KR100804063B1 - Thermosetting resin composition for covering material of photo-device - Google Patents

Abstract

The present invention relates to a thermosetting resin composition comprising a diamine acting as a crosslinking agent to an acrylic resin containing a carboxyl group or an epoxy group, and a polyfunctional monomer containing an ethylenically unsaturated group, a thermal radical polymerization initiator, and the like, which is coated In the case of forming a protective film, the color filter protective film of an optical device having high mechanical properties and heat resistance and excellent yellowing at high temperatures can be provided by satisfying the properties required as the protective film and effectively improving the crosslinking density.

Liquid Crystal Display * Protective Film * Thermosetting Resin * Polycarboxylic Acid Anhydride

Description

Thermosetting resin composition for covering material of photo-device

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition useful as a protective film forming material for an optical device, and more particularly, to a thermosetting resin composition suitable for forming a protective film provided to prevent alteration of a substrate generated during a manufacturing process of an optical device such as a liquid crystal display device. It is about.

Optical devices such as liquid crystal display devices are subjected to harsh processing such as being immersed by organic solvents, acids, alkaline solutions, etc. during the manufacturing process, or subjected to localized high temperature heating on the surface by sputtering when forming wiring electrode layers. . Therefore, in order to prevent the deterioration at the time of manufacture, these elements may provide a protective film in the surface.

This protective film withstands various treatments as described above, and has excellent adhesion to substrates or lower layers, high smoothness, surface hardness, and transparency, and excellent heat resistance and light resistance without alteration such as coloring, yellowing, and whitening over long periods. What is excellent in chemical-resistance, such as alkali resistance, water resistance, etc. is calculated | required.

On the other hand, when applying such a protective film to the color filter of a color liquid crystal display element, it is preferable that the base board can smooth the level difference of a general color filter.

That is, as the protective film, a material capable of satisfying the above characteristics and flattening the level difference on the surface of the color filter serving as the base substrate is required.

As a technique related to such a protective film, it has been proposed in Japanese Unexamined Patent Publication Nos. 2000-103937, 2000-119472 and 2000-143772.

As the material to be applied to such a protective film, a composition composed of an acrylic resin containing a carboxyl group or an epoxy group, a polyfunctional monomer containing an ethylenically unsaturated group serving as a crosslinking agent, and a thermal polymerization initiator are used. In the case of such a conventional thermosetting resin composition, mechanical properties are not excellent, and in particular, yellowing phenomenon is often exhibited due to poor heat resistance at high temperatures. Therefore, in order to prevent such a phenomenon, the polyfunctional monomer containing an ethylenically unsaturated group is excessively used, and such an excessive use has a disadvantage in that yellowing at a high temperature becomes severe.

An object of the present invention is to solve the problems of the prior art as described above, by using a diamine as a crosslinking agent to satisfy the characteristics required in the past as a protective film, while effectively improving the crosslinking density to excellent mechanical properties and heat resistance, It is providing the thermosetting resin composition which is very suitable as a protective film formation material for optical devices. Another object of the present invention is to provide a thermosetting resin composition free from yellowing at high temperatures.

Thermosetting resin composition of the present invention for achieving the above object is a-1) unsaturated carboxylic acid or a-2) unsaturated carboxylic acid anhydride and a-3) olefinically unsaturated compounds other than a-1), a-2) A thermosetting resin composition comprising a copolymer (referred to as Copolymer A), characterized by further comprising one or two or more compounds selected from the following general formula (1).

In the above formula, X is a monovalent amine group or an isocyanate group, and Y is one or two or more divalent groups selected from the following general formulas (2) or (3).

The present invention will be described in more detail as follows.

1) Copolymer A

In the present invention, a-1) unsaturated carboxylic acid or unsaturated carboxylic anhydride (hereinafter referred to as compound a-1), a-2) epoxy group-containing unsaturated compound (hereinafter referred to as compound a-2), a-3) said a- And copolymers of olefinically unsaturated compounds (hereinafter referred to as compound a-3) other than 1) and a-2). Let this copolymer be copolymer A.

Copolymer A used in the present invention contains 5 to 40% by weight, preferably 10 to 30% by weight of structural units derived from compound a-1. If the copolymer having less than 5% by weight of the structural unit tends to have low heat resistance, chemical resistance and surface hardness, and the copolymer having a content of more than 40% by weight is reduced in storage stability. Specific examples of the compound a-1 include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, straconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds a-1 can be used individually or in combination.

