CN107918245B - Curable composition, cured film thereof, and display element comprising cured film - Google Patents

Curable composition, cured film thereof, and display element comprising cured film Download PDF

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CN107918245B
CN107918245B CN201710649396.6A CN201710649396A CN107918245B CN 107918245 B CN107918245 B CN 107918245B CN 201710649396 A CN201710649396 A CN 201710649396A CN 107918245 B CN107918245 B CN 107918245B
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curable composition
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acrylate
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CN107918245A (en
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冈本优纪
目黒聡
堀田佑策
和田亜弥
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JNC Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
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    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
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    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • G—PHYSICS
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    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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Abstract

The invention relates to a curable composition, a cured film thereof and a display element comprising the cured film, wherein the curable composition comprises: a polymer (A) obtained by radical polymerization of a raw material monomer containing a trifunctional or higher (meth) acrylate (a 1) in the presence of a chain transfer agent (a 2); a photopolymerization initiator (B); and a solvent (C). The curable composition of the present invention is excellent in film-forming properties and low-temperature curability, and can form a cured film having high transparency. Therefore, the curable composition of the present invention has low-temperature curability and can be used for forming a color filter protective film, a transparent insulating film provided between a TFT and an alignment film or between a TFT and a transparent electrode, and the like.

Description

Curable composition, cured film thereof, and display element comprising cured film
Technical Field
The present invention relates to a curable composition that can be cured at a low temperature, a cured film thereof, and a display element including the cured film.
Background
With the rapid development of products for information terminals using liquid crystal display elements and the like, products using organic materials in portions using conventional inorganic materials such as glass or metal, such as electronic circuits, displays, and sensors, have been developed.
The use of an organic material has advantages in that the weight of the product and the process can be reduced, in addition to the ease of adjustment of each characteristic by molecular design or synthesis conditions. In particular, replacing a conventional glass substrate with an organic material substrate not only has the advantage of weight reduction, but also has high suitability for flexibility due to mechanical flexibility of the organic material, and a printing method such as roll-to-roll (roll) can be applied, thereby expecting a reduction in process cost. On the other hand, when a conventional glass is used as a substrate instead of an organic material, there is a problem that the heat resistance of the substrate is lowered.
In addition, in the case where a curable resin composition is used for forming a color filter protective Film or a transparent insulating Film provided between a Thin Film Transistor (TFT) and an alignment Film or between the TFT and a transparent electrode, it is desirable that the material be easily cured at a low temperature (a temperature lower than the glass transition point temperature of the substrate) and have high compatibility with organic materials in order to prevent deterioration due to thermal overload to the substrate. In addition, from the viewpoint of reduction of process energy, curing of a curable resin at a low temperature is also required.
Many studies have been made to cope with low-temperature curing, and the use of a soluble polymer (see patent document 1), the use of a curing accelerator (see patent documents 2 and 3), and the like have been proposed.
The present invention proposes a resin composition which overcomes the above problems, is easy to synthesize a polymer, has excellent storage stability, and can be cured at a low temperature (see patent document 4). However, the resin composition described in patent document 4 has a lower limit of a calcination temperature of 140 ℃, and cannot be used for a Polyethylene terephthalate (PET) substrate or a Triacetyl cellulose (TAC) substrate having a heat resistant temperature of 120 ℃ or lower.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2009-203414
[ patent document 2] International publication No. 2009/011304
[ patent document 3] Japanese patent laid-open No. 2002-69311
[ patent document 4] Japanese patent application No. 2015-104566
Disclosure of Invention
[ problems to be solved by the invention ]
The invention aims to provide a curable composition having excellent film forming properties, low-temperature curing properties, and cured film transparency.
[ means for solving the problems ]
The present inventors have found that a curable composition containing: a polymer (A) obtained by radical polymerization of a raw material monomer containing a trifunctional or higher (meth) acrylate (a 1) in the presence of a chain transfer agent (a 2); a photopolymerization initiator (B); and a solvent (C); the present invention has been completed based on this finding. The present invention includes the following items.
[1] A curable composition comprising: a polymer (A) obtained by radical polymerization of a raw material monomer containing a trifunctional or higher (meth) acrylate (a 1) in the presence of a chain transfer agent (a 2); a photopolymerization initiator (B); and a solvent (C).
[2] The curable composition according to item [1], wherein the chain transfer agent (a 2) is 2,4-diphenyl-4-methyl-1-pentene.
[3] The curable composition according to [1], wherein the weight-average molecular weight of the polymer (A) is from 2,000 to 200,000.
[4] The curable composition according to [1], wherein the photopolymerization initiator (B) is at least one selected from the group consisting of an α -aminophenylketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator and an oxime ester photopolymerization initiator.
[5] The curable composition according to [1], wherein the solvent (C) contains 50% by weight or more of a solvent having a boiling point of 150 ℃ or less based on the weight of the total solvent.
[6] A cured film obtained by using the curable composition according to any one of [1] to [5 ].
[7] A display element comprising the cured film according to item [6 ].
[ Effect of the invention ]
The curable composition of the present invention has low-temperature curing properties and can be used for forming a color filter protective film, a transparent insulating film provided between a TFT and an alignment film or between a TFT and a transparent electrode, and the like.
Detailed Description
In the present specification, the expression "(meth) acrylic acid" may be used to indicate both acrylic acid and methacrylic acid. Similarly, the term "(meth) acrylate" may be used to denote one or both of an acrylate and a methacrylate.
In the present specification, the term "alkyl" refers to a straight-chain or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, a pentyl group and a hexyl group.
<1 > curable composition of the present invention
The curable composition of the present invention comprises: a polymer (A) obtained by radical polymerization of a raw material monomer containing a trifunctional or higher (meth) acrylate (a 1) in the presence of a chain transfer agent (a 2); a photopolymerization initiator (B); and a solvent (C). The curable composition of the present invention can be obtained by further optionally adding other additives according to the objective characteristics and uniformly mixing and dissolving these.
<1-1. Trifunctional or higher (meth) acrylate (a 1) >
The trifunctional or higher (meth) acrylate (a 1) used in the present invention is not particularly limited as long as it has three or more (meth) acrylates in one molecule.
Specific examples of the trifunctional or higher (meth) acrylate (a 1) are:
trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, trimethylolpropane Ethylene Oxide (EO) modified tri (meth) acrylate, trimethylolpropane Propylene Oxide (PO) modified tri (meth) acrylate, glycerol EO modified tri (meth) acrylate, glycerol PO modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, epoxidized isocyanuric acid tri (meth) acrylate, and epsilon-caprolactone modified tri- (2- (meth) acryloyloxyethyl) isocyanurate;
tetrafunctional (meth) acrylates such as di-trimethylolpropane tetra (meth) acrylate, epoxidized pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate, and diglycerol EO-modified tetraacrylate;
pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate;
hexafunctional (meth) acrylates such as dipentaerythritol hexaacrylate; and
a polyfunctional (meth) acrylate having a carboxyl group.
Among the above compounds, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate are preferable from the viewpoints of ease of production of the polymer and physical properties of the polymer, for example, high solubility to the extent that precipitation of the polymer does not occur during production, and low viscosity of a polymer solution which is easy to handle.
The trifunctional or higher (meth) acrylate (a 1) may be a commercially available product as described below.
