KR101052766B1 - Thermosetting Resin Composition - Google Patents

Abstract

The present invention relates to a thermosetting resin composition, comprising a thermosetting resin composition comprising a bisphenol A-type alcohol and a methacrylate or epoxy derived therefrom which act as a crosslinking agent to an acrylic resin containing a carboxyl group or an epoxy group. When forming a protective film by coating, it is possible to provide a color filter protective film of an optical device which satisfies the properties required as a protective film and at the same time effectively improves the crosslinking density, and has excellent mechanical properties and heat resistance and no yellowing at high temperatures.

Description

Thermosetting resin composition

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

Optical devices such as liquid crystal display devices may be exposed to harsh conditions at high temperatures while being processed by organic solvents, acids, alkaline solutions, etc. in the manufacturing process, or by sputtering or the like to form transparent electrode patterns. A protective film is sometimes used to prevent deterioration from such a manufacturing process hazard.

This protective film withstands various treatments as described above, and has excellent adhesion to the substrate or lower layer, high smoothness, high surface hardness, excellent transparency, no change in coloration, yellowing, whitening, etc. over the long term, and excellent heat resistance and light resistance. It should be excellent in chemical resistance and water resistance such as solvent resistance, acid resistance and alkali resistance.

On the other hand, when such a protective film is applied to the color filter of the color liquid crystal display element, it is preferable that the base substrate can smooth the level difference of the 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. Techniques related to such a protective film have been proposed in Japanese Patent Laid-Open 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 that the yellowing phenomenon at a high temperature becomes severe. In addition, the conventional thermosetting resin composition may have an appearance unevenness depending on the surface state after curing, or the surface properties are unstable, so there is a problem in compatibility with other coating liquids used after the thermosetting resin composition, so that the inconvenience of having to modify the surface by irradiating with UV may occur. It was.

An object of the present invention is to solve the problems of the prior art as described above, while satisfying the characteristics required in the past as a protective film, and effectively improve the crosslinking density to excellent mechanical properties and heat resistance, modification of surface properties It is to provide a thermosetting resin composition which is excellent in compatibility with other coating liquids without a very suitable as a protective film forming 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, a-3) of olefinically unsaturated compounds other than a-1), a-2) Including a copolymer, characterized in that it further comprises one or two or more compounds selected from the compounds represented by the following formula (1) or (2).

Formula 1

또는

(여기서, n은 0 내지 5의 정수)이다. Where R ₁ is -H,

or

(Where n is an integer of 0 to 5).

Formula 2

,

,

(n은 1~5의 정수),

(n은 1~5의 정수),

(n은 1~5의 정수),

,

,

,

(n은 0~5의 정수),

(n은 1~5의 정수),

(n은 1~5의 정수) 또는

(n은 0~5의 정수)이다. In Formula 2, R ₁ , R _2, and R ₃ are -H, -OH,-(CH ₂ ) _n -OH (n is an integer of 1 to 5),-(CH ₂ ) _n -CH ₃ (n is An integer of 0 to 5),-(CH ₂ ) _n -CH = CH ₂ (n is an integer of 1 to 5),-(CH ₂ ) _n -CH = CH- (CH ₂ ) _{n '} -CH ₃ (n Is an integer of 1 to 5, n 'is an integer of 0 to 5),

,

,

(n is an integer from 1 to 5),

(n is an integer from 1 to 5),

(n is an integer from 1 to 5),

,

,

,

(n is an integer from 0 to 5),

(n is an integer from 1 to 5),

(n is an integer from 1 to 5) or

(n is an integer of 0-5).

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

1) copolymer

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- Olefin number other than 1) and a-2) includes a copolymer of an unsaturated compound (hereinafter referred to as compound a-3). This copolymer is called 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 this 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, metaconic 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 this structural unit is less than 10 weight% has the tendency for the heat resistance and surface hardness of the protective film obtained to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a copolymer to fall.                     

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; Cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isoacrylate, dicyclopentenyloxyethyl acrylate, isobononyl acrylic Acrylic acid cycloalkyl esters such as late; 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 fumarate 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 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; Aromatic hydrocarbons such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol 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, methyl 2-hydroxy acetate, ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate Ethyl lactic acid, lactic acid propyl, butyl lactic acid, 3-hydroxy propionate methyl, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy propionic acid butyl, 2-hydroxy-3-methyl butanoate, Methoxy methyl acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, ethoxy propyl acetate, butyl ethoxy acetate, propoxy methyl acetate, ethyl propoxy acetate, Propoxy Acetate, Butyl Propoxy Acetate, Butoxy Methyl Acetate, Butoxy Ethyl Acetate, Butoxy Propyl Acetate, Butoxy Butyl Acetate, 2-methoxy Propionic Acid Propyl, 2-methoxy Propionate Prop Phil, 2-Methoxy Propionate, 2-Ethoxy Propionate Methyl, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 3-Methoxy Propionate, 3-Methoxy Propionate, 3-methoxy Propionate Profile Butyl 3-methoxy propionate, methyl 3-ethoxy propionate, ethyl 3-ethoxy propionate, propyl 3-ethoxy propionate, butyl 3-ethoxy propionate, methyl 3-propoxy propionate, ethyl 3-butoxy propionate, Esters such as 3-butoxy propyl propionate and butyl 3-butoxy propionate.

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-2,4 Azo compounds such as -dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, you may use a high oxide together with a reducing agent as a redox initiator.

2) curable compound

In the present invention, the compound represented by Formula 1 or 2 acts as a curing agent for the copolymer A. Therefore, hereinafter, the compound represented by Chemical Formula 1 or 2 is referred to as "curable compound". The curable compounds in the present invention are bisphenol A alcohols and methacrylates, epoxys or phenols derived therefrom, and these curable compounds act as hardeners to effectively increase the crosslinking density to provide mechanical properties and heat resistance. It also serves to improve compatibility with other coating liquids without modification of surface properties.

The content of the curable compound is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the copolymer A.

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. When the content of the curable compound exceeds 100 parts by weight with respect to 100 parts by weight of Copolymer A, a large amount of unreacted curable compound is likely to remain inside the film of the resulting protective film, and as a result, the property of the protective film becomes unstable or the adhesion decreases. 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 a polymerizable compound), a thermal radical polymerization initiator, in addition to the copolymer A and the curable compound as described above.

As the polymerizable compound, monofunctional, bifunctional, trifunctional or higher methacrylate is preferably polymerizable, and is preferably used in order to improve the 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-hydrate Roxy propyl phthalate etc. are mentioned.

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.

Tris hydroxyethyl isocyanurate trimethacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned as trifunctional or more than trifunctional methacrylate.

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

Such a polymeric compound can be contained so that it may be 50-150 weight part with respect to 100 weight of copolymer A, Preferably it is 80-120 weight part. When the content of the polymerizable compound is less than 50 parts by weight with respect to 100 parts by weight of the copolymer A, the flattening property of the resulting protective film is not good.

On the other hand, as the thermal radical polymerization initiator, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (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 the present invention is prepared by uniformly mixing each component of Copolymer A, a curable compound or a polymerizable compound, and a thermal radical polymerization initiator. Usually, the thermosetting resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. That is, copolymer A, a curable compound, a polymerizable compound, a thermal radical polymerization initiator, and other additives are mixed in a predetermined ratio to prepare a thermosetting resin composition in a solution state. The composition of the present invention must include copolymer A and a curable compound.