In addition, copolymer A of the present invention contains 10 to 70% by weight, preferably 20 to 60% by weight of structural units derived from compound a-2. The copolymer of which the structural unit is less than 10% by weight tends to lower the heat resistance and surface hardness of the protective film obtained, and when it exceeds 70% by weight, the storage safety of the copolymer tends to be lowered.

Specific examples of the compound a-2 include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy heptyl , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds a-2 can be used alone or in combination.

On the other hand, copolymer A contains 10 to 70% by weight, preferably 20 to 50% by weight of structural units derived from compound a-3. When this structural unit is less than 10 weight%, the storage stability of copolymer A tends to fall, and when it exceeds 70 weight%, there exists a tendency for the heat resistance and surface hardness of copolymer A to fall. Specific examples of the compound a-3 include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isobononyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fmarate and diethyl itaconic acid; Hydroxyalkyl esters such as 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate; And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Dual styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene and the like are preferred in view of copolymerization reactivity and heat resistance. These compounds a-3 can be used alone or in combination.                     

Copolymer A obtained from the above compounds a-1, a-2 and a-3 has a carboxyl group or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating without using a special curing agent.

As a solvent which can be used for the synthesis | combination of copolymer A, Alcohol, such as methyl alcohol and ethyl alcohol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol ethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; Propylene glycol alkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxy propionate, methyl 2-hydroxy-2-methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl hydroxy acetate, hydroxy Ethyl acetate, butyl butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy propionate methyl, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy butyl propionate, 2- Hydroxy-3-methyl butyrate methyl, methoxy methyl acetate, methoxy ethyl acetate, methoxy acetate propyl, butyl acetate, ethoxy methyl, ethoxy ethyl acetate, ethoxy propyl, ethoxy butyl acetate, Methyl Propoxy Acetate, Propoxy Ethyl Acetate, Propoxy Acetate, Butyl Propoxy Acetate, Butoxy Methyl Acetate, Butoxy Ethyl Acetate, Butoxy Propyl Acetate, Butyl Propoxy Acetate, Butoxy Acetate Methoxyacetate , Butoxy ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxy propionate, ethyl 2-methoxy propionate, propyl 2-methoxy propionic acid, butyl 2-methoxy propionate, methyl 2-ethoxy propionate Ethyl 2-ethoxy propionate, propyl 2-ethoxy propionate, butyl 2-ethoxy propionate, methyl 2-butoxy propionate, ethyl 2-butoxy propionate, propyl 2-butoxy propionate, butyl 2-butoxy propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, 3-ethoxy propionic acid methyl, 3-ethoxy propionic acid, 3-ethoxy propionic acid propyl, 3 Butyl ethoxy propionate, 3-propoxy methyl propionate, 3-propoxy ethyl propionate, 3-propoxy propionic acid propyl, 3-propoxy propionic acid butyl, 3-butoxy propion Methyl, can be mentioned a 3-butoxy-ethyl, 3-butoxy-propionic acid propyl esters such as 3-butoxy-propionic acid butyl.

In addition, as a polymerization initiator which can be used for the synthesis | combination of copolymer A, as long as it is generally known as a radical polymerization initiator, any can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2 Azo compounds, such as (4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy pibarate, 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.

(2) Curable Compound B

In the present invention, the compound represented by Formula 1 (curable compound B) acts as a curing agent for the copolymer A.

The content is 1-100 weight part with respect to 100 weight part of said copolymers A, Preferably it is 10-50 weight part. If the content is less than 1 part by weight with respect to 100 parts by weight of copolymer A, it is difficult to obtain a protective film having a sufficiently high crosslink density, and the various resistances of the protective film may be lowered. And when curable compound B exceeds 100 weight part with respect to 100 weight part of copolymers A, a large amount of unreacted curable compound B tends to remain in the film | membrane of the protective film obtained, As a result, a property of a protective film becomes unstable or adhesiveness falls. Easy to be

(3) Other

The thermosetting resin composition of the present invention may contain a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as polymerizable compound C) and a thermal radical polymerization initiator in addition to the copolymer A and the curable compound B as described above.

As the polymerizable compound C, a monofunctional, bifunctional or trifunctional or higher methacrylate is preferable from the viewpoint of good polymerizability and improved heat resistance and surface hardness of the resulting protective film.