Specific examples of commercially available trimethylolpropane triacrylate as the trifunctional acrylate are: NK Ester (NK Ester) TMPT (trade name, new Zhongcun Industrial Co., ltd.), TMPTA (trade name, daicelAllnex Co., ltd.), and Luo Nisi (Aronix) M-309 (trade name, east Asia synthetic Co., ltd.);
specific examples of commercially available trimethylolpropane EO-modified triacrylate are: TMPEOTA (trade name, daicel Allnex, inc.), luo Nisi (Aronix) M-350, luo Nisi (Aronix) M-360 (both trade names, east Asia synthetic, inc.);
specific examples of commercially available trimethylolpropane PO-modified triacrylate are: ai Baixi lane (EBECRYIL) 135 (trade name, daicelAllnex, inc.), sub-Luo Nisi (Aronix) M-310, sub-Luo Nisi (Aronix) M-321 (both trade names, east Asia synthetic, inc.);
a specific example of a commercially available product of glycerin PO modified triacrylate is OTA 480 (trade name, xylonite alonos (Daicel Allnex) inc.);
specific examples of commercially available products of epoxidized isocyanuric acid triacrylate are NK Ester (NK Ester) A-9300 (trade name, ningmura industries, ltd.);
a specific example of a commercially available product of the epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate is NK Ester (NK Ester) A-9300-1CL (trade name, ningzhou Kogyo Co., ltd.).
A specific example of a commercially available product of trimethylolpropane trimethacrylate as a trifunctional methacrylate Ester is NK Ester (NK Ester) TMPT (trade name, ningmura industries, ltd.).
Specific examples of commercially available products of di-trimethylolpropane tetraacrylate as tetrafunctional acrylate are: NK Ester (NK Ester) AD-TMP (trade name, new Zhongcun Industrial Co., ltd.), ai Baixi Lo (EBECRYIL) 140, and Ai Baixi Lo (EBECRYIL) 1142 (both trade names, daicel Allnex Co., ltd.), and sub-Luo Nisi (Aronix) M-408 (trade name, east Asia synthetic Co., ltd.);
specific examples of commercially available products of epoxidized pentaerythritol tetraacrylate are NK Ester (NK Ester) ATM-35E (trade name, new Zhongcun Industrial Co., ltd.);
specific examples of commercially available products of pentaerythritol tetraacrylate are NK Ester (NK Ester) A-TMMT (trade name, new Zhongcun Industrial Co., ltd.);
specific examples of commercially available products of pentaerythritol alkoxy tetraacrylate are Ai Baixi lane (EBECRYIL) 40 (trade name, xylonite Allnex corporation);
a specific example of a commercially available diglycerol EO-modified tetraacrylate is Luo Nisi (Aronix) M-460 (trade name, toyo Synthesis Ltd.).
Specific examples of commercially available products of dipentaerythritol hexaacrylate as the hexafunctional acrylate are: NK Ester (NK Ester) A-DPH (trade name, ningmura industries, ltd.), and DPHA (trade name, daicel Allnex, ltd.).
Specific examples of commercially available products of polyfunctional acrylates having carboxyl groups are Luo Nisi (Aronix) M-510 and Luo Nisi (Aronix) M-520 (both trade names, toyo Synthesis Ltd.).
Specific examples of commercially available products of a mixture of an epoxidized isocyanurate diacrylate and an epoxidized isocyanurate triacrylate, which is a mixture of an epoxidized isocyanurate triacrylate as a trifunctional acrylate, are Luo Nisi (Aronix) M-313 (30 to 40 wt%) and Luo Nisi (Aronix) M-315 (3 to 13 wt%) (both trade names, manufactured by tokyo gmbh, and the content in parentheses is a value listed as the content of the epoxidized isocyanurate diacrylate in the mixture).
Specific examples of commercially available products of a mixture of pentaerythritol triacrylate as a trifunctional acrylate and pentaerythritol tetraacrylate as a tetrafunctional acrylate are PETIA, PETRA, and PETA (both trade names, celloineol Allnex corporation), luo Nisi (Aronix) M-306 (65 to 70 wt%), luo Nisi (Aronix) M-305 (55 to 63 wt%), luo Nisi (Aronix) M-303 (30 to 60 wt%), luo Nisi (Aronix) M-452 (25 to 40 wt%), and Luo Nisi (Aronix) M-450 (less than 10 wt%) (both trade names, synthetic aragonite corporation, the content in parentheses is the reported as the content of the pentaerythritol triacrylate in the mixture).
Specific examples of commercially available products of a mixture of dipentaerythritol pentaacrylate as a pentafunctional acrylate and dipentaerythritol hexaacrylate as a hexafunctional acrylate are Luo Nisi (aroix) M-403 (50 to 60 wt%), luo Nisi (aroix) M-400 (40 to 50 wt%), luo Nisi (aroix) M-402 (30 to 40 wt%), luo Nisi (aroix) M-404 (30 to 40 wt%), luo Nisi (aroix) M-406 (25 to 35 wt%), and Luo Nisi (aroix) M-405 (10 to 20 wt%) (trade name, east asian synthetic limited company, the content in parentheses is a table value of the content of pentaerythritol pentaacrylate in the mixture).
The trifunctional or higher (meth) acrylate (a 1) may be used alone or in combination of two or more. According to the method of the present invention, a branched polymer can be produced by radical polymerization without gelling two or more trifunctional or higher (meth) acrylates not reported in conventional production examples.
<1-2. Chain transfer agent (a 2) >
Specific examples of the chain transfer agent (a 2) used in the present invention include thioglycolic acid, mercaptopropionic acid, 2,4-diphenyl-4-methyl-1-pentene, kunoxter (Quinoexter) QE-2014 (trade name) manufactured by kawasaki chemical industry ltd, and kunoxter (Quinoexter) QE-3124 (trade name) manufactured by kawasaki chemical industry ltd.
Among the chain transfer agents (a 2), an addition/cleavage type chain transfer agent is more preferable, and among the addition/cleavage type chain transfer agents, 2,4-diphenyl-4-methyl-1-pentene is more preferable from the viewpoint of safety and reproducibility at the time of production.
The chain transfer agent (a 2) may be used alone or in combination of two or more.
<1-3 > Compound (a 3) having polymerizable double bond
The raw material monomers of the polymer (a) contained in the curable composition of the present invention may further contain a compound (a 3) having a polymerizable double bond in addition to the trifunctional or higher (meth) acrylate (a 1).
In the present invention, the compound (a 3) having a polymerizable double bond is roughly classified into "a compound having an alkoxysilyl group and a polymerizable double bond", "a compound having a carboxyl group and a polymerizable double bond", and "a compound having no alkoxysilyl group and no carboxyl group and having a polymerizable double bond".
The compound (a 3) having a polymerizable double bond contains a compound having an alkoxysilyl group and a polymerizable double bond, and thus the curable composition of the present invention has an effect of improving the adhesion between a cured film formed using the curable composition and a substrate. The compound having a carboxyl group and a polymerizable double bond has an effect of improving the alkali solubility of the curable composition of the present invention.
Further, the compound (a 3) having a polymerizable double bond, which does not have an alkoxysilyl group or a carboxyl group, has an effect of changing other properties. An example of the effect is a refractive index control effect of the hardened film.
The compound (a 3) having a polymerizable double bond may be used alone, or two or more kinds may be used in combination.
