, and curable resin composition containing organopolysiloxane
US9243007B2 (en) 2011-03-30 2016-01-26 Asahi Kasei Chemicals Corporation Organopolysiloxane, method for producing the same, and curable resin composition containing the organopolysiloxane
EP2692776A1 (en) * 2011-03-30 2014-02-05 Asahi Kasei Chemicals Corporation Organopolysiloxane, method for producing same, and curable resin composition containing organopolysiloxane
US11179029B2 (en) 2011-05-12 2021-11-23 DePuy Synthes Products, Inc. Image sensor with tolerance optimizing interconnects
US11109750B2 (en) 2011-05-12 2021-09-07 DePuy Synthes Products, Inc. Pixel array area optimization using stacking scheme for hybrid image sensor with minimal vertical interconnects
US11026565B2 (en) 2011-05-12 2021-06-08 DePuy Synthes Products, Inc. Image sensor for endoscopic use
US10863894B2 (en) 2011-05-12 2020-12-15 DePuy Synthes Products, Inc. System and method for sub-column parallel digitizers for hybrid stacked image sensor using vertical interconnects
US10709319B2 (en) 2011-05-12 2020-07-14 DePuy Synthes Products, Inc. System and method for sub-column parallel digitizers for hybrid stacked image sensor using vertical interconnects
US10517471B2 (en) 2011-05-12 2019-12-31 DePuy Synthes Products, Inc. Pixel array area optimization using stacking scheme for hybrid image sensor with minimal vertical interconnects
US11432715B2 (en) 2011-05-12 2022-09-06 DePuy Synthes Products, Inc. System and method for sub-column parallel digitizers for hybrid stacked image sensor using vertical interconnects
US11682682B2 (en) 2011-05-12 2023-06-20 DePuy Synthes Products, Inc. Pixel array area optimization using stacking scheme for hybrid image sensor with minimal vertical interconnects
US10537234B2 (en) 2011-05-12 2020-01-21 DePuy Synthes Products, Inc. Image sensor with tolerance optimizing interconnects
US11848337B2 (en) 2011-05-12 2023-12-19 DePuy Synthes Products, Inc. Image sensor
US9249313B2 (en) 2011-09-21 2016-02-02 The United States Of America As Represented By The Secretary Of The Air Force Synthesis of functional fluorinated polyhedral oligomeric silsesquioxane (F-POSS)
US9012673B1 (en) 2011-09-21 2015-04-21 The United States Of America As Represented By The Secretary Of The Air Force Synthesis and applications of peripherally asymmetric aryl POSS compounds
US11089192B2 (en) 2012-07-26 2021-08-10 DePuy Synthes Products, Inc. Camera system with minimal area monolithic CMOS image sensor
US11766175B2 (en) 2012-07-26 2023-09-26 DePuy Synthes Products, Inc. Camera system with minimal area monolithic CMOS image sensor
US11863878B2 (en) 2012-07-26 2024-01-02 DePuy Synthes Products, Inc. YCBCR pulsed illumination scheme in a light deficient environment
US9762879B2 (en) 2012-07-26 2017-09-12 DePuy Synthes Products, Inc. YCbCr pulsed illumination scheme in a light deficient environment
US11083367B2 (en) 2012-07-26 2021-08-10 DePuy Synthes Products, Inc. Continuous video in a light deficient environment
US9516239B2 (en) 2012-07-26 2016-12-06 DePuy Synthes Products, Inc. YCBCR pulsed illumination scheme in a light deficient environment
US10075626B2 (en) 2012-07-26 2018-09-11 DePuy Synthes Products, Inc. Camera system with minimal area monolithic CMOS image sensor
US11070779B2 (en) 2012-07-26 2021-07-20 DePuy Synthes Products, Inc. YCBCR pulsed illumination scheme in a light deficient environment
US10785461B2 (en) 2012-07-26 2020-09-22 DePuy Synthes Products, Inc. YCbCr pulsed illumination scheme in a light deficient environment
US10701254B2 (en) 2012-07-26 2020-06-30 DePuy Synthes Products, Inc. Camera system with minimal area monolithic CMOS image sensor
US10277875B2 (en) 2012-07-26 2019-04-30 DePuy Synthes Products, Inc. YCBCR pulsed illumination scheme in a light deficient environment
US10568496B2 (en) 2012-07-26 2020-02-25 DePuy Synthes Products, Inc. Continuous video in a light deficient environment
US9217064B2 (en) 2013-01-24 2015-12-22 The United States Of America, As Represented By The Secretary Of The Air Force Thermosetting resins with enhanced cure characteristics containing organofunctional silane moieties