Examples of monofunctional methacrylates include 2-hydroxy ethyl methacrylate, carbitol methacrylate, isobornyl methacrylate, 3-methoxy butyl methacrylate, 2-methacryloyl oxy ethyl 2-hydroxy Propyl phthalate, and the like.

As bifunctional methacrylate, ethylene glycol methacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol methacrylate, propylene glycol methacrylate, tetraethylene glycol methacrylate, bisphenoxy Ethyl alcohol fluorene diacrylate, etc. are mentioned.

Trifunctional or more than trifunctional methacrylates include trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dipentaeryth. Lithol hexamethacrylate etc. are mentioned.

These monofunctional, bifunctional or trifunctional or higher methacrylates may be used alone or in combination.

Such polymerizable compound C may be contained in an amount of 50 to 150 parts by weight, preferably 80 to 120 parts by weight, based on 100 parts by weight of copolymer A. When the content of the polymerizable compound C is less than 50 parts by weight with respect to 100 parts by weight of the copolymer A, the planarity of the protective film obtained is not good, and when it exceeds 150 parts by weight, the adhesion of the protective film obtained is likely to be lowered.

On the other hand, as a thermal radical polymerization initiator, 2,2'- azobis isobutyronitrile, 2,2'- abis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile) and 1,1'-azobis-1-cyclohexylnitrile; Organic peroxides such as benzoyl peroxide, t-butyl peroxide, 1,1'-bis- (t-butyl peroxy) cyclohexane, and the like.

The thermal radical polymerization initiator may be contained in an amount of 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of copolymer A. When the content of the thermal radical polymerization initiator is less than 1 part by weight, the heat resistance and flattening property of the protective film tend to be lowered, and when it exceeds 20 parts by weight, various resistances of the protective film tend to be lowered.

The thermosetting resin composition of this invention is manufactured by uniformly mixing each component of copolymer A, curable compound B, or polymeric compound C, and a thermal radical polymerization initiator as mentioned above. Usually, the thermosetting resin composition of the present invention is dissolved in a suitable solvent and used in solution. That is, copolymer A, curable compound B, polymerizable compound C, thermal radical polymerization initiator, and other additives are mixed in a predetermined ratio to prepare a thermosetting resin composition in solution. The composition of the present invention must include copolymer A and curable compound B.

As a solvent which can be used for preparation of a thermosetting resin composition, each component of copolymer A, the curable compound B, the polymeric compound C, and a thermal radical polymerization initiator can be melt | dissolved uniformly, and it does not react with any component. Can be used. Specifically, Alcohol, such as methyl alcohol and ethyl alcohol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol ethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; Propylene glycol alkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxy propionate, methyl 2-hydroxy-2-methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl hydroxy acetate, hydroxy acetate Ethyl, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy propionate methyl, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy butyl propionate, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, ethoxy propyl acetate, ethoxy butyl acetate, pro Methyl Foxpoxy, Ethyl Propoxy, Propyl Propoxy, Butyl Propoxy, Butoxy Methyl, Butoxy Ethyl, Butoxy Ethyl, Butoxy Propyl, Butyl Propoxy, Butoxy Acetate , Butoxy ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxy propionate, ethyl 2-methoxy propionate, propyl 2-methoxy propionic acid, butyl 2-methoxy propionate, methyl 2-ethoxy propionate Ethyl 2-ethoxy propionate, propyl 2-ethoxy propionate, butyl 2-ethoxy propionate, methyl 2-butoxy propionate, ethyl 2-butoxy propionate, propyl 2-butoxy propionate, butyl 2-butoxy propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, 3-ethoxy propionic acid methyl, 3-ethoxy propionic acid, 3-ethoxy propionic acid propyl, 3 Butyl ethoxy propionate, 3-propoxy methyl propionate, 3-propoxy ethyl propionate, 3-propoxy propionic acid propyl, 3-propoxy propionic acid butyl, 3-butoxy propion Methyl, can be mentioned a 3-butoxy-ethyl, 3-butoxy-propionic acid propyl esters such as 3-butoxy-propionic acid butyl. Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol ethers are preferable in view of solubility, reactivity with each component, and convenience of coating film formation.                     

Moreover, it is also possible to use a high boiling point solvent together with the said solvent. High boiling point solvents that can be used together include N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide and benzyl ethyl ether. Etc. can be mentioned.