In order to make the polymer (a) more strongly exhibit the properties of a branched polymer, it is preferable that the total amount of the compounds (a 3) having polymerizable double bonds is 0 to 49.9% by mass in 100% by mass of the raw material monomers.
<1-3-1 > Compound having alkoxysilyl group and polymerizable double bond >
The compound having an alkoxysilyl group and a polymerizable double bond that can be used in the present invention is a compound having at least one alkoxysilyl group per molecule and one to two polymerizable double bonds per molecule.
Specific examples of the compound having an alkoxysilyl group and a polymerizable double bond are:
(meth) acrylates having an alkoxysilyl group such as 3- (trimethoxysilyl) propyl (meth) acrylate and 3- (triethoxysilyl) propyl (meth) acrylate;
compounds having an alkoxysilane group and a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; and
compounds having an alkoxysilyl group and a styryl group such as p-styryltrimethoxysilane and p-styryltriethoxysilane.
Among these specific examples of the compound having an alkoxysilyl group and a polymerizable double bond, 3- (trimethoxysilyl) propyl methacrylate and vinyltrimethoxysilane, which are easily available and have good compatibility with the photopolymerization initiator (B) when a polymer is produced, are preferable, and 3- (trimethoxysilyl) propyl methacrylate is more preferable.
In the compound (a 3) having a polymerizable double bond, compounds having an alkoxysilane group and a polymerizable double bond may be used alone, or two or more of them may be used in combination.
In order to make the polymer more strongly exhibit the properties of a branched polymer and to exhibit sufficient adhesion, the total amount of the compound having an alkoxysilyl group and a polymerizable double bond is preferably 1 to 30% by mass in 100% by mass of the raw material monomer.
<1-3-2 > Compound having carboxyl group and polymerizable double bond >
The compound having a carboxyl group and a polymerizable double bond that can be used in the present invention is a compound having at least one carboxyl group per molecule and one to two polymerizable double bonds per molecule.
Specific examples of the compound having a carboxyl group and a polymerizable double bond are:
unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid;
unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and
and (meth) acrylates having a carboxyl group such as monohydroxyethyl (meth) acrylate phthalate.
Among specific examples of the compound having a carboxyl group and a polymerizable double bond, (meth) acrylic acid and phthalic acid monohydroxyethyl (meth) acrylate which are easily available and have good compatibility with the photopolymerization initiator (B) when they are produced into a polymer are preferable, and (meth) acrylic acid is more preferable.
In the compound (a 3) having a polymerizable double bond, compounds having a carboxyl group and a polymerizable double bond may be used alone, or two or more of them may be used in combination.
In order to make the polymer (a) more strongly exhibit the properties of a branched polymer and exhibit appropriate alkali solubility, the total amount of the compounds having a carboxyl group and a polymerizable double bond is preferably 5 to 40% by mass in 100% by mass of the raw material monomer. When the amount is within this range, a difference in the dissolution rate between the exposed portions and the unexposed portions is easily formed, and the curable composition has good pattern formability against alkali development.
<1-3-3 > Compound having polymerizable double bond without alkoxysilyl group and carboxyl group >
The compound having no alkoxysilyl group and no carboxyl group and having a polymerizable double bond that can be used in the present invention is a compound having no alkoxysilyl group and no carboxyl group and having one to two polymerizable double bonds per molecule.
Specific examples of the compound having no alkoxysilyl group and no carboxyl group and having a polymerizable double bond are: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate;
cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, and isobornyl (meth) acrylate;
(meth) acrylates having an ether bond such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate;
(meth) acrylates having cyclic ethers such as glycidyl (meth) acrylate and (3-ethyloxetan-3-yl) methyl (meth) acrylate;
(meth) acrylates having alcoholic hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
aryl methacrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and ethoxylated O-phenylphenol (meth) acrylate;
fluorine-containing (meth) acrylates such as trifluoroethyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate;
n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
styrene, and α -butyl- ω - (3-methacryloxypropyl) polydimethylsiloxane.
<1-4 > Process for producing Polymer (A) >
The method for producing the polymer (a) contained in the curable composition of the present invention is preferably radical polymerization in solution using one or more trifunctional or higher (meth) acrylates (a 1) in the presence of a chain transfer agent (a 2). The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, and is usually in the range of 50 ℃ to 140 ℃, and preferably 90 ℃ or lower from the viewpoint of suppressing gelation. The polymerization time is also not particularly limited, but is usually in the range of 1 hour to 24 hours, and preferably 8 hours or less from the viewpoint of workability. The polymerization may be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.
The solvent used in the polymerization reaction is preferably a solvent in which the trifunctional or higher (meth) acrylate (a 1) to be used, the chain transfer agent (a 2) used in combination therewith, the compound (a 3) having a polymerizable double bond used as needed, and the obtained polymer (a) can be dissolved. Specific examples of such solvents are methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl methyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N-dimethylformamide, acetic acid, and water. The solvent may be one of these solvents, or may be a mixture of two or more of these solvents.
The amount of the solvent used in the production of the polymer (a) is not limited as long as it is a uniform solution at the start of production, and is preferably 40 to 90 wt%, more preferably 60 to 80 wt%, based on the total amount charged at the time of production, in order to suppress gelation.
As the polymerization initiator used for producing the polymer (a), a compound which generates radicals by heat, an azo initiator such as azobisisobutyronitrile, or a peroxide initiator such as benzoyl peroxide can be used.
Specific examples of the thermal radical generating agent are: 2,2 '-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70; trade name, wako pure chemical industries, ltd.), 2,2' -azobis (2,4-dimethylvaleronitrile) (V-65; trade name, wako pure chemical industries, ltd.), 2,2 '-azobis (isobutyronitrile) (V-60; trade name, wako pure chemical industries, ltd.), 040 2,2' -azobis (2-methylbutyronitrile) (V-59; trade name, wako pure chemical industries, ltd.), 2,2 '-azobis [ N- (2-propenyl) -2-methylpropionamide ] (VF-096; trade name, wako pure chemical industries, ltd.), 2,2' -azobis (N-butyl-2-methylpropionamide) (3579-110; trade name, wako pure chemical industries, W1-25-VPE, W1-601, wako pure chemical industries, VPE 1, VPE, VPI pure chemical industries, VPE, or more).
The weight average molecular weight of the polymer (a) is preferably 2,000 to 200,000, and more preferably 5,000 to 100,000 from the viewpoint of suppressing gelation.
The weight average molecular weight herein is a value in terms of polystyrene determined by a Gel Permeation Chromatography (GPC) method (column temperature: 35 ℃ C., flow rate: 1 mL/min). The weight average molecular weight can be determined using the following conditions: the standard polystyrene is polystyrene having a molecular weight of 645 to 285,300 (for example, agilent S-M2-10 polystyrene calibration set (calibretion kit) PL2010-0102 (trade name, agilent Technologies), inc.), the column is PLgel MIXED-D (trade name, agilent Technologies, inc.), and the mobile phase is Tetrahydrofuran (THF). In addition, the weight average molecular weight of a commercially available product in the present specification is a value described in the table.
The polymer (a) obtained as described above can be used in the curable composition of the present invention in the state of a solution containing a solvent used in the reaction. The reaction solvent in this case preferably contains 50% by weight or more of a solvent having a boiling point of 150 ℃ or less, as will be described later. When the composition ratio of the solvent is to be adjusted in the preparation of the curable composition, the reaction solvent may be once distilled off under reduced pressure and dissolved in a solvent having a new composition.