WO2014128303A1 (en) * 2013-02-25 2014-08-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photoresist having positive resist characteristics, process for photochemical structuring thereof, process for preparing silanes and silica (hetero)poly(co)condensates having positive resist characteristics and silica (hetero)poly(co)condensates
US9625817B2 (en) 2013-02-25 2017-04-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photoresist with positive-resist behaviour, method for photochemical structuring thereof, method for the production of silanes and of silicic acid (hetero)poly(co)condensates with positive-resist behaviour and also silicic acid (hetero)poly(co)condensates
US9777913B2 (en) 2013-03-15 2017-10-03 DePuy Synthes Products, Inc. Controlling the integral light energy of a laser pulse
US11903564B2 (en) 2013-03-15 2024-02-20 DePuy Synthes Products, Inc. Image sensor synchronization without input clock and data transmission clock
US10670248B2 (en) 2013-03-15 2020-06-02 DePuy Synthes Products, Inc. Controlling the integral light energy of a laser pulse
US10205877B2 (en) 2013-03-15 2019-02-12 DePuy Synthes Products, Inc. Super resolution and color motion artifact correction in a pulsed color imaging system
US9641815B2 (en) 2013-03-15 2017-05-02 DePuy Synthes Products, Inc. Super resolution and color motion artifact correction in a pulsed color imaging system
US10881272B2 (en) 2013-03-15 2021-01-05 DePuy Synthes Products, Inc. Minimize image sensor I/O and conductor counts in endoscope applications
WO2014144986A1 (en) * 2013-03-15 2014-09-18 Olive Medical Corporation Scope sensing in a light controlled environment
US10917562B2 (en) 2013-03-15 2021-02-09 DePuy Synthes Products, Inc. Super resolution and color motion artifact correction in a pulsed color imaging system
US10980406B2 (en) 2013-03-15 2021-04-20 DePuy Synthes Products, Inc. Image sensor synchronization without input clock and data transmission clock
US11344189B2 (en) 2013-03-15 2022-05-31 DePuy Synthes Products, Inc. Image sensor synchronization without input clock and data transmission clock
US11253139B2 (en) 2013-03-15 2022-02-22 DePuy Synthes Products, Inc. Minimize image sensor I/O and conductor counts in endoscope applications
US11185213B2 (en) 2013-03-15 2021-11-30 DePuy Synthes Products, Inc. Scope sensing in a light controlled environment
US11674677B2 (en) 2013-03-15 2023-06-13 DePuy Synthes Products, Inc. Controlling the integral light energy of a laser pulse
US10251530B2 (en) 2013-03-15 2019-04-09 DePuy Synthes Products, Inc. Scope sensing in a light controlled environment
CN103204872A (en) * 2013-04-14 2013-07-17 吉林大学 Dyhydroxyl cage-type silsesquioxane monomer and preparation method thereof
US9394408B2 (en) 2013-08-29 2016-07-19 The United States Of America As Represented By The Secretary Of The Air Force Controlled polymerization of functional fluorinated polyhedral oligomeric silsesquioxane monomers
US9150596B2 (en) 2014-03-10 2015-10-06 Adam Mickiewicz University Functionalized unsaturated double-decker derivatives of divinylsilsesquioxanes
US10911649B2 (en) 2014-03-21 2021-02-02 DePuy Synthes Products, Inc. Card edge connector for an imaging sensor
US11438490B2 (en) 2014-03-21 2022-09-06 DePuy Synthes Products, Inc. Card edge connector for an imaging sensor
US10084944B2 (en) 2014-03-21 2018-09-25 DePuy Synthes Products, Inc. Card edge connector for an imaging sensor
WO2016001154A1 (en) * 2014-07-01 2016-01-07 Wacker Chemie Ag Method for producing siloxanes from alkali salts of silanols
US10017526B2 (en) 2014-07-01 2018-07-10 Wacker Chemie Ag Method for producing siloxanes from alkali salts of silanols
US11401440B2 (en) 2014-12-31 2022-08-02 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for adhering steel alloy to rubber
CN104804033A (en) * 2015-03-30 2015-07-29 兰州大学 Difluoro POSS (polyhedral oligomeric silsesquioxane) monomer, polymers derived from same as well as preparation method of monomer
CN106279246A (en) * 2015-05-21 2017-01-04 北京化工大学 Furan functionalization double tower type polyhedral oligomeric silsesquioxane and preparation method thereof
CN106279247A (en) * 2015-05-21 2017-01-04 北京化工大学 A kind of furan functionalization cage modle polyhedral oligomeric silsesquioxane and preparation method thereof
CN110191889A (en) * 2017-01-10 2019-08-30 捷恩智株式会社 Silsesquioxane derivative, its composition and low cure shrinkage cured film with free-radical polymerised functional group

