CN106232684A - Resin combination for transparent plastic substrate - Google Patents

Resin combination for transparent plastic substrate Download PDF

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Publication number
CN106232684A
CN106232684A CN201580021114.7A CN201580021114A CN106232684A CN 106232684 A CN106232684 A CN 106232684A CN 201580021114 A CN201580021114 A CN 201580021114A CN 106232684 A CN106232684 A CN 106232684A
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alkyl
substituted
unsubstituted
resin
resin combination
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CN106232684B (en
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车爀镇
朴陈圭
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Hu Net Gain Co Ltd
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Hu Net Gain Co Ltd
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    • 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
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • C08L83/06Polysiloxanes containing silicon bound to oxygen-containing groups

Abstract

Provided a kind of resin combination for transparent plastic substrate.This resin combination includes the silsesquioxane resin that (A) is represented by formula 1:

Description

Resin combination for transparent plastic substrate
Technical field
The present invention relates to a kind of resin combination for transparent plastic substrate, be applicable to system more particularly, to one Make the resin combination of the transparent plastic substrate with high flexible and very good mechanical properties.
Background technology
Along with modern society enters an advanced information age, electronical display industry is just becoming more and more important.Recently Technology/the product development of flat faced display (FPD), have been based on high-quality Findings and over a large area manufacture achieve into Exhibition.Price and pliability are predicted to be the key factor of future display industry development.In current information guiding society, greatly Type, flat and multiple functional displays are devices indispensable in vision industry.Also need to record whenever and wherever possible and exchange information. In this case it is necessary to be easy to carry with lightweight display.Existing cathode ray tube cannot meet these requirements, because of And not Portable belt the heaviest for them.Therefore, many researchs focus on the flat faced display that exploitation can manufacture over a large area And the most ultralight flexible display of sensitive paper (FPD).
Current display glass base material has high transparency, absorbance and pencil hardness (>=7H), and represents good Soil resistance and chemical resistance, be therefore applicable to display industry.But, current display glass base material is when being clashed into Brittle, therefore, it is difficult to use, particularly as in the flexible display aroused attention on display of future generation.
Summary of the invention
It is an object of the invention to provide and be applicable to manufacture there is good heat resistance, high-transmission rate, high rigidity, good scratch resistance Property and the resin combination of flexible transparent base material of improvement impact resistance.
A kind of resin combination for transparent plastic substrate is provided according to a scheme of the present invention, including:
(A) silsesquioxane resin represented by formula 1:
Wherein R1、R2, and R3Each stand alone as singly-bound, the C being substituted or being unsubstituted1-C6Stretch alkyl, be substituted or without Substituted C1-C6The C that-O-stretches alkyl or is substituted or is unsubstituted2-C12Stretch alkyl-O-and stretch alkyl,
Each R1aAll stand alone as the C being substituted or being unsubstituted1-C12Alkyl or the C being substituted or being unsubstituted3-C18Ring Alkyl,
Each R2aAll stand alone as C that be substituted or be unsubstituted, that there is ethylenic linkage2-C12Alkyl,
Each R3aAll stand alone as be substituted or be unsubstituted containing C2-C10Cyclic ether group,
L is the integer of 2 to 500, and
M and n each stands alone as the integer of 0 to 500, and premise is that in m and n, at least one is not 0;And
(B) photopolymerization initiator or thermal curing agents.
One is provided to use said composition formed and have in 5 μm to 5,000 μm models according to the further scheme of the present invention The overlay of the thickness in enclosing.
A kind of base material including this overlay is provided according to another scheme of the present invention.
For the resin combination of transparent plastic substrate, there is high absorbance, pliability and hardness according to the present invention, and Show good thermostability, scratch resistance and impact resistance.Due to these advantages, the resin combination of the present invention can be applied to Various hard coat films, display protection window and the base material for flexible device.
Detailed description of the invention
Will be described in now the present invention.
Term used herein " alkyl " is intended to include straight chain, side chain and cyclic hydrocarbon group.Term " is stretched alkyl " and is referred to spread out It is conigenous the divalent group of alkyl.Such as, stretch alkyl include methylene, stretch ethyl, stretch isobutyl group, stretch cyclohexyl, cyclopenta stretches second Base, 2-stretch acrylic and 3-stretches butynyl.
Unless otherwise stated, term " miscellaneous alkyl " itself or with another term combination mean that the carbon by described number is former Stable straight chain that son and one or more hetero atom of group selecting free O, N, P, Si and S to be formed are formed, side chain, Cyclic hydrocarbon group or combinations of the above, and wherein nitrogen, phosphorus and sulphur atom can be the most oxidized, and nitrogen heteroatom is permissible The most quaternized.Similarly, term " miscellaneous stretch alkyl " refers to the divalent group derived from miscellaneous alkyl.
Unless otherwise stated, otherwise term " aryl " means polyunsaturated aromatic hydrocarbon substituent group, its can be monocycle or It is fused together or covalently bound multi-ring (1 to 3 ring).Term " heteroaryl " refers to containing one to four selected from N, O and S The aryl (or ring) of hetero atom (in the case of multi-ring in each single ring), wherein nitrogen and sulphur atom are alternatively by oxygen Change, and nitrogen-atoms is the most quaternized.Heteroaryl can be connected to the remainder of molecule by carbon or hetero atom.Aryl Phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl, 1-pyrrole radicals, 2-pyrrole radicals, 3-pyrrole is included with the limiting examples of heteroaryl Cough up base, 3-pyrazolyl, 2-imidazole radicals, 4-imidazole radicals, pyrroleBase, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-dislike Oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3- Furyl, 2-thienyl, 3-thienyl, 2-pyridine radicals, 3-pyridine radicals, 4-pyridine radicals, 2-pyrimidine radicals, 4-pyrimidine radicals, 5-benzo Thiazolyl, purine radicals, 2-benzimidazolyl, 5-indyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinolineQuinoline base, 5-quinoline Quinoline base, 3-quinolyl and 6-quinolyl.In above-mentioned aryl and heteroaryl, the substituent group of each is the most following can accept of choosing The group that substituent group is formed.Term " stretches aryl " and " miscellaneous stretch aryl " refers respectively to the divalent group of aryl and heteroaryl.
In the statement of " be substituted or be unsubstituted " described herein, term " be substituted " meant in hydrocarbon or More hydrogen atoms are substituted by identical or different substituent group independently of one another.
Suitable substituent group is including, but not limited to-Ra,-halogen ,-O-,=O ,-ORb、-SRb、-S-,=S ,-NRcRc,= NRb,=N-ORb, trihalomethyl ,-CF3、-CN、-OCN、-SCN、-NO、-NO2,=N2、-N3、-S(O)2Rb、-S(O)2NRb、-S (O)2O-、-S(O)2ORb、-OS(O)2Rb、-OS(O)2O-、-OS(O)2ORb、-P(O)(O-)2、-P(O)(ORb)(O-)、-P(O) (ORb)(ORb)、-C(O)Rb、-C(S)Rb、-C(NRb)Rb、-C(O)O-、-C(O)ORb、-C(S)ORb、-C(O)NRcRc、-C(NRb) NRcRc、-OC(O)Rb、-OC(S)Rb、-OC(O)O-、-OC(O)ORb、-OC(S)ORb、-NRbC(O)Rb、-NRbC(S)Rb、-NRbC (O)O-、-NRbC(O)ORb、-NRbC(S)ORb、-NRbC(O)NRcRc、-NRbC(NRb)Rb, and-NRbC(NRb)NRcRc, wherein Ra It is the group selecting free alkyl, cycloalkyl, miscellaneous alkyl, cycloheteroalkyl, aryl, aralkyl, heteroaryl and heteroaryl alkyl to be formed Group;Each RbAll stand alone as hydrogen or Ra;Each RcAll stand alone as Rb, premise is two RcGroup nitrogen-atoms in connection is permissible Form 4-, 5-, 6-or 7-membered cycloheteroalkyl group together, and 1 to 4 group selecting free O, N and S to be formed can be included alternatively Other identical or different hetero atom of group.As instantiation ,-NRcRcMean to include-NH2,-NH-alkyl, N-Pyrrolizidine Base and N-forint base.As another example, the alkyl being substituted mean to include-stretch alkyl-O-alkyl ,-stretch alkyl-miscellaneous Aryl ,-stretch alkyl-cycloheteroalkyl ,-stretch alkyl-C (O) ORb,-stretch alkyl-C (O) NRbRb, and-CH2-CH2-C(O)-CH3.Should The atom that one or more substituent group is connected with them can together with optionally form and include cycloalkyl and cycloheteroalkyl Cyclic rings.
One embodiment of the present of invention provides a kind of for transparent plastic substrate, the combination that includes silsesquioxane resin Thing.Specifically, this resin combination can include (A) silsesquioxane resin, (B) photopolymerization initiator or thermal curing agents, (C) there is the polyfunctional compound of vinylation unsaturated bond, (D) toughener, (methyl) acrylated that (E) adjusts for viscosity Compound or organic solvent, and (F) additive.This resin combination can farther include (G) inorganic particle alternatively.
The following is the more detailed description of the individual components about this resin combination.
(A) silsesquioxane resin
Silsesquioxane resin is the scalariform silsesquioxane polymer represented by formula 1:
In one embodiment, silsesquioxane resin has silsesquioxane structure in main chain, and can include Photosensitive functional group, such as photocuring pi-allyl, vinyl or acrylic acid groups.The existence of photosensitive functional group allows in photocuring group Compound uses silsesquioxane resin.In a further embodiment, silsesquioxane resin has silicon sesquialter in main chain Oxygen alkyl structure, and cyclic ether group can be included, such as thermal curable epoxide group.The existence of cyclic ether group allows can thermosetting Change and compositions uses silsesquioxane resin.Silsesquioxane resin can include that other functional group various is required to realize Physical property.
It is known that silsesquioxane resin have with category of glass as chemical constitution.Due to this structure, silsesquioxane Resin can show the scratch resistance of good thermostability, high-transmission rate, high rigidity and improvement, and above-mentioned is all the characteristic of glass.
In formula 1, R1、R2And R3The C that can each stand alone as singly-bound, be substituted or be unsubstituted1-C6Stretch alkyl, be substituted Or the C being unsubstituted1-C6The C that-O-stretches alkyl or is substituted or is unsubstituted2-C12Stretch alkyl-O-and stretch alkyl.
In formula 1, each R1aAll can stand alone as the C being substituted or being unsubstituted1-C12Alkyl or be substituted or without taking The C in generation3-C18Cyclic hydrocarbon radical.
Including R1And R1aRepetitive (I) can be single form, but it is preferred that the repetitive of multi-form Combination, to be controlled in desired level by the physical property of silsesquioxane resin.Such as, oligomeric silsesquioxane polymer can contain Have the repetitive (I) ' of three kinds of multi-forms, (I) " and (I) " ' combination as repetitive (I), wherein R1And R1aGroup Can be same to each other or different to each other.
The C being substituted or being unsubstituted1-C12Alkyl can be such as methyl, ethyl, propyl group, butyl, hexyl or octyl group.
The C being substituted or being unsubstituted3-C18Cyclic hydrocarbon radical can be cycloalkyl, bicyclic alkyl, aryl or heteroaryl.Cyclic hydrocarbon radical can To include hetero atom or at least one double bond of at least one such as N, P, O or S in the structure.Preferably, it is substituted or not The C being substituted3-C18Cyclic hydrocarbon radical is that choosing freely but is not limited to The group formed.
The C being substituted or being unsubstituted1-C12It is poly-that alkyl makes oligomeric silsesquioxane polymer have enough flexible and permissions Silsesquioxane polymer has suitable glass transition temperature.The C being substituted or being unsubstituted3-C18Cyclic hydrocarbon radical improves photosensitive The thermostability of resin combination and hardness.
In formula 1, each R2aThe photosensitive sense of curing reaction is may participate in when being all and be exposed to light in the presence of light initiator Base, and stand alone as there is being substituted or being unsubstituted C of at least one vinylation unsaturated bond2-C12Alkyl.Photosensitive functional group Can be containing end 3-methylacryloyl, 3-acryloyl group, vinyl or the alkyl of pi-allyl, its instantiation includes 3- Methacryloxypropyl, 3-acryloxypropyl, 3-methylacryloyl, 3-acryloyl group, vinyl and pi-allyl.
In formula 1, each R3aIt is all the functional group and solely that may participate in curing reaction during heating in the presence of thermal curing agents Stand for be substituted or be unsubstituted containing C2-C10Cyclic ether group.Be substituted or be unsubstituted containing C2-C10Cyclic ether group can be Containing terminal glycidyl group, 2-(3,4-epoxycyclohexyl) or the alkyl of oxetanes-3-base, its instantiation includes 3- Glycidoxypropyl, 3-glycidyl, 2-(3,4-epoxycyclohexyl) ethyl, 3-ethyl-3-[3-propoxy methyl] Oxetanyl and oxetanes-3-ylmethyl.Preferably, be substituted or be unsubstituted containing C2-C10Cyclic ether group Containing epoxy radicals.
In formula 1, l is the integer of 2 to 500, m and n each stands alone as the integer of 0 to 500, and premise is in m and n at least one Individual is not 0.
In silsesquioxane resin the ratio of repetitive (I), (II) and (III) can be respectively 1 to 90 mole of %, 0 To 30 moles of % and 0 to 30 mole of %.In the range of these, it can be ensured that use the flexibility that silsesquioxane resin manufactures thoroughly The excellent physical properties of bright plastic basis material.
The weight average molecular weight of silsesquioxane resin is preferably 2,000 to 100,000.If silsesquioxane resin Mean molecule quantity less than 2,000, then be difficult to manufacture plastic basis material.Meanwhile, if the weight average of silsesquioxane resin divides Son is measured more than 100, and 000, then the stickiness of resin combination uprises, thus produces in the processing procedure manufacturing plastic basis material and ask Topic.The polydispersity index of silsesquioxane resin is preferably 1 to 10.Use the average polydispersity index silsesquioxane more than 10 The problem that resin may cause base material flatness.
In formula 1, m can not be 0, and n can be 0.It is to say, repetitive (II) can exist and repetitive (III) can not exist in silsesquioxane resin.In this case, silsesquioxane resin can be used for light-cured resin In compositions.Or, in formula 1, m can be 0, and n can not be 0.It is to say, repetitive (II) can not exist And repetitive (III) may reside in silsesquioxane resin.In this case, silsesquioxane resin can be used for In thermally curable resin composition.In some cases, repetitive (II) and (III) can coexist in silsesquioxane resin In.In these cases, can be manufactured by heat cure after photocuring there is the base material improving thermostability.
Gross weight based on resin combination, the amount of preferably including of silsesquioxane resin is 5 to 80 weight %.If silicon The content of sesquioxyalkane resin less than the lower limit defined above, then is likely difficult to manufacture the base material with desired thickness.Meanwhile, false The content making silsesquioxane resin exceedes the above upper limit defined, then resin combination is probably full-bodied, making it difficult to Manufacture base material.
(B) photopolymerization initiator or thermal curing agents
It is with visible ray, ultraviolet light, extreme ultraviolet light, charged according to the photopolymerization initiator of resin combination of the present invention The composition of the active specy that silsesquioxane resin can be caused to be polymerized is produced when particle radiation, X-ray etc. are irradiated.
Such as, photopolymerization initiator can be selected from: oxime ester compound, united imidazole, benzoin compound, 1-Phenylethanone. Compound, benzophenone cpd, α-dione compounds, multinuclear naphtoquinone compounds, phosphine compound and triaizine compounds.Wherein, benzene Ethanone compounds or oxime ester compound are preferred.