From the viewpoint of curability of the curable composition, the polymer (a) obtained as described above is preferably subjected to reprecipitation to remove unreacted materials. As a purification method by reprecipitation, a nonpolar solvent in an amount 3 to 10 times the volume of the obtained polymer solution is stirred, and the polymer solution is dropped thereto to precipitate the polymer. After removing the supernatant, the precipitate is dissolved again in the solvent, whereby purification can be performed.
The non-polar solvent used in the reprecipitation method is preferably hexane or heptane.
<1-5. Photopolymerization initiator (B) >
The photopolymerization initiator contained in the curable composition of the present invention is not particularly limited as long as it can initiate polymerization of a composition containing the polymer (a), the photopolymerization initiator (B), and the solvent (C).
Specific examples of the photopolymerization initiator contained in the curable composition of the present invention include: benzophenone, milrinone, 4,4 '-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4' -isopropylphenylacetone, 1-hydroxycyclohexylphenylketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] ethanone]-2-morpholinopropan-1-one (Irgacure) 907, trade name, nippon Basfu (BASF Japan) Co., ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Brilliant Racure) 369, trade name, nippon Basfu (BASF Jap)an) Co., ltd.), ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4 '-bis (t-butylperoxycarbonyl) benzophenone, 3,4,4' -tris (t-butylperoxycarbonyl) benzophenone, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-2- (O-benzoyl oxime) (Irgacure OXE01; trade name, manufactured by BASF Japan Ltd.), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-1- (O-acetyloxime) (Irgacure (IRGACURE) OXE02; trade name, BASF (BASF Japan) Co., ltd.), brilliant OXE03 (trade name, BASF (BASF Japan) Co., ltd.), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio]Phenyl radical]-2- (O-acetyloxime) (Ai Dike Kurilz (ADEKA ARKLS) NCI-930; trade name, ai Dike (ADEKA) GmbH), ai Dike Kurilz (ADEKA ARKLS) NCI-831 (trade name, ai Dike (ADEKA) GmbH), ai Dike Otorma (ADEKA OPTOMER) N-1919 (trade name, ai Dike (ADEKA) GmbH), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4 ' -methoxystyryl) -24 zxft 24-bis (trichloromethyl) -s-triazine, 2- (3 ',4' -dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ',4' -dimethoxystyryl) -8583 zzft-bis (trichloromethyl) -s-triazine, 2- (2 ',4' -dimethoxystyryl) -3583-bis (trichloromethyl) -s-triazine, 2- (trichloromethyl) -3543-bis (trichloromethyl) -s-carbonylmethyl) -s-triazine, 2- (2 ',4' -dimethoxystyryl) -3543, 2' -bis (trichloromethyloxy) -3 ' -trichloromethyltriazine)]-2,6-bis (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2 '-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4' -methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-1,2' -biimidazole, 2,2 '-bis (2-chlorophenyl) -56 zxft 3256', 5,5 '-tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2,2 '-bis (6595-3295-dichlorophenyl) -34zxft 3298', 3476 '-tetraphenylbenzimidazole, 34zzft 3527' -bis (3475 '-bromophenyl) -3727' -biazoxazole 3527 '-biazoxazole, 3475' -tetraphenylbenzimidazole, 3427 '-biazoxazole 3527' -biazoxazolePhenyl-1,2 ' -biimidazole, 2,2' -bis (2,4,6-trichlorophenyl) -4,4',5,5' -tetraphenyl-1,2 ' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (. Eta.5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
The photopolymerization initiator may be used alone or in combination of two or more. Among the photopolymerization initiators, α -aminophenylalkyl ketone, acylphosphine oxide, or oxime ester photopolymerization initiators are preferable from the viewpoint of transparency of the cured film.
Among the photopolymerization initiators, 1,2-octanedione, 1- [4- (phenylthio) phenyl ] -2- (O-benzoyl oxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime), or 1,2-propanedione, and 1- [4- [4- (2-hydroxyethoxy) phenylthio ] phenyl ] -2- (O-acetyl oxime) are more preferably 20% by weight or more based on the total weight of the photopolymerization initiator, from the viewpoint of the transparency of the cured film. Further, it is more preferably 50% by weight or more. The photopolymerization initiator may comprise 1,2-octanedione, 1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) or 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio ] phenyl ] -2- (O-acetyloxime) alone.
<1-6. Solvent (C) >
The solvent to be added to the curable composition of the present invention is preferably a solvent in which the polymer and other additives are soluble. <xnotran> , , , , ,1- ,2- , ,2- , , , , , , , , , , , , , ,3- ,3- ,3- ,3- ,3- ,3- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,2- -2- ,2- -2- ,2- -2- ,2- -2- , , , , , ,2- ,2- , , , , , , , , , , 8978 zxft 8978- , , , , , </xnotran> Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, toluene, xylene, gamma-butyrolactone, N-dimethylacetamide, and N, N-dimethylformamide. These compounds may be used alone, or two or more of them may be used in combination.
The solvent (C) is preferably blended so that the solid polymer (a), the photopolymerization initiator (B) and other additives in the curable composition of the present invention are 5 to 90 wt% in total.
It is preferable that 100% by weight of the solvent (C) contained in the curable composition of the present invention contains 50% by weight or more of a solvent having a boiling point of 150 ℃. If the solvent composition is set as described above, the load of the drying step at the time of curing is reduced.
From the viewpoint of reducing the load of the drying step of the curable composition of the present invention and from the viewpoint of safety to the human body, an example of a preferred solvent is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and butyl acetate.
<1-7. Additives >
The curable composition of the present invention may contain an additive. The additive to be added to the curable composition of the present invention is added to improve the properties of the curable composition of the present invention, such as coating uniformity, adhesion, and stability. Examples of the additives are polymerization inhibitors, acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, silicone resin coating property improvers, adhesion improvers such as silane coupling agents, anti-agglomeration agents such as sodium polyacrylate, thermal crosslinking agents such as epoxy compounds, melamine compounds or bisazide compounds, antioxidants such as hindered phenols, and imidazole-or polyfunctional acrylate hardening accelerators.