Also Published As

Publication number Publication date
JP2004331647A (en) 2004-11-25
US8420764B2 (en) 2013-04-16
US8236917B2 (en) 2012-08-07
US7705105B2 (en) 2010-04-27
JP4483344B2 (en) 2010-06-16
US20100240855A1 (en) 2010-09-23
US20120178894A1 (en) 2012-07-12
US20070190344A1 (en) 2007-08-16

Similar Documents

Publication Publication Date Title
US7705105B2 (en) Compound having silsequioxane skeleton and its polymer
US10563091B2 (en) Curable composition, and moulded body
CN109575289B (en) Polyorganosilsesquioxane, hard coat film, adhesive sheet and laminate
US6787625B2 (en) Polyorganosilsesquioxane and process for preparing the same
KR101596880B1 (en) Epoxy Compound Having Alkoxysilyl Group, Preparing Method Thereof, Composition Comprising the Same and Cured Product and Use Thereof
CN110494466B (en) Curable composition, cured product, and hard coat film
CN107683299B (en) Curable composition, adhesive sheet, cured product, laminate, and method and device for producing adhesive sheet
JP6820646B2 (en) Bisphenols having a fluorene skeleton and methods for producing them, and polyarylate resins, (meth) acrylate compounds and epoxy resins derived from the bisphenols.
TWI691574B (en) Method for producing curd product, curd product, and a laminate containing the cured product
JP5082258B2 (en) Organosilicon compound and polymer compound having cage silicon skeleton
KR20190082944A (en) Hard coating film
CN105873983B (en) It being capable of the molding silsesquioxane of hot-melt extrusion technology, high transparency and high heat resistance plastic, transparent substrate and its manufacturing method using it
US20180362803A1 (en) Moulded body
KR20190138652A (en) Laminate
CN107873033B (en) High RI siloxane monomers, polymerization and use thereof
KR20200057724A (en) Plastic lenses
Harada et al. Synthesis and improved mechanical properties of twin‐mesogenic epoxy thermosets using siloxane spacers with different lengths
KR20200007893A (en) Curable Compositions, Adhesive Sheets, Cured Products, Laminates and Devices for Adhesives
WO2006077862A1 (en) Epoxy resin composition and optical material using same
KR101637399B1 (en) Polyorganosiloxane compound and copolycarbonate resin containing the same
WO2020175338A1 (en) Polyorganosilsesquioxane and hard coat layer-forming composition
CA1310329C (en) Substituted aromatic silane compounds and method for preparation of same
TWI656028B (en) Surface-reinforced transparent substrate and method of manufacturing same
WO2020230786A1 (en) Curable composition and cured product of same
TW561162B (en) Epoxy resin composition for encapsulation of optical semiconductor device

Legal Events

Date Code Title Description
AS Assignment

Owner name: CHISSO CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:INAGAKI, JYUN-ICHI;SASADA, YASUYUKI;KATO, TAKASHI;REEL/FRAME:015608/0392

Effective date: 20040324

Owner name: CHISSO PETROCHEMICAL CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:INAGAKI, JYUN-ICHI;SASADA, YASUYUKI;KATO, TAKASHI;REEL/FRAME:015608/0392

Effective date: 20040324

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION