WO2015163681A1 - Composition de résine pour substrat en plastique transparent - Google Patents

Composition de résine pour substrat en plastique transparent Download PDF

Info

Publication number
WO2015163681A1
WO2015163681A1 PCT/KR2015/003990 KR2015003990W WO2015163681A1 WO 2015163681 A1 WO2015163681 A1 WO 2015163681A1 KR 2015003990 W KR2015003990 W KR 2015003990W WO 2015163681 A1 WO2015163681 A1 WO 2015163681A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
unsubstituted
transparent plastic
resin composition
group
Prior art date
Application number
PCT/KR2015/003990
Other languages
English (en)
Korean (ko)
Inventor
차혁진
박진규
Original Assignee
(주)휴넷플러스
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 (주)휴넷플러스 filed Critical (주)휴넷플러스
Priority to CN201580021114.7A priority Critical patent/CN106232684B/zh
Publication of WO2015163681A1 publication Critical patent/WO2015163681A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the technology disclosed in the present specification relates to a resin composition for a transparent plastic substrate, and a resin composition suitable for producing a transparent plastic substrate with a substrate having excellent flexibility and excellent mechanical properties.
  • glass substrates used in displays are useful in the display industry because of their high transparency, transparency, pencil hardness of more than 7H, antifouling properties, and chemical resistance, but they can be easily broken when impact is applied. It is difficult to implement flexible flexible displays.
  • the problem to be solved by the present invention is to provide a resin composition suitable for producing a transparent plastic substrate having flexibility, high heat resistance, high permeability, high hardness, scratch resistance and impact resistance properties.
  • a resin composition for a transparent plastic substrate comprising (A) a silsesquioxane resin represented by the following formula (1), and (B) a photopolymerization initiator or a thermosetting agent.
  • R 1 , R 2 and R 3 are each independently a single bond, substituted or unsubstituted C 1 -C 6 alkylene or substituted or unsubstituted C 1 -C 6 -O-alkylene or substituted or unsubstituted C 2 -C 12 alkylene-O-alkylene,
  • R 1a is a substituted or unsubstituted C 1 -C 12 alkyl or a substituted or unsubstituted C 3 -C 18 hydrocarbon ring group
  • R 2a is a substituted or unsubstituted C 2 -C 12 hydrocarbon group having an ethylene bond
  • R 3a is a substituted or unsubstituted C 2 -C 10 cyclic ether containing group
  • l is an integer from 2 to 500
  • m and n are integers from 0 to 500
  • at least one of m and n is not zero.
  • a transparent plastic film having a thickness in the range of 5 ⁇ m to 5,000 ⁇ m formed from the above-described composition.
  • a substrate including the above-mentioned transparent plastic film is provided.
  • the resin composition for transparent plastic substrates according to the present invention has high heat resistance, high permeability, flexibility, and exhibits hardness, scratch resistance, and impact resistance. Therefore, the present invention can be applied to various hard coating films, display protection windows, and substrates for flexible devices.
  • alkyl includes straight, branched or cyclic hydrocarbon radicals
  • alkylene refers to a divalent radical derived from alkyl.
  • alkylene includes methylene, ethylene, isobutylene, cyclohexylene, cyclopentylethylene, 2-propenylene, 3-butynylene and the like.
  • heteroalkyl by itself or in combination with other terms, unless defined otherwise, means one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si and S Stable straight or branched chain or cyclic hydrocarbon radicals or combinations thereof, wherein the nitrogen, phosphorus and sulfur atoms can be optionally oxidized and the nitrogen heteroatoms can be optionally quaternized.
  • heteroalkylene means a divalent radical derived from heteroalkyl.
  • aryl means a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (1 to 3 rings) fused or covalently bonded together unless otherwise specified.
  • heteroaryl means an aryl group (or ring) comprising 1 to 4 heteroatoms selected from N, O and S (in each separate ring in the case of multiple rings), and nitrogen and sulfur atoms Optionally oxidized and the nitrogen atom (s) are optionally quaternized. Heteroaryl groups can be attached to the rest of the molecule via carbon or heteroatoms.
  • Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2- Imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5 Isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4- Pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, furinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinoly
  • arylene and heteroarylene refer to divalent radicals of aryl and heteroaryl, respectively.
  • Substituted in the expression "substituted or unsubstituted” as used herein means that one or more hydrogen atoms in the hydrocarbon are each replaced with the same or different substituents, independently of one another.
  • -NR c R c is meant to include -NH 2 , -NH-alkyl, N-pyrrolidinyl and N-morpholinyl.
  • substituted alkyl is -alkylene-O-alkyl, -alkylene-heteroaryl, -alkylene-cycloheteroalkyl, -alkylene-C (O) OR b , -alkylene-C (O ) NR b R b , and —CH 2 —CH 2 —C (O) —CH 3 .
  • the one or more substituents may be selected with the atoms to which they are attached to form a cyclic ring comprising cycloalkyl and cycloheteroalkyl.
  • the resin composition for transparent plastic substrates comprises (A) a silsesquioxane resin, (B) a photopolymerization initiator or a thermosetting agent, (C) a polyfunctional compound having an ethylenically unsaturated bond, (D) toughening agent, and (E) It may include a (meth) acrylic compound or an organic solvent for viscosity adjustment, (F) additive.
  • the resin composition for transparent plastic substrates may further include (G) inorganic particles.
  • the silsesquioxane resin of the present invention is a ladder-like silsesquioxane polymer represented by the following formula (1).
  • the silsesquioxane resin has a silsesquioxane structure having a main chain, and may include photosensitive functional groups such as an allyl group, a vinyl group, an acryl group, and the like which can be used in a photocurable composition.
  • the silsesquioxane resin may have a silsesquioxane structure and include a cyclic ether group such as an epoxy group capable of thermosetting, and thus may be used in a thermosetting composition.
  • the silsesquioxane resin is a polymer resin that may include various functional groups to have specific physical properties.
  • the silsesquioxane resin as is well known, has a structure similar to glass in terms of chemical structure, and may exhibit excellent properties such as high heat resistance, high permeability, high hardness, and scratch resistance that the glass may have.
  • R 1 , R 2 and R 3 are each independently a single bond, substituted or unsubstituted C 1 -C 6 alkylene or substituted or unsubstituted C 1 -C 6 -O-alkylene or substituted or unsubstituted C 2 -C 12 alkylene-O-alkylene.
  • R 1a may be substituted or unsubstituted C 1 -C 12 alkyl or substituted or unsubstituted C 3 -C 18 hydrocarbon ring group.
  • the repeating unit (I) including the R 1 and R 1a may be one kind, but preferably, a plurality of different repeating units may be combined to adjust desired physical properties.
  • the polysilsesquioxane polymer may simultaneously contain three kinds of repeating units (I): (I) ', (I)''and(I)''', and three kinds of repeating.
  • Each of R 1 and R 1a belonging to a unit may be the same or different from each other.
  • the substituted or unsubstituted C 1 -C 12 alkyl may be, for example, methyl, ethyl, propyl, butyl, hexyl or octyl.
  • the substituted or unsubstituted C 3 -C 18 hydrocarbon ring group may be cycloalkyl, bicycloalkyl, aryl or heteroaryl.
  • heteroatoms such as N, P, O, or S or a double bond may be included in the structure of the hydrocarbon ring group.
  • the substituted or unsubstituted C 1 -C 12 alkyl group allows the polysilsesquioxane polymer to have a moderate flexibility and glass transition temperature.
  • the substituted or unsubstituted C 3 -C 18 hydrocarbon ring group increases the heat resistance and hardness of the photosensitive resin composition.
  • R 2a is a photosensitive functional group capable of causing a curing reaction by exposure in the presence of a photoinitiator and is a substituted or unsubstituted C 2 -C 12 hydrocarbon group having an ethylene bond.
  • the photosensitive functional group may be a hydrocarbon group containing 3-methacryl, 3-acryl, vinyl or allyl groups at the end, and specific examples thereof include 3-methacryloxypropyl, 3-acryloxypropyl, 3-methacryl, 3 -Acrylic, vinyl or allyl group.
  • R 3a is a functional group capable of causing a curing reaction with a thermosetting agent by heat, and is a substituted or unsubstituted C 2 -C 10 cyclic ether containing group.
  • the substituted or unsubstituted C 2 -C 10 cyclic ether-containing group may be a hydrocarbon group containing a glycidyl, 2- (3,4-epoxycyclohexyl) or oxetan-3-yl group as a terminal, and specific examples For example, 3-glycidoxypropyl, 3-glycidyl, 2- (3,4-epoxycyclohexyl) ethyl, 3-ethyl-3- [3-propoxymethyl] oxetanyl or oxetane-3 -There is a monomethyl group.
  • the substituted or unsubstituted C 2 -C 10 cyclic ether containing group may contain an epoxy group.
  • l is an integer of 2 to 500
  • m and n are each an integer of 0 to 500, at least one of m and n is not zero.
  • the repeating unit (I) may occupy 1 to 90 mol%, the repeating unit (II) 0 to 30 mol%, and the repeating unit (III) may occupy 0 to 30 mol%.
  • the silsesquioxane resin When the silsesquioxane resin is applied to the transparent plastic flexible substrate in the above range, it may have excellent physical properties.
  • the weight average molecular weights of the said silsesquioxane resin are 2,000-100,000.
  • the average molecular weight is less than 2,000, it is difficult to form a plastic substrate, and when the molecular weight exceeds 100,000, a high viscosity may cause a process problem when forming the plastic substrate.
  • the polydispersity of the silsesquioxane resin is preferably 1 to 10. If the average dispersion exceeds 10, problems may occur in substrate flatness.
  • the silsesquioxane resin when m is not 0 and n is 0, that is, when the repeating unit (II) is present and there is no repeating unit (III), the silsesquioxane resin may be used in the photocurable resin composition. Meanwhile, when m is 0 in Formula 1 and n is not 0, that is, when there is no repeating unit (II) and there is a repeating unit (III), the silsesquioxane resin may be used in a thermosetting resin composition. In some cases, repeating unit (II) and repeating unit (III) may be present at the same time. In this case, heat resistance of the substrate may be improved through thermal curing after photocuring.
  • the silsesquioxane resin When the silsesquioxane resin is used in a resin composition for forming a transparent plastic substrate, the silsesquioxane resin preferably contains 5 to 80% by weight of the total composition. When the content of the silsesquioxane resin is less than the above range, it is difficult to form the thickness of the substrate, and when the content exceeds the above range, the viscosity may be high, so that the substrate forming process may be difficult.
  • a photoinitiator means the component which generate
  • photopolymerization initiator examples include oxime ester compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, alpha-diketone compounds, polynuclear quinone compounds, phosphine compounds, and tria A true compound, etc. are mentioned. Among these, an acetophenone type compound or an oxime ester type compound is preferable.
  • oxime ester compound examples include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) and 1,3-octanedione-1 [(4-phenylthio) phenyl] 2-benzoyl-oxime and the like.
  • acetophenone type compound an alpha-hydroxy ketone type compound, an alpha-amino ketone type compound, and a compound other than these are mentioned, for example.
  • alpha-hydroxyketone compound examples include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, etc. Specific examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like. Can be mentioned. These acetophenone type compounds can be used individually or in mixture of 2 or more types. By using these acetophenone compounds, it is possible to further improve the strength of the thin film.
  • biimidazole-based compound examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2 '-Biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 ' -Tetraphenyl-1,2
  • 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4-difluorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferable, and particularly preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.
  • the content of the photopolymerization initiator is 1 to 30 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the silsesquioxane resin.
  • the content of the photopolymerization initiator is less than the above range, hardening may not occur, and when it exceeds the above range, precipitation may occur due to a decrease in solubility after curing.
  • thermosetting agent of this invention plays a role which hardens the compound which has an epoxy group.
  • curing agent for epoxy resins can be used.
  • the thermosetting agent is not particularly limited as long as it can react with epoxy resin. Usually, it is a compound which has a phenolic hydroxyl group, the compound which has an acid anhydride, or an amine.
  • Examples of the compound having two or more phenolic hydroxyl groups in the molecule include phenol novolak resins, cresol novolak resins, phenol aralkyl resins, novolak resins synthesized from bisphenol A and resorcinol, and tris (hydroxyphenyl). Methane, dihydrobiphenyl, and polyhydrogen phenol compounds.
  • Examples of compounds having acid anhydrides include maleic anhydride, phthalic anhydride, and pyromellitic anhydride.
  • Examples of amines include aromatic amines, ie metaphenylenediamine, di (aminophenyl) methane, and diaminodiphenylsulfone.
  • curing agent contains a latent amine hardening component.
  • the latent curing agent means that the curing component does not react at room temperature, but reacts rapidly to cause curing once the onset temperature of the epoxy curing reaction is exceeded. This allows the structural adhesive to be readily applied at room temperature or by moderate heating without activating the curing agent.
  • Suitable latent amines include, for example, guanidine, substituted guanidines (e.g., methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobaiguanidine, dimethylisobaiguanidine, tetramethylisobaiguanidine, hexa Methylisobaiguanidine, heptamethylisobaiguanidine and dicyandiamide), melamine resins, guanamine derivatives (such as alkylated benzoguanamine resins, benzoguanamine resins and methoxymethylethoxymethylbenzoguanamine), cyclic 3 Primary amines, aromatic amines, substituted ureas (eg, p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea (phenuron), 3,4-di Chlorophenyl-N, N-di
  • latent amines include Adeka Hadner series (EH-3615, EH-3842 and EH-4342S) available from Adeka Corp. of Japan and Aji available from Ajinomoto Corp. of Japan. Cure series (PN-40J) is included.
  • the usage-amount (content) of a thermosetting agent is not specifically limited, It is 50-200 weight part with respect to 100 weight part of compounds which have an epoxy group contained in the resin composition of this invention, Preferably it is 100-145 weight part. More specifically, it is preferable to use in the ratio used as 0.5-1.5 equivalent with respect to 1 equivalent of epoxy groups in the compound which has all the epoxy groups contained in the resin composition of this invention.
  • the usage-amount of a thermosetting agent is less than the said range, hardening becomes inadequate and there exists a tendency for the toughness of hardened
  • the usage-amount of a thermosetting agent exceeds the said range, hardened
  • Multifunctional compounds having ethylenically unsaturated bonds are generally crosslinkable units having at least two ethylenic double bonds.
  • Examples of the polyfunctional compound having an ethylenically unsaturated bond include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , Tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacryl
  • the polyfunctional compound is preferably 10 to 200 parts by weight, preferably 30 to 150 parts by weight based on 100 parts by weight of the silsesquioxane resin.
  • the content of the multifunctional compound is less than the above range, it may be impossible to use it as a substrate due to the low degree of curing with the photosensitive resin, and when it exceeds the above range, there is a concern that the physical properties of the photosensitive resin may be lowered.
  • Toughening agents are intended to enhance the toughness of the cured composition.
  • Typical toughening agents include core-shell polymers, butadiene-nitrile rubbers, acrylic polymers and copolymers.
  • Cores of core-shell polymer toughening agents are often prepared from butadiene polymers or copolymers, styrene polymers or copolymers, acrylonitrile polymers or copolymers, acrylate polymers or copolymers, or combinations thereof. These polymers or copolymers may or may not be crosslinked. Some exemplary shells are polymethylmethacrylates that are crosslinked or not crosslinked. Another exemplary shell is a butadiene-styrene copolymer that is crosslinked or not crosslinked.
  • Shells of core-shell polymer toughening agents are often formed from styrene polymers or copolymers, methacrylate polymers or copolymers, acrylonitrile polymers or copolymers, or combinations thereof.
  • the shell may be further functionalized with an epoxy group, acidic group or acetoacetoxy group.
  • Functionalization of the shell can be achieved, for example, by copolymerization with glycidylmethacrylate or acrylic acid or by reaction of hydroxyl groups with alkyl acetoacetoxy such as tert-butyl acetoacetoxy. The addition of these functional groups can cause the shell to crosslink into the polymer matrix.
  • Suitable core-shell polymers often have an average particle size of at least 10 nanometers, at least 20 nanometers, at least 50 nanometers, at least 100 nanometers, at least 150 nanometers or at least 200 nanometers.
  • the average particle size can be up to 400 nanometers, up to 500 nanometers, up to 750 nanometers, or up to 1000 nanometers.
  • the average particle size can be, for example, in the range of 10 to 1000 nanometers, in the range of 50 to 1000 nanometers, in the range of 100 to 750 nanometers, or in the range of 150 to 500 nanometers.
  • a modified epoxy resin is used, and a modified epoxy resin is frequently used in adhesives or structural materials requiring toughness of resins when thermosetting the resin, and the reason is hardened silses. Since quinoxane resin has low brittleness, the quinoxane resin has a weak disadvantage in impact or vibration, and therefore, its use as a structural material requiring toughness is limited.
  • modified epoxy resin due to the high crosslinking density of the epoxy curing group of silsesquioxane.
  • the high crosslinking density shows many advantages and excellent strengths of the silsesquioxane resin, but on the contrary, it is weak in brittleness.
  • the height requires a modified epoxy resin.
  • the most representative examples are the method of imparting soft segments to the backbone of the curing agent and epoxy resin and the method of reducing the crosslinking density due to reactive additives in the crosslinking reaction.
  • CBN Carboxyl terminated butadiene acrylonitrile
  • ABN acrylonitrile
  • CR chloroprene rubber
  • the content of the toughening agent is preferably used 5 to 30 parts by weight with respect to 100 parts by weight of the silsesquioxane resin, and less than 5 parts by weight of the effect of improving the physical properties is insignificant. The balance of scratchability and workability may be lowered.
  • the viscosity property and the adhesive property of the composition can be controlled.
  • 15-70 weight part of the said (meth) acrylic-type compound for viscosity adjustment is contained with respect to 100 weight part of said silsesquioxane resins. If the content of the viscosity-controlling (meth) acrylic compound is less than the above range, the viscosity may be too high, and if it exceeds the above range, the physical properties of the formed substrate may be reduced.
  • the organic solvent used in the present resin composition is not particularly limited as long as the polymer can be dissolved in organic solvents such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general photopolymerization compositions.
  • organic solvents such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general photopolymerization compositions.
  • organic solvents such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general photopolymerization compositions.
  • organic solvents such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general photopolymerization compositions.
  • organic solvents such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general photopolymerization compositions.
  • the content of the organic solvent is 0 to 95 parts by weight, preferably 10 to 90 parts by weight based on 100 parts by weight of the total composition. If the content of the solvent exceeds the above range it may not be possible to obtain a thin film of the desired thickness after coating.
  • the resin composition for the transparent plastic substrate according to the embodiment of the present invention may further include at least one additive selected from the group consisting of antioxidants, light stabilizers, and surfactants.
  • the surfactant is a component having an effect of improving the coating property, coating property, uniformity and stain removal on the substrate, and at least one selected from the group consisting of fluorine-based surfactants, silicone-based surfactants and non-ionic surfactants. Can be used interchangeably.
  • the antioxidant that can be used include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1222 (Shibagai Corporation, Japan) and the like.
  • the light stabilizer may include Tinuvin 292, Tinuvin 144, Tinuvin 622LD (Shibagai Corporation, Japan), sanol LS-770, sanol LS-765, sanol LS-292, sanol LS-744 (Sankyo, Japan), and the like. have.
  • the additive may be changed according to the user's selection within the range that does not change the physical properties required by the entire photosensitive resin composition, and is usually 0.001 to 2 parts by weight, preferably 0.01 to 1 based on 100 parts by weight of the silsesquioxane resin. Parts by weight may be used.
  • the above-described resin composition may further include (G) inorganic particles as needed in addition to the components (A) to (F).
  • the inorganic particles serve to improve surface hardness and wear resistance, and for example, silica particles, alumina particles, titania particles, zirconia particles, antimony oxide particles or zinc oxide may be used.
  • the inorganic particles may be used 0.1 to 15 parts by weight based on 100 parts by weight of the silsesquioxane resin. If it is less than the above range, the hardness improvement is not sufficient, and if it exceeds the above range, the transmittance decrease or haze may be generated.
  • the resin composition for a transparent plastic substrate according to the present invention has high heat resistance, high permeability, flexibility, and shows hardness, scratch resistance, and impact resistance, it is possible to obtain a substrate having excellent physical properties.
  • Using the resin composition according to an embodiment of the present invention can form a thick plastic substrate.
  • the manner of thick film formation is not particularly limited, and methods known in the art may be used. For example, spin coating, dip coating, roll coating, screen coating, flow coating, screen pring, drop casting coating method such as casting) can be used.
  • the solvent is volatilized by applying vacuum, infrared rays or heat.
  • the exposure process then uses excimer lasers, far ultraviolet rays, ultraviolet rays, visible light, electron beams, X-rays or g-rays (wavelength 436 nm), i-rays (365 nm wavelength), h-rays (wavelength 405 nm) or mixed rays thereof.
  • Investigate using Exposure can use exposure methods, such as a contact type, a proximity type, and a projection type.
  • heating can be efficiently obtained by heating to 200 ° C. or lower, preferably 100 to 150 ° C., and a high-strength cured film can be obtained.
  • the heating time is preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour. Can be.
  • a transparent plastic film formed from the above-described resin composition is provided.
  • the thickness of the transparent plastic film may be selected in the range of 5 ⁇ m to 5,000 ⁇ m depending on the application.
  • the substrate may be a semiconductor device substrate, a liquid crystal display (LCD) substrate, an organic light emitting diode (OLED) substrate, a solar cell substrate, a flexible display substrate, a touch screen substrate, or a nanoimprint lithography substrate.
  • LCD liquid crystal display
  • OLED organic light emitting diode
  • a polymer resin represented by Formula 2 below was prepared in the following manner.
  • Tetrahydrofuran 200 mL was added as a solvent, potassium carbonate (1 g) was added thereto, and the mixture was stirred at room temperature to dissolve.
  • Methyltrimethoxy silane 3mol
  • 5-bicyclo [2.2.1] hept-2-enyl) triethoxysilane 0.3mol
  • 3- (triethoxysilyl) propylmethacryl were added to the reaction solution.
  • the rate (0.4 mol) mixture was slowly added dropwise over 2 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and then potassium carbonate was filtered through a micro filter, and tetrahydrofuran was distilled under reduced pressure to obtain a target liquid copolymer of the following Chemical Formula 2.
  • the product was confirmed molecular weight and polydispersity through GPC analysis based on polystyrene.
  • the weight average molecular weight of the polymer resin was 24,000, and the polydispersity was 2.8.
  • a polymer resin represented by Formula 3 below was prepared in the following manner.
  • the product was confirmed molecular weight and polydispersity through GPC analysis based on polystyrene.
  • the weight average molecular weight of the polymer resin was 28,000, and the polydispersity was 3.2.
  • Photocuring and thermosetting compositions of Examples 1 to 10 were prepared using the respective polymer resins prepared in Synthesis Examples 1 to 2.
  • the photocuring composition 40 parts by weight of the polymer resin of Synthesis Example 1 or 2 synthesized by the above synthesis example, Irgacure 184 as a photopolymerization initiator, 2 parts of TPM-P07 (Tacoma Technology, Inc.), and amine-based Jeffamine D230 as a thermal polymerization initiator.
  • a polymethyl methacrylate (PMMA) sheet having a thickness of 800 ⁇ m was used as a transparent plastic substrate material.
  • each of the photocurable compositions obtained through Examples 1 to 8 was applied to a spin coater at 600 to 1000 rpm for 15 seconds and then dried at 90 ° C. for 100 seconds on a hot plate. After exposure using a UVA wavelength metal lamp as a light source, a film having a thickness of 100 ⁇ m was formed.
  • thermosetting composition of Examples 9 to 10 each spin-coated to dry for 100 seconds at 90 °C in a hot plate and then cured for 30 minutes at 150 °C to form a film of 100 ⁇ m was evaluated as follows.
  • the hardness was measured using a pencil with a low hardness under the condition of a load of 1 Kg and a pencil core angle of 45 °, and the step before the time point at which scratches or crushes were visually indicated was the hardness of the coated surface.
  • Mitsubishi pencil was used and the hardness level was 2B ⁇ B ⁇ HB ⁇ H ⁇ 2H ⁇ 3H ⁇ 4H ⁇ 5H ⁇ 6H.
  • a rubber eraser was attached to the coated surface at a load of 1 kg and repeated 2,000 times at a rate of 69 times / min to observe the degree of haze on the surface.
  • Steel wool (# 0000) was attached to the coated surface with a load of 500 g and repeated 100 times at a rate of 69 times / min to observe the degree of scratches on the surface.
  • KS M 3332 coffee, milk, soy sauce, kimchi broth, cola, ketchup, 5% acetic acid, 5% ammonia water, etc. were dropped on the coated surface and left at room temperature for 24 hours, and then washed with water to observe whether it was contaminated. .
  • UV-spectrometer was used to measure the average transmittance from 400nm to 800nm.

Abstract

La présente invention concerne une composition de résine pour un substrat en plastique transparent, ladite composition comprenant : (A) une résine silsesquioxane représentée par la formule chimique 1 et (B) un initiateur de photopolymérisation ou un agent de durcissement thermique.
PCT/KR2015/003990 2014-04-23 2015-04-21 Composition de résine pour substrat en plastique transparent WO2015163681A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580021114.7A CN106232684B (zh) 2014-04-23 2015-04-21 用于透明塑料基材的树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0048892 2014-04-23
KR20140048892 2014-04-23

Publications (1)

Publication Number Publication Date
WO2015163681A1 true WO2015163681A1 (fr) 2015-10-29

Family

ID=54332772

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/003990 WO2015163681A1 (fr) 2014-04-23 2015-04-21 Composition de résine pour substrat en plastique transparent

Country Status (4)

Country Link
KR (1) KR101611935B1 (fr)
CN (1) CN106232684B (fr)
TW (1) TWI572677B (fr)
WO (1) WO2015163681A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109426072A (zh) * 2017-09-01 2019-03-05 胡网加成股份有限公司 阻隔性树脂组合物、光固化隔离膜的制造方法与电子元件
US10457837B2 (en) 2016-12-28 2019-10-29 Industrial Technology Research Institute Coating composition and method of preparing the same
US11260638B2 (en) 2019-08-29 2022-03-01 Shpp Global Technologies B.V. Transparent, flexible, impact resistant, multilayer film comprising polycarbonate copolymers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102412888B1 (ko) 2017-05-12 2022-06-28 삼성디스플레이 주식회사 하드코팅용 조성물, 및 하드코팅층을 포함하는 윈도우 부재

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080088441A (ko) * 2007-03-28 2008-10-02 린텍 가부시키가이샤 광 소자용 밀봉재 및 광 소자 밀봉체
KR20100131904A (ko) * 2009-06-08 2010-12-16 한국과학기술연구원 유-무기 하이브리드 그라프트 폴리실세스퀴옥산의 제조 방법 및 이에 의하여 제조된 그라프트 폴리실세스퀴옥산
US8338351B2 (en) * 2006-01-30 2012-12-25 Ashland Licensing And Intellectual Property, Llc Coating compositions for producing transparent super-hydrophobic surfaces

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100481911B1 (ko) * 2000-02-17 2005-04-13 주식회사 인터실리콘 폴리오르가노실세스퀴옥산 및 그의 제조방법
JP2005089705A (ja) * 2003-09-19 2005-04-07 Jsr Corp スルホン酸基含有ラダーシリコーン及び組成物
JP2009138059A (ja) * 2007-12-04 2009-06-25 Canon Inc 成形用材料、それを用いた成形品およびその製造方法
JP5281607B2 (ja) * 2010-03-18 2013-09-04 新日鉄住金化学株式会社 積層体フィルム
KR101344872B1 (ko) 2011-10-17 2013-12-26 이근수 중합체 조성물, 이로부터 얻어진 필름 및 그 제조 방법
JP2013129766A (ja) 2011-12-22 2013-07-04 Nippon Steel & Sumikin Chemical Co Ltd ガラス繊維複合化樹脂基板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8338351B2 (en) * 2006-01-30 2012-12-25 Ashland Licensing And Intellectual Property, Llc Coating compositions for producing transparent super-hydrophobic surfaces
KR20080088441A (ko) * 2007-03-28 2008-10-02 린텍 가부시키가이샤 광 소자용 밀봉재 및 광 소자 밀봉체
KR20100131904A (ko) * 2009-06-08 2010-12-16 한국과학기술연구원 유-무기 하이브리드 그라프트 폴리실세스퀴옥산의 제조 방법 및 이에 의하여 제조된 그라프트 폴리실세스퀴옥산

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CAO, M. ET AL.: "Synthesis and characterization of ladder-like copolymethyl- epoxysilsesquioxane.", REACTIVE & FUNCTIONAL POLYMERS., vol. 45, 2000, pages 119 - 130, XP004210450 *
GNANASEKARAN, D. ET AL.: "Developments of polyhedral oligomeric silsesquioxanes (POSS), POSS nanocomposites and their applications: A review.", JOURNAL OF SCIENTIFIC & INDUSTRIAL RESEARCH., vol. 68, June 2009 (2009-06-01), pages 437 - 464, XP008155833 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10457837B2 (en) 2016-12-28 2019-10-29 Industrial Technology Research Institute Coating composition and method of preparing the same
CN109426072A (zh) * 2017-09-01 2019-03-05 胡网加成股份有限公司 阻隔性树脂组合物、光固化隔离膜的制造方法与电子元件
CN109426072B (zh) * 2017-09-01 2022-12-06 胡网加成股份有限公司 阻隔性树脂组合物、光固化隔离膜的制造方法与电子元件
US11260638B2 (en) 2019-08-29 2022-03-01 Shpp Global Technologies B.V. Transparent, flexible, impact resistant, multilayer film comprising polycarbonate copolymers

Also Published As

Publication number Publication date
TWI572677B (zh) 2017-03-01
CN106232684A (zh) 2016-12-14
KR20150122597A (ko) 2015-11-02
CN106232684B (zh) 2019-09-24
TW201540784A (zh) 2015-11-01
KR101611935B1 (ko) 2016-04-12

Similar Documents

Publication Publication Date Title
JP6196363B2 (ja) 新規なβ‐オキシムエステルフルオレン化合物、それを含む光重合開始剤及びフォトレジスト組成物
JP5423004B2 (ja) ネガ型感光性樹脂組成物およびそれを用いたタッチパネル用材料
KR101518774B1 (ko) 신규한 옥심에스테르 플로렌 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물
JP6171573B2 (ja) 感光性樹脂組成物および硬化膜
WO2013187699A1 (fr) Composition de résine de revêtement dur de siloxane
KR101963931B1 (ko) 흑색 감광성 수지 조성물, 이를 이용한 블랙매트릭스 및 이를 구비한 화상 표시 장치
JP2010152302A (ja) ネガ型感光性樹脂組成物およびそれを用いたタッチパネル用材料
JP6432075B2 (ja) 感光性樹脂組成物および硬化膜
JP6404557B2 (ja) 硬化性樹脂組成物
WO2015163681A1 (fr) Composition de résine pour substrat en plastique transparent
KR20160103040A (ko) 경화성 수지 조성물, 이것을 이용한 반사 방지막, 고체 촬상 소자 및 카메라 모듈
WO2018097580A1 (fr) Photo-initiateur et composition de résine photosensible de protection contre la lumière le contenant
WO2015160229A1 (fr) Copolymère de polysilsesquioxane et composition de résine photosensible le contenant
WO2015141979A1 (fr) Composition de résine durcissable par rayonnement
JP2014130186A (ja) 感光性組成物及び硬化物
WO2012044070A2 (fr) Composition de résine photosensible pour isolant organique
WO2017195927A1 (fr) Nouveau composé de type uréthane-acrylate à base de 2,4,6-triaminotriazine et procédé pour sa préparation
WO2020017920A1 (fr) Résine polyimide et composition de résine photosensible de type négatif comprenant celle-ci
WO2017209449A1 (fr) Composés photo-actifs, composition d'initiateurs photo-polymérisables et composition photo-résine les comprenant
KR101911739B1 (ko) 표면 개질된 무기입자를 포함하는 광경화 수지 조성물
WO2018124826A1 (fr) Compositions de revêtement susceptible de ne former qu'une faible incurvation et film fabriqué à partir de celles-ci
KR101406298B1 (ko) 고내열성 네거티브 레지스트 조성물
KR101235254B1 (ko) 고내열성 음성 레지스트 조성물
WO2017090879A1 (fr) Composition de résine photosensible et film durci préparé à partir de cette dernière
WO2022050661A1 (fr) Copolymère soluble dans les alcalis comprenant un dérivé de maléimide en tant qu'unité de polymérisation, et composition de résine photosensible le comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15782829

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15782829

Country of ref document: EP

Kind code of ref document: A1