<1-7-1. Surfactant and coating Performance improving agent >
The curable composition of the present invention may contain a surfactant and a coating property improving agent. The surfactant and the coating property improving agent are used to improve wettability, leveling property, or coating property to the base substrate. Specific examples of the surfactant and the coating property improving agent optionally added to the curable composition of the present invention include: perot Li Fuluo (Polyflow) No.45, perot Li Fuluo (Polyflow) KL-245, perot Li Fuluo (Polyflow) No.75, perot Li Fuluo (Polyflow) No.90, perot Li Fuluo (Polyflow) No.95 (all trade names, co., ltd.); BYK (BYK) -300, BYK (BYK) -306, BYK (BYK) -310, BYK (BYK) -320, BYK (BYK) -330, BYK (BYK) -342, BYK (BYK) -346 (all of which are trade names, japan Bi Kehua science (BYK-Chemie Japan) gmbh); KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (trade name, shin-Etsu chemical industry Co., ltd.); sha Fulong (Surflon) SC-101, sha Fulong (Surflon) KH-40, sha Fulong (Surflon) S611 (all of which are trade names, AGC beauty culture (AGC Seimi Chemical) Co., ltd.); foger (Ftergent) 222F, foger (Ftergent) 208G, foger (Ftergent) 251, foger (Ftergent) 710FL, foger (Ftergent) 710FM, foger (Ftergent) 710FS, foger (Ftergent) 601AD, foger (Ftergent) 602A, foger (Ftergent) 650A, FTX-218 (all of which are tradenames, nieuss (Neos) GmbH); ai Futa (EFTOP) EF-351, ai Futa (EFTOP) EF-352, ai Futa (EFTOP) EF-601, ai Futa (EFTOP) EF-801, ai Futa (EFTOP) EF-802 (all of which are trade names, mitsubishi materials, inc.); meijia method (Megafac) F-171, meijia method (Megafac) F-177, meijia method (Megafac) F-410, meijia method (Megafac) F-430, meijia method (Megafac) F-444, meijia method (Megafac) F-472SF, meijia method (Megafac) F-475, meijia method (Megafac) F-477, meijia method (Megafac) F-552, meijia method (Megafac) F-553, meijiafac method (Megafac) F-554, meijiafac (Megafac) F-555, meijiafac method (Megafac) F-556, meijiafa (Megafac) F-558, meijiafac method (Megafac) R-30, meijiafac method (Megafac) R-94, meijiafac method (Megafac) F-75, meijiafac method (Megafac) F-72) RS-72, meijiafac RS-RS 72, or above; di Gao Tewen (TEGO Twin) 4000, di Gao Tewen (TEGO Twin) 4100, di Gao Fuluo (TEGO Flow) 370, di golay (TEGO Glide) 420, di golay (TEGO Glide) 440, di golay (TEGO Glide) 450, di Gao Lade (TEGO Rad) 2200N, di Gao Lade (TEGO Rad) 2250N (all of which are trade names, japan winning the division of gudgesso (Evonik Degussa Japan) division ltd); fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene lauryl amine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyldiphenyl ether disulfonate. At least one selected from these is preferably used in the additive.
Among these surfactants and coating property enhancers, at least one silicone coating property enhancer selected from fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl sulfamate, meijia (Megafac) R-08, meijia (Megafac) R-30, meijia (Megafac) F-477, meijia (Megafac) F-556, and Meijia (Megafac) F-554, and Bike (BYK) -306, bike (BYK) -342, bike (BYK) -344, bike (BYK) -346, KP-341, KP-358, and KP-368 is preferably added from the viewpoint of enhancing the coating uniformity of the curable composition of the present invention.
The content of the surfactant and the coating property improving agent in the curable composition of the present invention is preferably 0.001 to 0.1% by weight based on the total amount of the composition.
<1-7-2. Hardening accelerator >
The curable composition of the present invention may contain a curing accelerator. The curing accelerator is used to accelerate the curing reaction of the curable composition and to improve the hardness, heat resistance and chemical resistance of the cured film. Specific examples of the hardening accelerator optionally added to the curable composition of the present invention are: trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, glycerol EO-modified tri (meth) acrylate, glycerol PO-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, epoxidized isocyanurate tri (meth) acrylate, epsilon-caprolactone-modified tri- (2- (meth) acryloyloxyethyl) isocyanurate, di-trimethylolpropane tetra (meth) acrylate, epoxidized pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate, diglycerol EO-modified tetra (acrylate), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, and polyfunctional (meth) acrylate having a carboxyl group, and compounds such as 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [ 3262 zxft ] benzimidazole. The trifunctional or higher (meth) acrylate is communicated with the component (a 1) which is a raw material of the polymer (A) of the present invention, and the compounds listed in the specific examples can be used. Among them, it is preferable to use Luo Nisi (Aronix) M-510, luo Nisi (Aronix) M-520, luo Nisi (Aronix) M-450, luo Nisi (Aronix) M-403, and Luo Nisi (Aronix) M-402.
By adding the curing accelerator to the curable composition of the present invention, a cured film can be formed quickly, and mechanical strength such as solvent resistance and scratch resistance can be imparted to the cured film. The hardening accelerator may be used alone or in combination of two or more.
<1-7-3 > adhesion improving agent >
The curable composition of the present invention may contain an adhesion improver. The adhesion improver is used to improve the adhesion between the curable composition and the substrate. The adhesion improver optionally added to the curable composition of the present invention may be a coupling agent. The adhesion improver may be one kind, or two or more kinds. Silane, aluminum or titanate compounds can be used as the coupling agent. Specific examples of such coupling agents are: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, aluminum acetoalkoxydiisopropoxide, and tetraisopropylbis (dioctylphosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.
<1-7-4 > anti-agglomeration agent
The curable composition of the present invention may contain an anti-agglomeration agent. The anti-agglomeration agent may be dissolved in a solvent to prevent agglomeration. Specific examples of the anti-agglomeration agent optionally added to the curable composition of the present invention are: dipper (DISPERBYK) -145, dipper (DISPERBYK) -161, dipper (DISPERBYK) -162, dipper (DISPERBYK) -163, dipper (DISPERBYK) -164, dipper (DISPERBYK) -182, dipper (DISPERBYK) -184, dipper (DISPERBYK) -185, dipper (DISPERBYK) -2163, dipper (DISPERBYK) -2164, BYK-220S, dipper (DISPERBYK) -191, dipper (DISPERBYK) -199, dipper (DISPERBYK) -2015 (all trade names), japan Bi Kehua (BYK-Chemie Japan) Co., ltd.), FTX-218, foger (Ftergent) 710FM, foger (Ftergent) 710FS (all trade names, nieuss (Neos) Inc.), floren (FLOWLEN) G-600, and Floren (FLOWLEN) G-700 (trade names, kyoeisha chemical industry Co., ltd.).
<1-7-5 > antioxidant
An antioxidant may be added to the curable composition of the present invention. As the antioxidant, hindered phenol compounds, hindered amine compounds, phosphorus compounds and sulfur compounds can be suitably used. The antioxidant may be used alone or in combination of two or more. The antioxidant is preferably an antioxidant of a hindered phenol compound from the viewpoint of weather resistance.
The antioxidant optionally added to the curable composition of the present invention may be a hindered amine-based antioxidant or a hindered phenol-based antioxidant. The antioxidants are specifically: yi Lufo s (IRGAFOS) XP40, yilingfoss (IRGAFOS) XP60, yi Lunuo s (IRGANOX) 1010, yi Lunuo s (IRGANOX) 1035, yi Lunuo s (IRGANOX) 1076, yi Lunuo s (IRGANOX) 1135, yi Lunuo s (IRGANOX) 1520L (both trade names, japanese Basefo (BASF Japan) GmbH), 8652 zx8652 staff (ADK STAB) AO-20, addick stapf (ADSTAK B) AO-30, ai Dike staff (ADK STAB) AO-50, ikestaco STAB (ADK STAB) AO-60, ai Dike (ADK STAB) XP-70, ikex TAB 3580, ADK 3580, EK-25, ADGANOX). Of these, yi Lunuo s (IRGANOX) 1010 and addustabeta (ADK STAB) AO-60 are more preferable from the viewpoint of suppressing discoloration of the curable composition of the present invention.
<1-7-6. Crosslinking agent >
The curable composition of the present invention may optionally contain a crosslinking agent from the viewpoint of improving heat resistance, chemical resistance, uniformity within the film surface, flexibility and elasticity.
Specific examples of the thermal crosslinking agent optionally added to the curable composition of the present invention are: jER807, jER815, jER825, jER827, jER828, jER190P and jER191P (all trade names, mitsubishi chemical corporation), jER1004, jER1256, YX8000 (all trade names, mitsubishi chemical corporation), alada (Araldite) CY177, alada (Araldite) CY184 (all trade names, huntsman (Huntsman Japan) corporation), sai Luo Xide (Celloxide) 2021P, EHPE-3150 (all trade names, dacellosolve chemical industry Co., ltd.), teckomo A (Techmore) VG3101L (trade name, P Lin Taike (Printec) Co., ltd.), nicaraglan library (NIKALAC) MW-30HM, nicaraglan library (NIKALAC) MW-100LM, nicaraglan library (NIKALAC) MW-270, nicaraglan library (NIKALAC) MW-280, nicaraglan library (NIKALAC) MW-290, nicaraglan library (NIKALAC) MW-390, and nicaraglan library (NIKALAC) MW-750LM (both trade names, three and chemical Co., ltd.).
<1-7-8 > photoacid generators
The curable composition of the present invention may optionally contain a photoacid generator in order to exhibit excellent resolution. The photoacid generator may be exemplified by 1,2-quinonediazide compounds.
Specific examples of 1,2-quinonediazide compounds are: 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate (e.g., NT-200; trade name, toyo Synthesis chemical industry), 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate; 2,2',4,4' -tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonate, 2,2',4,4' -tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate, 2,3,3', 4-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonate, 2,3,3', 4-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonate, 2,3,4,4' -tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonate ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonate ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonate ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonate ester; tris (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonate, 1,1,1-tris (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-4-sulfonate, 1,1,1-tris (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-5-sulfonate; bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide-4-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide-5-sulfonate; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-4-sulfonate, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-5-sulfonate, 4,4'- [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol-3265 zxf3265-naphthoquinone diazide-4-sulfonate, 4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol-3525 zxf 3525-naphthoquinone diazide-5-sulfonate; bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-4-sulfonate, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-5-sulfonate, 3,3,3',3' -tetramethyl-1,1 '-spirobiindan-5,6,7,5', 6',7' -hexanol-1,2-naphthoquinone diazide-4-sulfonate, 3,3,3',3' -tetramethyl-1,1 '-spirobiindan-5,6,7,5', 6',7' -hexanol-1,2-naphthoquinone diazide-5-sulfonate; 2,2,4-trimethyl-7,2 ',4' -trihydroxyflavan-1,2-naphthoquinone diazide-4-sulfonate, and 2,2,4-trimethyl-7,2 ',4' -trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonate.
<1-8 > storage of curable composition >
The curable composition of the present invention is preferably stored in the range of-30 to 25 ℃ in the absence of light, because the composition has good stability with time. More preferably, the storage is carried out at-10 ℃ to 20 ℃.
<2 > cured film obtained from curable composition >
When the curable composition of the present invention is applied to the surface of a substrate and the solvent is removed by, for example, heating, a coating film can be formed.
The curable composition of the present invention can be applied by a known method such as spin coating, roll coating, dipping, slit coating, ink jet printing, flexographic printing, and gravure printing to form a coating film.
Examples of the substrate used for film formation include a plastic, a glass, and a glass having a transparent electrode such as Fluorine-doped Tin Oxide (FTO) or Indium Tin Oxide (ITO). Specific examples of the plastic include polycarbonate, poly (meth) acrylate, polyurethane, polyethylene terephthalate, cycloolefin, and triacetyl cellulose.
The coating film can be heated (prebaked) by a hot plate, an oven or the like. The heating conditions vary depending on the kind and mixing ratio of each component, and are usually 60 to 100 ℃ for 1 to 15 minutes. Thereafter, the coating film is cured by heat treatment (postbaking) at 80 to 140 ℃, preferably 80 to 120 ℃ for 5 to 60 minutes.
The curable composition of the present invention can be cured by heat at a low temperature of 85 to 120 ℃ to obtain a cured film. Therefore, when the curable composition of the present invention is applied to a substrate having a low glass transition point such as plastic, a cured film can be obtained without causing deterioration or breakage of the substrate.
About thisThe curable composition of the invention can be used for irradiating a pre-baked coating film with ultraviolet rays. Suitably, the amount of ultraviolet radiation is 5mJ/cm in terms of i-ray2～1000mJ/cm2. The curable composition irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of a compound having a polymerizable double bond, and the film curability is improved.
[ examples ]
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. The method for evaluating the curable composition of the present invention is shown below.
For each component, compounds used in polymerization examples, and comparative examples are described.
Trifunctional or higher (meth) acrylate (a 1):
asia Luo Nisi (Aronix) M-402 (trade name, toyo synthetic products Co., ltd., hereinafter, abbreviated as "M-402")
Chain transfer agent (a 2):
2,4-Diphenyl-4-methyl-1-pentene (hereinafter abbreviated as "α -MSD")
Compound (a 3) having a polymerizable double bond:
3- (trimethoxysilyl) propyl methacrylate (trade name, sila-ace S710, JNC Co., ltd., hereinafter abbreviated as "S710") as a compound having an alkoxysilyl group and a polymerizable double bond
Methacrylic acid as a compound having a carboxyl group and a polymerizable double bond
Polymerization initiator:
v-65 (trade name, wako pure chemical industries, ltd., hereinafter abbreviated as "V-65")
Polymerization solvent:
propylene glycol monomethyl ether (hereinafter, abbreviated as "PGME")
Photopolymerization initiator (B):
brilliant beauty (IRGACURE) OXE01 (trade name, manufactured by BASF Japan Ltd., hereinafter abbreviated as "OXE 01")
Brilliant beauty (IRGACURE) OXE02 (trade name, manufactured by BASF Japan Ltd., hereinafter abbreviated as "OXE 02")
Ai Dike Sukuluz (ADEKAARKLS) NCI-930 (trade name, ai Dike (ADEKA) Inc., hereinafter abbreviated as "NCI-930")
Diluting the solvent:
PGME
additive:
bike (BYK) -342 (trade name, BYK-Chemie Japan, inc., japan Bi Kehua, abbreviated as "BYK-342" hereinafter) as a silicone surfactant
A mixture of pentaerythritol triacrylate as a trifunctional acrylate and pentaerythritol tetraacrylate as a tetrafunctional acrylate, namely, luo Nisi (Aronix) M-450 (trade name, manufactured by east Asia synthetic Co., ltd., abbreviated as "M-450" hereinafter)
NT-200 (trade name, toyo chemical industry) as a photoacid generator
[ polymerization example 1]
In a four-necked flask with a stirrer, 18.0g of PGME as a polymerization solvent, 402.51g of M-402 as a trifunctional or higher (meth) acrylate (a 1), 0.90g of α -MSD as a chain transfer agent (a 2), and 0.23g of V-65 as a polymerization initiator were charged while bubbling with nitrogen gas, and after confirming the dissolution of the contents by stirring at 35 ℃ for 5 minutes, it took 15 minutes to heat the flask to 80 ℃. Then, the mixture was heated at 80 ℃ for 3 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A1). A part of the polymer-containing solution (A1) was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 11,800.