Oxime ester compound can be such as 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O- Acetyl group oxime) and 1,3-octadione-1 [(4-thiophenyl) phenyl]-2-benzoyl oximes.
Acetophenone compound can be such as alpha-hydroxyacetone compounds, α-saddle base ketonic compound and other 1-Phenylethanone. chemical combination Thing.
The instantiation of alpha-hydroxyacetone compounds includes 1-phenyl-2-hydroxy-2-methyl acrylate-1-ketone, 1-(4-cumene Base)-2-hydroxy-2-methyl acrylate-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone and 1-hydroxy cyclohexylphenyl Base phenyl ketone.The instantiation of α-amido ketonic compound includes 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-forint acrylate-1- Ketone and 2-base-2-dimethylamino-1-(4-forint phenyl)-butanone-1.The example of other acetophenone compound includes 2,2- Dimethoxy-acetophenone, 2,2-diethoxy acetophenone and 2,2-dimethoxy-2-phenyl acetophenone.These 1-Phenylethanone. chemical combination Thing can be used alone or mixture as wherein both or more person uses.Acetophenone compound is used to contribute to further Improve thin film strength.
The instantiation of united imidazole includes double (2-chlorphenyl)-4,4', 5,5'-tetra-(the 4-carbethoxyl group benzene of 2,2'- Base)-1,2'-bisglyoxaline, double (2-bromophenyl)-4,4', 5,5'-tetra-(4-the carbethoxy phenyl)-1,2'-bisglyoxaline of 2,2'-, 2, Double (2-chlorphenyl)-4,4', the 5,5'-tetraphenyl-1,2'-bisglyoxaline of 2'-, double (2,4 dichloro benzene the base)-4,4', 5,5'-of 2,2'- Tetraphenyl-1,2'-bisglyoxaline, 2,2'-double (2,4,6-trichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-bisglyoxaline, 2,2'- Double (2,4-the dibromo phenyl)-4,4', 5,5'-tetra-of double (2-bromophenyl)-4,4', 5,5'-tetraphenyl-1,2'-bisglyoxaline, 2,2'- Phenyl-1,2'-bisglyoxaline and double (2,4,6-tribromo phenyl)-4,4', the 5,5'-tetraphenyl-1,2'-bisglyoxaline of 2,2'-.
In these imidazolium compoundss, 2,2'-double (2-chlorphenyls)-4,4', 5,5'-tetraphenyl-1,2'-bisglyoxaline, 2, Double (2,4 dichloro benzene base)-4,4', the 5,5'-tetraphenyl-1,2'-bisglyoxaline of 2'-and double (the 2,4,6-trichlorophenyl)-4 of 2,2'-, 4', 5,5'-tetraphenyl-1,2'-bisglyoxaline is preferred, 2,2'-double (2,4-Dichlorobenzene base)-4,4', 5,5'-tetraphenyl-1, 2'-bisglyoxaline is particularly preferred.
Silsesquioxane resin based on 100 weight portions, the content of photopolymerization initiator is 1 to 30 weight portion, preferably 5 To 20 weight portions.If the content of photopolymerization initiator is less than the lower limit defined above, then it is less likely to occur solidification.Meanwhile, false The content making photopolymerization initiator exceedes the above upper limit defined, then low it may happen that precipitate due to the dissolubility after solidification.
Thermal curing agents has the compound of epoxy radicals for solidification.Thermal curing agents can be typically used for cured epoxy resin Any firming agent.Thermal curing agents has no particular limits, as long as it can react with epoxy resin and cured epoxy resin is Can.Thermal curing agents is typically have the compound of phenolic hydroxyl group, the compound with anhydride group or amine.
The example of the suitable compound in molecule with two or more phenolic hydroxyl groups includes phenol resol resins, first Phenol novolac resin, phenol aralkyl resin, bisphenol-A and the resorcinol novolac resin synthesized, three (hydroxy benzeness Base) methane, dihydro biphenyl and polyphenol compound.The example of the suitable compound with anhydride group includes maleic anhydride, neighbour Phthalate anhydride and pyromellitic dianhydride.The example of suitable amine includes aromatic amine, such as m-diaminobenzene., two (aminocarbonyl phenyl) first Alkane and two amido sulfobenzide .s.
Other type of firming agent can also be used, including latent property amine cure component.Term " latent property " means cure component Do not react but once exceed the beginning temperature of curable epoxide reaction, react rapidly to realize solidification.This allows knot Structure adhesive agent at room temperature or is easily used under the conditions of without the mild heat of activated firming agent.
Guanidine (such as methylguanidine, dimethylguanidine, trimethyl guanidine, the tetramethyl that suitable latent property amine includes such as guanidine, is substituted The different bisguanides of guanidine, methyl, the different bisguanides of dimethyl, the different bisguanides of tetramethyl, the different bisguanides of hexamethyl, the seven different bisguanides of methyl and dicyandiamides), Melmac, guanamine derivatives (such as alkylation benzoguanamine resin, benzoguanamine resin and methoxy ethoxy Ylmethyl benzoguanamine), cyclic tertiary amine, aromatic amine, urea (such as rubigan-N, the N-dimethyl urea (weed eradication that is substituted Grand), 3-phenyl-1,1-dimethyl urea (fenuron), 3,4-Dichlorobenzene base-N, N-dimethyl urea (diuron), tertiary acrylic acid-or Alkyl-amine (such as base dimethyl amine, three (dimethyl amido) phenol, piperidines and piperidine derivative) and imdazole derivatives (such as 2-Ethyl-2-Methyl imidazoles, N-1-Butyl-1H-imidazole, benzimidazole, N-C1To C12-alkyl imidazole and N-Aryimidazole).This A little latent property amine can be used alone or are applied in combination.
Commercially available latent property amine includes Adeca Hardener series (EH-3615, EH-from Adeka company of Japan 3842 and EH-4342S) and from Ajinomoto Co., Japan Ajicure series (PN-40J).
The compound in this resin combination with epoxy radicals, the consumption of thermal curing agents it is included in based on 100 weight portions It is 50 to 200 weight portions, preferably 100 to 145 weight portions, but it is not particularly limited to this content.More particularly, every epoxide equivalent Being included in this resin combination all compounds with epoxy radicals, the preferable amount of thermal curing agents is equivalent to 0.5 to 1.5 Equivalent.If the consumption of thermal curing agents is less than the lower limit defined above, then cannot realize sufficiently solidifying, have and make cured product Toughness reduce tendency.Meanwhile, if the consumption of thermal curing agents exceedes the above upper limit defined, then cured product may become Color so that it is color deteriorates.
(C) there is the polyfunctional compound of vinylation unsaturated bond
The polyfunctional compound with vinylation unsaturated bond is typically have the cross-linking of at least two vinylation double bond Unit.Such as, the polyfunctional compound with vinylation unsaturated bond can be selected from: multifunctional (methyl) acrylic monomers and widow Polymers, such as glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 2,2'-ethylenedioxybis(ethanol). two propylene Acid esters, triethylene glycol dimethacrylate, Aronix M 240, TEG dimethylacrylate, butanediol diformazan Base acrylate, propylene glycol diacrylate, dimethacrylate, trimethylolpropane trimethacrylate, three hydroxyls Trimethacrylate, tetra methylol tetraacrylate, tetra methylol propane tetramethyl acrylate, new penta Tetrol triacrylate, new penta tetrol trimethyl acrylic ester, new penta tetra-acrylate, new penta tetrol tetramethyl acrylic acid Ester, two new penta tetrol five acrylate, two new penta tetrol pentamethacrylates, two new penta tetrol six acrylate, two new penta Tetrol hexamethacrylate, 1,6 hexanediol diacrylate, 1,6-HD dimethylacrylate and pendency epoxy two Acrylate (cardoepoxy diacrylate);The polyester obtained by making (methyl) acrylic acid and polyester prepolyer react (methyl) acrylate, this polyester prepolyer is condensed to yield with unitary or polyprotic acid by polyhydric alcohol;Many by making to have The compound of unit's alcohol radical and two NCOs reacts and makes the polyamine that product is reacted with (methyl) acrylic acid and obtained Ester (methyl) acrylate;And by making (methyl) acrylic acid react epoxy (methyl) acrylate obtained with epoxy resin Resin, this epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresol Phenolic resin varnish type epoxy resin, solvable phenol aldehyde type epoxy resin, tris-phenol type epoxy resin, polycarboxylic acids poly epihydric alcohol Ester, poly glycidyl ester, polyhydric alcohol poly glycidyl ester, aliphatic series or alicyclic epoxy resin, amine epoxy resin or dihydroxy benzenes Type epoxy resin.When considering the factor of such as exposure sensitive, multifunctional (methyl) acrylic monomers is used to be probably favorably 's.
Silsesquioxane resin based on 100 weight portions, the amount of including of polyfunctional compound is 10 to 200 weight portions, excellent Elect 30 to 150 weight portions as.If the content of polyfunctional compound is less than the lower limit defined above, the then curing degree of photosensitive resin May reduce so that said composition is not suitable for manufacturing base material.Meanwhile, if the content of polyfunctional compound exceedes with the upper bound , then there is the risk that the physical property of photosensitive resin may deteriorate in the fixed upper limit.
(D) toughener
Toughener is for strengthening the toughness of solidification compositions.Typical toughener include core-shell polymer, nitrile rubber, And acrylate copolymer and copolymer.
Toughener can be core-shell polymer, and its core uses butadiene polymer or copolymer, styrene polymer often Or copolymer, acrylonitrile polymer or copolymer, acrylate polymer or copolymer or combinations of the above are formed.These gather Compound or copolymer can be crosslinkings or uncrosslinked.Some exemplary shells are to use by the polymethyl of optional crosslinking Acid methyl ester is formed.Other exemplary shell is to use to be formed by the BS of optional crosslinking.
The shell of core-shell polymer is to use styrene polymer or copolymer, methacrylate polymers or be total to often Polymers, acrylonitrile polymer or copolymer or combinations of the above are formed.Shell can be by further by epoxy radicals, acidity or second Acyl acetoxyl group functionalization.The functionalization of this shell can such as by with glycidyl methacrylate or acrylic acid copolymer Or reacted with alkyl acetoacetates acetoxyl group (such as tert-butyl group acetoacetoxy groups) by hydroxyl.Add these functional groups Shell can be cross-linked with polymeric matrix.
Core-shell polymer has at least 10 nanometers, at least 20 nanometers, at least 50 nanometers, at least 100 nanometers, at least 150 receives Rice or the mean diameter of at least 200 nanometers.The mean diameter of core-shell polymer can be maximum 400 nanometers, maximum 500 nanometers, Maximum 750 nanometers or maximum 1000 nanometers.The mean diameter of core-shell polymer can such as 10 to 1000 nanometers, 50 to In the scope of 1000 nanometers, 100 to 750 nanometers or 150 to 500 nanometers.
Or, it is possible to use modified epoxy is as toughener.Modified epoxy was primarily used in the heat cure phase Between need control the adhesive agent of resin flowing or need the structural material of toughness.The reason using modified epoxy is because solid The silsesquioxane resin changed is susceptible to due to its low fragility clash into or vibration, thus limits it and needing the knot of toughness Purposes in structure material.
The necessity of modified epoxy is the high crosslink density of the curable epoxy base due to silsesquioxane resin.Though So the high crosslink density of curable epoxy base is that silsesquioxane resin provides many advantages and high intensity, but it causes silicon The fragility of sesquioxyalkane resin is poor.Modified epoxy is for improving the toughness of silsesquioxane resin.Increase silsesquioxane Other representative example of the toughness of resin is in the main chain that soft chain segment introduces firming agent and epoxy resin, during curing adds Enter reaction material to reduce crosslink density and the butadiene acrylonitrile (CTBN) of adding liquid rubber, such as carboxy blocking, amine The butadiene acrylonitrile (ATBN) of end-blocking and chloroprene rubber (CR).Improve one of most effectual way of epoxy resin toughness It is addition rubber in silsesquioxane resin.According to the method, rubber grain is dispersed in silsesquioxane resin by physical property In or rubber molecule be incorporated into epoxy resin.Have been carried out substantial amounts of research in this respect, and epoxy resin is with CTBN's Complex is the most commercially available.
Silsesquioxane resin based on 100 weight portions, the preferable amount of toughener is 5 to 30 weight portions.Usage amount is few Toughener in 5 weight portions improves physical property hardly.Meanwhile, usage amount produces low firmly more than the toughener of 30 weight portions Degree, causes the imbalance between scratch resistance and processability.
(E) (methyl) acyclic compound adjusted for viscosity or organic solvent
(methyl) acyclic compound for viscosity adjustment can provide the control of the viscosity to resin combination or stickiness System.In this case, resin combination is used not having under any solvent.
As for (methyl) acyclic compound adjusted for viscosity, it is possible to use such as methacrylate, phenyl Maleimide, cyclohexyl methacrylate, acrylic acid tetrahydrofuran ester, THFMA, methacrylic acid Tetrahydropyrans ester, N-vinyl pyrrole pyridine ketone, isobornyl methacrylate, EHA, n-butyl acrylate, third Olefin(e) acid ethyl ester, acrylic acid methyl ester., vinyl acrylate, 2-hydroxy acrylate, β-acryloxy propionic or acrylic acid.
Silsesquioxane resin based on 100 weight portions, for viscosity adjust (methyl) acyclic compound preferably with The amount of 15 to 70 weight portions exists.If (methyl) acyclic compound adjusted for viscosity is less than the lower limit defined above, Then the viscosity of compositions may be too high.Meanwhile, if (methyl) acyclic compound being used for viscosity adjustment exceedes above defining The upper limit, then the physical property of the base material produced may deterioration.
Organic solvent has no particular limits, as long as it can dissolve polymer.Organic solvent can be general In photopolymerizable composition use any organic solvent, the example include acetas system, ether system, ethylene glycol system, ketone system, alcohol system, And carbonic ester system organic solvent.Such as, organic solvent can select free ethyl Sai Lusu, butyl Sai Lusu, ethyl carbitol, fourth Base carbitol, ethylcarbitol acetate, acetate of butyl carbitol, ethylene glycol, Ketohexamethylene, Ketocyclopentane, 3-ethoxy-propionic acid, The group that DMAC N,N' dimethyl acetamide, N-methylpyrrole pyridine ketone, N-methyl caprolactam and above-mentioned mixture are formed.
Compositionss based on 100 weight portions, organic solvent can be with 0 to 95 weight portion, the amount of preferably 10 to 90 weight portions Exist.If the content of solvent exceedes the above upper limit defined, the most possibly cannot obtain and there is the thin of desired thickness Film.
(F) additive
According to one embodiment of the present of invention, additive is to select free antioxidant, light stabilizer and interfacial agent institute The group of composition.
Interfacial agent have improve on substrate coating, compositions coating homogeneity function and from compositions In remove the composition of ability of spot.Interfacial agent can select freely be fluorinated interfacial agent, silica-based interfacial agent, non-from The group that sub-interfacial agent and above-mentioned mixture are formed.
The representative example of the antioxidant being applicable to said composition include Irganox 1010, Irganox 1035, Irganox 1076 and Irganox 1222 (Ciba-Geigy, Japan).The suitably example of light stabilizer includes: Tinuvin 292, Tinuvin 144 and Tinuvin 622LD (Ciba-Geigy, Japan);And sanol LS-770, sanol LS- 765, sanol LS-292 and sanol LS-744 (Sankyo, Japan).
Silsesquioxane resin based on 100 weight portions, the consumption of additive is usually 0.001 to 2 weight portion, is preferably 0.01 to 1 weight portion.The amount of additive can change according to the selection of user, if thing required in Photosensitve resin composition Rationality matter does not changes.
In certain embodiments, in addition to composition (A) to (F), resin combination can farther include (G) alternatively Inorganic particle.Inorganic particle is in order to improve case hardness and the wearability of resin combination.Such as, inorganic particle can be dioxy Silicon carbide particle, titanium dioxide granule, zirconia particles, antimony oxide particle or Zinc oxide particles.
Silsesquioxane resin based on 100 weight portions, the consumption of inorganic particle can be 0.1 to 15 weight portion.If The amount of inorganic particle is less than the lower limit defined above, then it could not be expected that the hardness of resin combination is fully enhanced.Meanwhile, false The amount making inorganic particle exceedes the above upper limit defined, then the absorbance of resin combination may be caused low or mist degree is high.
For the resin combination of transparent plastic substrate, there is high-transmission rate and pliability according to the present invention, and show Good thermostability, scratch resistance and impact resistance.Due to these advantages, the resin combination of the present invention can be used for manufacture and has excellent The base material of different physical property.
According to one embodiment of the present of invention, resin combination can be used for producing thick plastic basis material.Can be in not limit Use known any technology in art to form thick base material under system, and the example includes spin coating, dip-coating, roller It is coated with, nets painting, flow coat, screen painting and drip casting.In UV curing schedule subsequently, solvent is under vacuo by using infrared light Irradiate or pass through heating evaporation.Then, compositions is made to be exposed selectively to excimer laser, extreme ultraviolet light, ultraviolet light, visible Optical, electrical sub-bundle, X-ray, g line (wavelength 436nm), i line (wavelength 365nm), h line (wavelength 405nm) or above-mentioned mixed light.Example As, it is possible to use contact, neighbouring or projection exposure.Resin combination can be by being heating and curing.In such a case, it is possible to it is logical Cross and resin combination is heated to less than 200 DEG C, preferably 100 to 150 DEG C effectively obtains the cured film with high intensity.Heating Preferably carry out 5 minutes to 2 hours, more preferably carry out 10 minutes to 1 hour.
Further embodiment of the present invention provides the overlay using this resin combination to be formed.Overlay Thickness can select in 5 μm to 5, the scope of 000 μm, depending on expection purpose.
An alternative embodiment of the invention provides the base material including this overlay.This base material can be used for semiconductor group Part, liquid crystal display (LCD) device, Organic Light Emitting Diode (OLED) assembly, solar battery apparatus, flexible display device or tactile Control screen apparatus, or can be applied to manufacturing device by nano-imprint lithography art.
The present invention will be explained in greater detail with reference to following instance.The purpose that these examples illustrate that is provided, and The scope of the present invention is not limited to this.
Example
1. the synthesis of oligomeric silsesquioxane fluoropolymer resin
[synthesis example 1]
The fluoropolymer resin represented by following procedure formula 2.
Under stirring at room temperature potassium carbonate (1g) is dissolved in solvents tetrahydrofurane (200mL).The periods of 2 hours to this Solution is slowly added dropwise MTMS (0.3 mole), (5-dicyclo [2.2.1] hept-2-ene" base) triethoxysilane (0.3 mole) and methacrylic acid 3-(triethoxy is silica-based) propyl ester (0.4 mole).After being added dropwise to complete, react 12 hours. Filtered by micro-filter and remove potassium carbonate.Oxolane is under reduced pressure evaporated off, obtains the subject copolymers of formula 2, be a liquid.
Measured molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer The weight average molecular weight of resin is 24,000, and polydispersity index is 2.8.
[synthesis example 2]
Prepare, in the way of identical with synthesis example 1, the fluoropolymer resin represented by formula 3, the difference is that only use front three Epoxide (3-(oxirane-2-ylmethoxy) propyl group) silane (0.4 mole) substituent methyl acrylic acid 3-(triethoxy is silica-based) Propyl ester.
Measured molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer The weight average molecular weight of resin is 28,000, and polydispersity index is 3.2.
Example 1-10
The fluoropolymer resin using synthesis example 1-2 prepares photocuring and heat-curing composition.Specifically, by 40 weight portions The fluoropolymer resin of synthesis example 1 or 2, the Irgacure 184 or TPM-P07 (TAKOMA technical concern company limited) of 2 weight portions As the Jeffamine D230 of photopolymerization initiator or 5 weight portions as amido thermal polymerization initiator, two seasons of 15 weight portions (M500, MIWON spy uses chemistry stock to penta 4 alcohol radicals (dipentahexaerythritol-based) acrylic acid polyfunctional compound Part company limited), five vinyls pentamethyl cyclopentasiloxane (Gelest) of 10 weight portions or modified epoxy (KDSF180, Kukdo chemistry limited company) as toughener, dimethylbenzene as the bonding reinforcing agent (KBM of organic solvent and 2 weight portions 403, SHIN-ETSU) mix.After being stirred at room temperature 4 hours, mixture is filtered by 10 μm filters to obtain Solids content is adjusted to the compositions of 35%.Composition and the content thereof of compositions (example 1 to 10) are listed in table 1.