In addition, the thermosetting resin composition of this invention may contain other components of that excepting the above as needed in the range which does not impair the objective of this invention.

Here, as another component, surfactant for improving applicability | paintability is mentioned. Examples of the surfactant include fluorine and silicone-based surfactants, and examples thereof include FC-129, FC-170C, and FC-430 of 3M. Such surfactant can be used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of copolymer A. When the amount of the surfactant exceeds 5 parts by weight, bubbles are likely to occur during application.

Moreover, in order to improve the adhesiveness with gas, an adhesion | attachment adjuvant can be used. As the adhesion aid, a functional silane coupling agent is preferably used. For example, trimethoxy silyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate Propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. Such adhesion aid may be used in an amount of 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of copolymer A. When the amount of the adhesion aid exceeds 20 parts by weight, the heat resistance tends to be lowered.

The composition solution prepared as described above is used after filtering using a Millipore filter having a pore diameter of about 0.2 to 0.5㎛.

The target protective film can be obtained by apply | coating the thermosetting resin composition of this invention to a base substrate, and processing it for 20 to 80 minutes at 160-260 degreeC in oven.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, and after stirring with nitrogen, the stirring was started gently. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing a copolymer (hereinafter referred to as copolymer A-1). Solid content concentration of the obtained polymer solution was 33 weight%.

100 parts by weight of the obtained copolymer A-1 (solid content), 30 parts by weight of 1,4-bis-4-aminophenoxybenzene as the curable compound B, and 0.1 parts by weight of FC-430 (3M) as the surfactant were mixed with diethylene. After dissolving in glycol dimethyl ether and N-methyl pyrrolidone, the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (henceforth S-1).

Example 2

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer A-1.

100 parts by weight of the obtained copolymer A-1 (solid content), 30 parts by weight of 2,2-bis-4-aminophenoxyphenylpropane as the curable compound B, and 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid. And 0.1 parts by weight of KP341 (manufactured by Shin-Etsu Silicone) as a surfactant was dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone so that the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (henceforth S-2).

Example 3

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer A-1. Solid content concentration of the obtained polymer solution was 33 weight%.

100 parts by weight of the obtained copolymer A-1 (solid content), 20 parts by weight of 1,3-bis-4-aminophenoxybenzene as the curable compound B, 100 parts by weight of trimethylpropane trimethacrylate as the polymerizable compound C, 5 parts by weight of benzoyl peroxide as a thermal radical polymerization initiator and 0.1 parts by weight of FC-170C (3M) as a surfactant were mixed and dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone so that the solid content was 25% by weight. It was. Then, it filtered by the filter of 0.45 micrometer of pore diameters, and prepared the thermosetting resin composition solution (henceforth S-3).

Example 4

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen replacement, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer A-1. Solid content concentration of the obtained polymer was 33 weight%.

100 parts by weight of the obtained copolymer A-1 (solid content), 20 parts by weight of 1,4-bis-4-aminophenoxybenzene as the curable compound B, and 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound C. , 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as a thermal radical polymerization initiator, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and KP341 (manufactured by Shin-Etsu Silicone) as a surfactant. The parts by weight were mixed and dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone so that the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometer of pore diameters, and prepared the thermosetting resin composition solution (S-4).

Example 5

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer A-1. Solid content concentration of the obtained polymer solution was 33 weight%.

100 parts by weight of the obtained copolymer A-1 (solid content), 20 parts by weight of bis-4,4-aminophenoxy sulfone as the curable compound B, 100 parts by weight of dipentaerythritol pentamethacrylate as the polymerizable compound C, 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as thermal radical polymerization initiator D, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and KP341 (manufactured by Shin-Etsu Silicone) as a surfactant 0.1 The weight parts were mixed and dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone so that the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometer of pore diameters, and prepared the thermosetting resin composition solution (henceforth S-5).

Comparative Example 1

A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that the curable compound B was not used.                     

Comparative Example 2

A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that the curable compound B was not used.

The thermosetting resin composition as described above was applied to a film thickness of 2 μm on a glass substrate using a spin coater, and then fired at 220 ° C. for 30 minutes in a clean oven to form a protective film on the glass substrate.

After the protective film was formed, the adhesion, surface hardness, transparency, planarization, UV resistance, heat resistance, acid resistance, and alkali resistance were measured by the following methods, and the results are shown in Table 1 below.