As a solvent which can be used for preparation of a thermosetting resin composition, the copolymer A and the curable compound can be melt | dissolved uniformly, and what 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 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; Aromatic hydrocarbons such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol 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, methyl 2-hydroxy acetate, ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate Ethyl lactic acid, lactic acid propyl, butyl lactic acid, 3-hydroxy propionate methyl, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy propionic acid butyl, 2-hydroxy-3-methyl butanoate, Methoxy methyl acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy, ethyl propoxy, Propoxy Propyl Acetate, Butyl Propoxy Acetate, Butoxy Methyl Acetate, Butoxy Ethyl Acetate, Butoxy Propyl Acetate, Butoxy Butyl Acetate, 2-methoxy Methyl Propionate, 2-methoxy Propionate Propionate , 2-methoxy propyl propionate, butyl 2-methoxy propionate, methyl 2-ethoxy propionate, ethyl 2-ethoxy propionate, butyl 2-ethoxy propionate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, 3-methoxy propionic acid propyl, 3-methoxy butyl propionate, 3-ethoxy propionate methyl, 3-ethoxy propionate ethyl, 3-ethoxy propionic acid propyl, 3-ethoxy propionate butyl, 3-propoxy propionate methyl, 3 Ester, such as -butoxy ethyl propionate, propyl 3-butoxy propionate, and butyl 3-butoxy propionate, is mentioned. Among these solvents, glycol ethers, ethylene glycol alkyl ether acetate 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. As the high boiling point solvent which can be used together, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide and benzyl ethyl Ether and the like.

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. Examples thereof include FC-129, FC-170C, and FC-430 manufactured by 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, and 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 μm.

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 the following Examples, but the present invention is not limited by the Examples.

<Manufacture 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 cooler 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 a copolymer (hereinafter referred to as copolymer A-1). Solid content concentration of the obtained polymer solution was 33 weight%.

&Lt; Example 1 >

100 parts by weight of the copolymer A-1 obtained in Preparation Example 1 (based on the solid content), 30 parts by weight of 4,4'-isopropylidenediphenol as the curable compound, and 0.1 parts by weight of FC-430 (3M) as the surfactant. The solution was dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone to give a solid content of 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>

100 parts by weight of the copolymer A-1 obtained from Preparation Example 1 (based on the solid content), 30 parts by weight of bisphenol A diglycidyl ether as the curable compound, and 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid. 0.1 parts by weight of KP341 (manufactured by Shin-Etsu Silicone) as a part and a surfactant 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-2).

<Example 3>

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

<Example 4>

100 parts by weight of Copolymer A-1 obtained from Preparation Example 1 (based on the solid content), 20 parts by weight of resorcinol as the curable compound, 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound, and a thermal radical polymerization initiator. 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as an adhesive, 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. After dissolving in ethylene glycol dimethyl ether and N-methyl pyrrolidone, 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-4).

Example 5

100 parts by weight of Copolymer A-1 obtained from Preparation Example 1 (based on the solid content), 20 parts by weight of resorcinol monoacetate as a curable compound, and 100 parts by weight of dipentaerythritol pentamethacrylate as a polymerizable compound, heat 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as a radical polymerization initiator, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and 0.1 part by weight of KP341 (manufactured by Shin-Etsu Silicone) as a surfactant After mixing and dissolving in dimethylethylene dimethyl ether and N-methyl pyrrolidone, 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).

<Example 6>

100 parts by weight of the copolymer A-1 obtained from Preparation Example 1 (based on the solid content), 70 parts by weight of 4,4'-isopropylidenediphenol as the curable compound, and 0.1 parts by weight of FC-430 (3M) as the surfactant. The solution was dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone to give a solid content of 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-6).

<Example 7>

100 parts by weight of the copolymer A-1 obtained from Preparation Example 1 (based on the solid content), 30 parts by weight of 1,1'-biphenyl-4,4'-diol as the curable compound, and FC-430 (3M) 0.1 as the surfactant. By weight, the mixture was dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone, and 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-7).

Comparative Example 1

A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that no curable compound was used.

Comparative Example 2

A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that no curable compound was 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: The surface hardness of the protective film was evaluated by performing a pencil hardness test on the protective film according to the pencil hardness method.

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 irradiation, and the UV resistance of the protective film was evaluated according to the following criteria.

○-within 1% of change in transmission spectrum

×-1% or more change in transmission spectrum

6) Heat resistance: After the protective film was heated in a clean oven at 250 ° C. for 1 hour, the change of the residual film rate was measured.