Table 1
[comparative example 1]
Use polymethyl methacrylate (PMMA) sheet material as transparent plastic substrate of 800 μ m-thick.
[physical property assessment]
It is applied on spin coater carry out 15 with 600-1000rpm by every kind of Photocurable composition of preparation in example 1 to 8 Second, and be dried 100 seconds on the hot plate of 90 DEG C.The compositions being dried is made to be exposed to the metalized lamp using UVA wavelength as light source, To form the film of 100 μ m-thick.In spin coating example 9 and 10 preparation every kind of heat-curing composition and on the hot plate of 90 DEG C be dried 100 seconds, and at 150 DEG C, solidify 30 minutes to form the film of 100 μ m-thick.Film is assessed following parameter.
(1) pencil hardness
According to KS D6711 method of testing, use Mitsubishi pencil with the pencil lead angle amount of 45 ° under the load of 1kg Survey the hardness of each film.Pencil is used according to the minimum order to maximum hardness.It is defined as visually seeing by the hardness of coating surface Observe the grade before cut or impression formation.The hardness level of pencil carries with the order of 2B < B < HB < H < 2H < 3H < 4H < 5H < 6H High.
(2) wearability
Under the load of 1kg, erasing rubber is attached to coating surface, and with reciprocal 2,000 time of the speed of 69 beats/min.See Examine and whether be atomized on surface.
(3) scratch resistance
By steel wool (#0000) at 500g/cm2Load under move back and forth on coating surface with the speed of 69mm/sec After 100 times, observe whether form cut on surface.
(4) chemical resistance
The chemical resistance of each film is assessed according to ASTM D 2792 method of testing.First, by 5% hydrochloric acid, 5% sulphuric acid, MEK, acetone and DMF drip on coating surface.After at room temperature standing 4 hours, observe the change on surface.
(5) antiscale
The antiscale of each film is assessed according to KS M 3332 method of testing.First, by coffee, milk, soybean juice, Pickles Juice, cola, tomato sauce, 5% acetic acid, 5% ammonia etc. drop on coating surface.Clean with water after at room temperature standing 24 hours Surface.Observe whether surface is contaminated.
(6) absorbance
The absorbance using each film of UV spectrometer measurement under 400-800nm is average.
(7) crackle
The state of each film of visualization after photocuring and heat cure, to judge whether form crackle on film.
By result record at table 2.
Table 2
From the results shown in Table 2, compared with general plastic basis material (PMMA), the transparent of example 1,3,5,7 and 9 is moulded Material base material film shows the physical property of excellence.

Claims (9)

1., for a resin combination for transparent plastic substrate, comprise:
(A) silsesquioxane resin represented by formula 1:
Wherein R1、R2, and R3Each stand alone as singly-bound, the C being substituted or being unsubstituted1-C6Stretch alkyl, be substituted or be unsubstituted C1-C6The C that-O-stretches alkyl or is substituted or is unsubstituted2-C12Stretch alkyl-O-and stretch alkyl,
Each R1aAll stand alone as the C being substituted or being unsubstituted1-C12Alkyl or the C being substituted or being unsubstituted3-C18Cyclic hydrocarbon Base,
Each R2aAll stand alone as C that be substituted or be unsubstituted, that there is ethylenic linkage2-C12Alkyl, each R3aAll stand alone as through taking Generation or be unsubstituted containing C2-C10Cyclic ether group,
L is the integer of 2 to 500, and
M and n each stands alone as the integer of 0 to 500, and premise is that in m and n, at least one is not 0;And
(B) photopolymerization initiator or thermal curing agents.
2. resin combination as claimed in claim 1, wherein at R1aIn, this C being substituted or being unsubstituted1-C12Alkyl is Methyl, ethyl, propyl group, butyl, hexyl or octyl group, this C being substituted or being unsubstituted3-C18Cyclic hydrocarbon radical is cycloalkyl, dicyclo alkane Base, aryl or heteroaryl.
3. resin combination as claimed in claim 1, wherein R2aFor containing end 3-methylacryloyl, 3-acryloyl group, Vinyl or the alkyl of pi-allyl.
4. resin combination as claimed in claim 1, wherein at R3aIn, this be substituted or be unsubstituted containing C3-C12Cyclic ethers Group is containing terminal glycidyl group, 2-(3,4-epoxycyclohexyl) or the alkyl of oxetanes-3-base.
5. resin combination as claimed in claim 1, wherein this silsesquioxane resin has the weight of 2,000 to 100,000 Amount mean molecule quantity.
6. resin combination as claimed in claim 1, wherein repetitive (I) in this silsesquioxane resin, (II) and (III) ratio is respectively 1 to 90 mole of %, 0 to 30 mole of % and 0 to 30 mole of %.
7. resin combination as claimed in claim 1, comprises (C) further and has the multifunctional chemical combination of vinylation unsaturated bond Thing, (D) toughener, (E) for viscosity adjust (methyl) acyclic compound or organic solvent, and (F) at least one be selected from The additive of antioxidant, light stabilizer and interfacial agent.
8. an overlay, is to use the compositions as according to any one of claim 1 to 7 formed and have in 5 μm Thickness to 5,000 μ m.
9. a base material, comprises overlay as claimed in claim 8.
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