[ polymerization example 2]
16.0g of PGME as a polymerization solvent, 402.51g of M-402 of a trifunctional or higher (meth) acrylate (a 1) as a raw material monomer, 0.34g of S710 of a compound (a 3) having a polymerizable double bond as a raw material monomer, 1.37g of α -MSD as a chain transfer agent (a 2), and 0.34g of V-65 as a polymerization initiator were put into a four-necked flask with a stirrer while bubbling with nitrogen, and stirred at 35 ℃ for 5 minutes to confirm dissolution of the contents, and then the temperature was raised to 80 ℃ over 15 minutes. Then, the mixture was heated at 80 ℃ for 5 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A2). A part of the polymer-containing solution (A2) was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 12,600.
[ polymerization example 3]
16.0g of PGME as a polymerization solvent, 5363 g of M-4024.80g of a trifunctional or higher (meth) acrylate (a 1) as a raw material monomer, 2.06g of methacrylic acid as a compound (a 3) having a polymerizable double bond in a raw material monomer, 1.37g of alpha-MSD as a chain transfer agent (a 2) and 650.34g as a polymerization initiator were charged into a four-necked flask with a stirrer while bubbling with nitrogen gas, and after stirring at 35 ℃ for 5 minutes to confirm dissolution of the contents, it took 15 minutes to heat up to 80 ℃. Then, the mixture was heated at 80 ℃ for 3 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A3). A part of the polymer-containing solution (A3) was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 18,800.
[ polymerization example 4]
16.0g of PGME as a polymerization solvent, 402.91g of a trifunctional or higher (meth) acrylate (a 1) as a raw material monomer, 2.13g of methacrylic acid as a compound (a 3) having a polymerizable double bond in a raw material monomer, 0.82g of S710, 1.37g of a-MSD as a chain transfer agent (a 2), and 0.34g of V-65 as a polymerization initiator were charged into a four-necked flask with a stirrer while bubbling with nitrogen gas, and after stirring at 35 ℃ for 5 minutes to confirm dissolution of the contents, it took 15 minutes to heat up to 80 ℃. Then, the mixture was heated at 80 ℃ for 3 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A4). A portion of the polymer-containing solution (A4) was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 35,200.
[ polymerization example 5]
16.0g of PGME as a polymerization solvent, 5.35g of M-520.35g of a trifunctional or higher (meth) acrylate (a 1) as a raw material monomer, 1.51g of methacrylic acid as a compound (a 3) having a polymerizable double bond in a raw material monomer, 1.37g of α -MSD as a chain transfer agent (a 2), and 0.34g of V-65 as a polymerization initiator were charged into a four-necked flask with a stirrer while bubbling with nitrogen, and stirred at 35 ℃ for 5 minutes to confirm dissolution of the contents, and then the temperature was raised to 80 ℃ over 15 minutes. Then, the mixture was heated at 80 ℃ for 3 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A5). A part of the polymer-containing solution (A5) was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight was 23,600.
[ polymerization example 6]
16.0g of PGME as a polymerization solvent, 4.11g of M-402 of a trifunctional or higher (meth) acrylate (a 1) as a raw material monomer, 2.19g of methacrylic acid of a compound (a 3) having a polymerizable double bond as a raw material monomer, 0.55g of butyl methacrylate, 1.37g of α -MSD as a chain transfer agent (a 2), and 0.34g of V-65 as a polymerization initiator were charged into a four-necked flask with a stirrer while bubbling with nitrogen gas, and after confirming the dissolution of the contents by stirring at 35 ℃ for 5 minutes, it took 15 minutes to heat up to 80 ℃. Then, the mixture was heated at 80 ℃ for 3 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A6). A portion of the polymer-containing solution (A6) was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight was 26,800.
[ polymerization example 7]
16.0g of PGME as a polymerization solvent, 402.18g of a trifunctional or higher (meth) acrylate (a 1) as a raw material monomer, 2.19g of methacrylic acid as a compound (a 3) having a polymerizable double bond in a raw material monomer, 0.48g of 2-hydroxyethyl methacrylate, 1.37g of α -MSD as a chain transfer agent (a 2), and 0.34g of V-65 as a polymerization initiator were charged into a four-necked flask equipped with a stirrer while bubbling with nitrogen gas, and stirred at 35 ℃ for 5 minutes to confirm dissolution of the contents, followed by heating to 80 ℃ over 15 minutes. Then, the mixture was heated at 80 ℃ for 3 hours to effect polymerization.
The solution after polymerization was cooled to room temperature to obtain a polymer-containing solution (A7). A part of the polymer-containing solution (A7) was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 37,200.
[ example 1]
The polymer-containing solution (A1) obtained in polymerization example 1, OXE01 as a photopolymerization initiator (B), BYK (BYK) -342 as an additive, and PGME as a diluting solvent were mixed and dissolved at the ratio (unit: g) shown in Table 1, and filtered through a membrane filter (0.2 μm) to obtain a thermosetting composition.
The total amount of the solvent contained in the curable composition is the total amount of PGME contained in the polymer-containing solution (A1) and PGME of the diluting solvent, and the solid content concentration is adjusted to about 20 wt% in this step. The same applies to examples 2 to 13 and comparative examples 1 and 2.
The curable composition was spin-coated on a glass substrate at 300rpm for 10 seconds and pre-baked on a hot plate at 85 ℃ for 2 minutes. Then, exposure was performed in air using a proximity exposure machine TME-150PRC (trade name, topcon, inc.). The exposure amount was measured by an integrated calorimeter UIT-102 (trade name, oxtail (USHIO) Ltd.) and a photoreceiver UVD-365PD (trade name, oxtail (USHIO) Ltd.) to be 100mJ/cm2. Further, the glass substrate was post-baked on a hot plate at 85 ℃ for 30 minutes to obtain a glass substrate having a film thickness of 3.0 μm and an 85 ℃ bake-cured film. Except that the temperature of the hot plate during post-baking was changed from 85 ℃ to 140 DEG CExcept for this, the same procedure was carried out to obtain a glass substrate having a 140 ℃ bake-hardened film.
[ evaluation method of film Forming Property ]
The substrate end of the obtained glass substrate with the cured film baked at 85 ℃ was observed with an optical microscope, and the distance from the substrate end to the cured film end, that is, the width distance of the region where the cured film was not present on the glass substrate was measured, and the measured values are shown in table 1. However, when a region where no cured film is present on the glass substrate cannot be observed, it is described as "none". The film-forming property "o" was evaluated when the distance from the substrate end to the cured film end was less than 100 μm, and the film-forming property "x" was evaluated when the distance from the substrate end to the cured film end was 100 μm or more, and the evaluation results are shown in table 1.
[ evaluation method of Low temperature curing Property ]
The glass substrate with the 85 ℃ bake-cured film subjected to the film thickness measurement was immersed in PGME maintained at 24 ℃ for 2 minutes. An immersion test was performed in which the PGME was removed from the PGME by air blowing. Thereafter, the film thickness was measured to calculate the residual immersion film ratio = (film thickness after immersion/film thickness before immersion) × 100, and the calculated values are shown in table 1. Further, the same immersion test and the immersion residual film ratio were calculated using the glass substrate with the 140 ℃ bake-hardened film subjected to the film thickness measurement, and the calculated values are shown in table 1. The case where both the immersion residual film ratio of the glass substrate with the 85 ℃ bake-cured film and the immersion residual film ratio of the glass substrate with the 140 ℃ bake-cured film were 95% or more was evaluated as "o" for low-temperature curing, and the other cases were evaluated as "x" for low-temperature curing, and the evaluation results are shown in table 1.