○-Residual rate change within 3%

×-Residual rate change over 3%

7) Acid resistance: After 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., the change in appearance 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.

9) The presence or absence of yellowing at high temperature: The protective film was heated in a clean oven at 250 ° C. for 60 minutes, and the permeability at 400 nm was measured before and after heating. In general, when the transmittance at 400 nm is low, the yellowing degree of the sample is large.

Transmittance change over U-400nm is over 1%

Transmittance change at no-400nm within 1%

(Table 1)

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example
One Comparative Example 2 Adhesion ○ ○ ○ ○ ○ ○ ○ ○ ○ Surface hardness 5H 5H 5H 5H 5H 5H 5H 3H 3H Transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ Flatness 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than Less than 0.4㎛ Less than 0.3㎛ UV resistance ○ ○ ○ ○ ○ ○ ○ × × Heat resistance ○ ○ ○ ○ ○ ○ ○ × × Acid resistance No change No change No change No change No change No change No change No change No change Alkali resistance No change No change No change No change No change No change No change No change No change Yellowing at high temperature radish radish radish radish radish radish radish U U

From the results in Table 1, as in Examples 1 to 7, bisphenol A alcohols of Formula 1 and methacrylates or epoxy derived therefrom, which act as a crosslinking agent to the acrylic resin containing a carboxyl group or an epoxy group, In the case of forming a protective film by coating a composition including the phenols of Chemical Formula 2, it can be seen that it satisfies the properties required as the protective film and effectively improves the crosslinking density, thereby providing excellent mechanical properties and heat resistance, and no yellowing at high temperatures.

As described in detail above, bisphenol A alcohols of Formula 1 and methacrylates or epoxy derived therefrom which act as crosslinking agents in acrylic resins containing carboxyl or epoxy groups according to the present invention, phenols of Formula 2 In the case of forming a protective film by coating a thermosetting resin composition comprising a satisfies the properties required as a protective film and at the same time effectively improves the crosslinking density, excellent mechanical properties and heat resistance, a color filter protective film of an optical device without yellowing at high temperatures Can provide.

Claims (5)

In the thermosetting resin composition containing the copolymer of a-1) unsaturated carboxylic acid or a-2) unsaturated carboxylic anhydride, a-3) olefinic unsaturated compounds other than said a-1) and a-2), The following bisphenol A alcohols represented by the general formula (1) and methacrylates or epoxys derived therefrom; Or one or two or more compounds selected from the phenols represented by the following formula (2) further comprises a thermosetting resin composition. Formula 1

Where R ₁ is -H,

or

(Where n is an integer of 0 to 5). Formula 2

In Formula 2, R ₁ , R _2, and R ₃ are -H, -OH,-(CH ₂ ) _n -OH (n is an integer of 1 to 5),-(CH ₂ ) _n -CH ₃ (n is An integer of 0 to 5),-(CH ₂ ) _n -CH = CH ₂ (n is an integer of 1 to 5),-(CH ₂ ) _n -CH = CH- (CH ₂ ) _{n '} -CH ₃ (n Is an integer of 1 to 5, n 'is an integer of 0 to 5),

,

,

(n is an integer from 1 to 5),

(n is an integer from 1 to 5),

(n is an integer from 1 to 5),

,

,

,

(n is an integer from 0 to 5),

(n is an integer from 1 to 5),

(n is an integer from 1 to 5) or

(n is an integer of 0-5). The thermosetting resin composition according to claim 1, wherein one or two or more compounds selected from the compounds of Formula 1 or 2 are included in an amount of 1 to 100 parts by weight based on 100 parts by weight of the copolymer. The thermosetting resin composition according to claim 1, further comprising a polymerizable compound having an ethylenically unsaturated bond in an amount of 50 to 150 parts by weight based on 100 parts by weight of the copolymer. The thermosetting resin composition according to claim 1, further comprising 1 to 20 parts by weight of a thermal radical polymerization initiator with respect to 100 parts by weight of the copolymer. The protective film for optical devices formed from the thermosetting resin composition of any one of Claims 1-4.