1) Adhesiveness: According to the checkered tape method, 100 checkered patterns were formed on the protective film by a cutter knife, and the adhesion test was carried out to measure the number of peeled checkered patterns, and the adhesiveness of the protective film was evaluated according to the following criteria.

○-5 or less peeled checkerboard patterns,

△-6 to 49 peeled checkered patterns

×-Number of peeled checkered tiles 50 or more

2) Surface hardness: According to the pencil hardness method, the surface hardness of the protective film was evaluated by the pencil hardness test method for the protective film.

3) Transparency: The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer, and the transparency of the protective film was evaluated according to the following criteria.                     

○-95% minimum transmittance

△-minimum transmittance above 90-95%

×-minimum transmittance below 90%

4) Flattenability: The surface irregularities of the protective film were irradiated using an α step to measure the level difference of the substrate.

5) UV resistance: The protective film was irradiated with UV. The transmission spectrum of the protective film was measured before and after UV irradiation, and the UV resistance of the protective film was evaluated according to the following criteria.

○-within 1% of change in transmission spectrum

×-change of transmission spectrum is more than 1%

6) Heat resistance: The protective film was heated in a clean oven at 240 ° C. for 60 minutes, the transmission spectrum was measured before and after heating, and the heat resistance of the protective film was evaluated according to the following criteria.

○-within 1% of change in transmission spectrum

× 1% change in transmission spectrum

7) Acid Resistance: The glass substrate on which the protective film was formed was immersed in a 25 wt% aqueous hydrochloric acid solution for 30 minutes at 30 ° C., and then the appearance change of the protective film was observed to evaluate the acid resistance of the protective film.

8) Alkali resistance: After the glass substrate on which the protective film was formed was immersed in 10 wt% sodium hydroxide aqueous solution for 30 ° C. for 60 minutes, the change in appearance of the protective film was observed to evaluate the alkali resistance of the protective film.                     

From the results of Table 1, a protective film is coated by coating a composition of an example in which an acrylic resin containing a carboxyl group or an epoxy group, a diamine of the general formula (1) serving as a crosslinking agent, a polyfunctional monomer containing an ethylenically unsaturated group, a thermal radical polymerization initiator, and the like are combined. It can be seen that when forming the satisfies the properties required as a protective film and at the same time effectively improve the crosslinking density, excellent mechanical properties and heat resistance, there is no yellowing at high temperatures.

As described above in detail, according to the present invention, a polyfunctional monomer and a thermal radical polymerization initiator including a diamine of the general formula (1) serving as a crosslinking agent in an acrylic resin containing a carboxyl group or an epoxy group and containing an ethylenically unsaturated group When forming a protective film by coating the blended thermosetting resin composition, it satisfies the characteristics required as a protective film, and effectively improves the crosslinking density, thereby providing a color filter protective film of an optical device having excellent mechanical properties and heat resistance and no yellowing at high temperatures. can do.

Claims (4)

Thermosetting resin containing a copolymer of a-1) unsaturated carboxylic acid or a-2) unsaturated carboxylic acid anhydride, and a-3) olefinic unsaturated compounds other than said a-1) and a-2) (referred to as copolymer A) In the composition, The olefinically unsaturated compound is methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cycloalkyl ester, acrylic acid cycloalkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, dicarboxylic acid diester, hydroxyalkyl ester, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, At least one compound selected from the group consisting of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, The thermosetting resin composition for a photonic device protective film, characterized in that it further comprises one or two or more compounds selected from the group represented by the following formula (1). Formula 1

In the above formula, X is a monovalent amine group or isocyanate group, Y is 1 type, or 2 or more types of bivalent groups chosen from following General formula (2) or (3). Formula 2

Formula 3

The thermosetting resin composition for an optical device protective film according to claim 1, wherein at least one compound represented by Chemical Formula 1 is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the copolymer A. The thermosetting resin composition for an optical device protective film according to claim 1, further comprising 50 to 150 parts by weight of at least one monofunctional, bifunctional or trifunctional or higher methacrylate, based on 100 parts by weight of the copolymer A. . The thermosetting resin composition for an optical device protective film according to claim 1 or 3, further comprising 1 to 20 parts by weight of a thermal radical polymerization initiator based on 100 parts by weight of the copolymer A.