[ method for evaluating transparency ]
The transmittance of only the 85 ℃ bake-cured film at a wavelength of 400nm of light was measured using an ultraviolet-visible near-infrared spectrophotometer (trade name, V-670, japan spectro corporation) provided with a glass substrate having no cured film on the reference side of the ultraviolet-visible near-infrared spectrophotometer and a glass substrate having an 85 ℃ bake-cured film on the sample side, and the measured values are shown in table 1. The case where the light transmittance was 95% or more was evaluated as "o" in transparency, and the case where the light transmittance was less than 95% was evaluated as "x" in transparency, and the evaluation results are shown in table 1.
Examples 2 to 9 and comparative examples 1 to 2
The curable composition was obtained by mixing and dissolving the components in the proportions (unit: g) shown in Table 1 by the method of example 1. The distance from the substrate end to the cured film end and the light transmittance were measured by the method of example 1, and the film formability, low-temperature curing properties and transparency were evaluated by calculating the percentage of the residual film after immersion. These results are set forth in table 1.
TABLE 1-1
Figure BDA0001366634810000241
Figure BDA0001366634810000251
Tables 1 to 2
Figure BDA0001366634810000252
[ adhesion test (examples 6 to 8 and 10) ]
The glass substrates with the cured films baked at 85 ℃ obtained in examples 6 to 8 were subjected to a cross-cut test (JIS-K5600, ISO 2409) for peeling of the cured films, and the number of remaining products was counted. Since the results of both tests were classified into class 0, the adhesiveness of the curable composition was judged to be good.
[ Pattern formability test (examples 9 to 13) ]
The curable composition was spin-coated on a glass substrate at 300rpm for 10 seconds and pre-baked on a hot plate at 85 ℃ for 2 minutes. Then, a proximity exposure machine TME-150PRC (trade name, topcon) was used in the air through a mask having a square pattern of 50 μm squareCompany limited) to perform the exposure. The exposure amount was measured by a cumulative light quantity meter UIT-102 (trade name, oxtail (USHIO) Ltd.) and a light receiver UVD-365PD (trade name, oxtail (USHIO) Ltd.) to 100mJ/cm2. The exposed coating film was subjected to coating solution development with a 2.38 wt% aqueous tetramethylammonium hydroxide solution for 60 seconds, then washed with pure water for 20 seconds, and then dried with a hot plate at 85 ℃ for 2 minutes. Further, after post-baking on a hot plate at 85 ℃ for 30 minutes, the curable composition was observed with an optical microscope, and as a result, a dot pattern having a pattern width of about 50 μm was observed, and the pattern formability of the curable composition was judged to be good.
As is clear from the results in table 1, the curable compositions containing the polymer (a), the photopolymerization initiator (B) and the solvent (C) of examples 1 to 13 are excellent in film-forming properties, low-temperature curing properties and transparency.
The curable composition of comparative example 1 did not contain the photopolymerization initiator (B) and cured in the baking at 140 ℃. The curable composition of comparative example 2 does not contain the polymer (A), and is poor in film formability and transparency.
Further, as is clear from the results of the adhesion test, the curable compositions of examples 6 to 8 and example 10, in which the compound having an alkoxysilyl group and a polymerizable double bond was used as a part of the raw material monomer of the polymer (a), were also excellent in adhesion.
Further, as is clear from the results of the pattern formability test, the curable compositions of examples 9 to 13, in which a compound having a carboxyl group and a polymerizable double bond is used as a part of the raw material monomer of the polymer (a), are also excellent in pattern formability.
[ industrial applicability ]
The curable composition of the present invention is excellent in film formability, low-temperature curability, and transparency of a cured film, and the cured film obtained using the curable composition of the present invention can be used as a color filter protective film, a transparent insulating film provided between a TFT and an alignment film, or between a TFT and a transparent electrode, or the like. Since the low-temperature curing property is excellent, it is effective particularly when an organic material is used as a substrate.

Claims (5)

1. A curable composition characterized by comprising: a polymer (A) obtained by radical polymerization of a starting monomer comprising a trifunctional or higher (meth) acrylate (a 1) by heating at 50 to 90 ℃ for 1 to 24 hours in the presence of a chain transfer agent (a 2); a photopolymerization initiator (B); and a solvent (C) in a solvent,
wherein the polymer (A) has a weight-average molecular weight of 2,000 to 200,000 and the solvent (C) contains 50 wt% or more of a solvent having a boiling point of 150 ℃ or less based on the weight of the total solvent.
2. The hardening composition of claim 1 wherein the chain transfer agent (a 2) is 2,4-diphenyl-4-methyl-1-pentene.
3. The curable composition according to claim 1, wherein the photopolymerization initiator (B) is at least one selected from the group consisting of an α -aminophenylketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator and an oxime ester photopolymerization initiator.
4. A cured film obtained by using the curable composition according to any one of claims 1 to 3.
5. A display element comprising the cured film according to claim 4.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211867A (en) * 2014-08-21 2014-12-17 苏州瑞红电子化学品有限公司 Acrylic copolymer with narrow molecular weight distribution and photosensitive resist composition of acrylic copolymer with narrow molecular weight distribution
CN104411746A (en) * 2012-06-25 2015-03-11 Jsr株式会社 Curable composition, cured film and display element
WO2015077161A1 (en) * 2013-11-21 2015-05-28 3M Innovative Properties Company Liquid optical adhesive compositions
CN104788613A (en) * 2014-01-22 2015-07-22 捷恩智株式会社 Thermosetting resin composition, cured film thereof, thermosetting hard coating agent and display element
JP2015158638A (en) * 2014-02-25 2015-09-03 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and coating film using the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5029836B2 (en) * 2008-03-19 2012-09-19 Ｊｓｒ株式会社 Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof
GB0910747D0 (en) * 2009-06-22 2009-08-05 Unilever Plc Branched polymer dispersants
JP5733557B2 (en) * 2010-06-04 2015-06-10 東レ・ファインケミカル株式会社 Acrylic resin composition for adhesives
JP6451500B2 (en) * 2015-05-22 2019-01-16 Jnc株式会社 Thermosetting resin composition and cured film thereof
JP2016216646A (en) * 2015-05-22 2016-12-22 Jnc株式会社 Method for producing polymer and polymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104411746A (en) * 2012-06-25 2015-03-11 Jsr株式会社 Curable composition, cured film and display element
WO2015077161A1 (en) * 2013-11-21 2015-05-28 3M Innovative Properties Company Liquid optical adhesive compositions
CN104788613A (en) * 2014-01-22 2015-07-22 捷恩智株式会社 Thermosetting resin composition, cured film thereof, thermosetting hard coating agent and display element
JP2015158638A (en) * 2014-02-25 2015-09-03 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and coating film using the same
CN104211867A (en) * 2014-08-21 2014-12-17 苏州瑞红电子化学品有限公司 Acrylic copolymer with narrow molecular weight distribution and photosensitive resist composition of acrylic copolymer with narrow molecular weight distribution

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