JPH115816A - Composition for color filter surface-protecting material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in heat resistance, chemical resistance, hardness, etc., curable in a short time by light or at a low temperature, excellent in productivity, applicable also to a substrate made of resin and useful for liquid display elements by including a specific homopolymer and a cation curing agent. SOLUTION: This composition comprises (A) a homopolymer of a compound such as glycidyl methacrylate having <=2,000 epoxy equivalent and <=2,500 weight-average molecular weight and represented by the formula [R<1> is H or a 1-5C alkyl; (n) is an integer of 1-5] and (B) a cation curing agent such as triphenylsulfonium hexfluorophosphate preferably in an amount of 1-10 pts.wt. based on 100 pts.wt. component A. The composition can be cured by heating at <=120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a color filter surface protective material, and more particularly, to a liquid crystal display device,
CCD (charge coupled device), BBD (bucket brig
ade device) and CID (charge injection device)
The present invention relates to a composition used as a surface protective material for a color filter such as a solid-state imaging device.

[0002]

2. Description of the Related Art A color filter used for a liquid crystal display device or a solid-state image pickup device such as a CCD is generally formed by a pigment dispersion method,
It is colored by methods such as dyeing, printing and electrodeposition,
A surface protection film is formed on the color filter for the purpose of protecting the surface and preventing contamination.

Since the protective film formed on the surface of the color filter is a component constituting an image, it is excellent not only in light transmittance and hue, but also in heat resistance, chemical resistance and surface smoothness. It is required to be excellent in insulation, adhesiveness to a substrate, hardness and the like. It is also required that the surface protective film be easily formed and have excellent productivity.

Conventionally, a thermosetting acrylic resin having high light transmittance in the visible light region has been widely used as the color filter surface protective material to satisfy the above-mentioned required characteristics.

[0005]

However, the acrylic resin has satisfactory properties such as heat resistance, chemical resistance, surface smoothness, adhesion to a substrate, and insulation properties required for a color filter protective film. However, there is a problem that the hardness is not sufficient and the material is easily damaged. In addition, there is another problem that productivity is inferior because curing requires a long time at a high temperature.

At present, a glass substrate is mainly used as a substrate for a color filter. Therefore, even if the substrate is cured at a high temperature for a long time, there is no major problem in terms of heat resistance of the substrate. However, in order to reduce the weight of the color filter and improve the impact resistance, the use of a resin film base as a color filter substrate is being studied in the future, and the resin color filter is being considered. There is a demand for a color filter surface protective material which can be cured at a low temperature and can be used for a substrate.

The present invention has been made in view of the above problems, and has excellent light transmittance and hue as well as heat resistance,
Excellent in chemical resistance, surface smoothness, insulation, adhesion to substrate, hardness, etc., and also applicable to resin substrates with excellent productivity that can be cured in a short time at light or low temperature. An object of the present invention is to provide a composition for a color filter surface protective material that can be used.

[0008]

Means for Solving the Problems and Their Effects In order to achieve the above object, the composition (1) for a color filter surface protective material according to the present invention has the following formula (1):

[0009]

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(Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5). It is characterized by being capable of being cured by light and / or heating to 120 ° C. or less.

Further, the composition (2) for a color filter surface protective material according to the present invention has the following formula (1):

[0012]

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(Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5), and a polymerizable double bond other than the compound. It comprises a copolymer of a compound having the compound and a cationic curing agent, and is characterized in that curing by light and / or heating at 120 ° C. or less is possible.

Further, the composition (3) for a color filter surface protective material according to the present invention has the following chemical formula (2):

[0015]

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(Wherein R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4), and a cationic curing agent. And is characterized by being capable of being cured by light and / or heating at 120 ° C. or lower.

The composition (4) for a color filter surface protective material according to the present invention is represented by the following chemical formula (2):

[0018]

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(Wherein, R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4) and a polymerizable double bond other than the compound. Comprising a copolymer of the compound and a cationic curing agent,
It is characterized in that curing by light and / or heating at 120 ° C. or less is possible.

The composition (5) for a color filter surface protective material according to the present invention has the following formula (1):

[0021]

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(Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5).

[0023]

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(Wherein R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4), and a cationic curing agent. And is characterized by being capable of being cured by light and / or heating at 120 ° C. or lower.

The composition (6) for a color filter surface protective material according to the present invention is represented by the following formula:

[0026]

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(Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5).

[0028]

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(Wherein R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4), and a compound represented by the above formula. It contains a copolymer of a compound having a polymerizable double bond other than the compound represented by the above formula 2, and a cationic curing agent, and can be cured by light and / or heating to 120 ° C. or less. It is characterized by.

According to any one of the color filter surface protective material compositions (1) to (6),
Or containing a polymer containing an epoxy group and a cationic curing agent from a compound represented by the above formula 2,
Since curing by light and / or heating at 120 ° C. or less is possible, after forming a film on the surface of the color filter by a spin coating method or the like, a crosslinking reaction of the polymer is performed in a short time by light or the low-temperature heating. In addition, the coating is cured, and the color filter surface is excellent in light transmittance and hue, and also excellent in heat resistance, chemical resistance, surface smoothness, insulation, adhesion to a substrate, hardness and the like. The surface protective film thus formed can be formed with high productivity.

The composition (7) for a color filter surface protective material according to the present invention is the composition for a color filter surface protective material (1) to (6), wherein the epoxy equivalent of the polymer is 2,000 or less. And a weight average molecular weight of 2500 or more.

According to the color filter surface protective material composition (7), the polymer in the color filter surface protective material composition has an epoxy equivalent of 2000 or less and a weight average molecular weight of 2500 or more. An excellent surface protective film can be formed on the surface of the color filter due to the above-mentioned various properties such as hardness.

The composition (8) for a color filter surface protective material according to the present invention has the reactivity to a cationic curing agent in any one of the compositions (1) to (6) for the color filter surface protective material. It is characterized by containing a reactive diluent.

According to the color filter surface protective material composition (8), since the reactive diluent having reactivity with the cationic curing agent is contained, the viscosity of the composition is reduced by the reactive diluent. , The polymerization reaction can be accelerated. In addition, by making the viscosity low, when forming a coating on the surface of the color filter, the coating can be easily formed by a spin coating method or the like. Further, when the coating formed on the surface of the color filter is cured, the reactive diluent also reacts and becomes a constituent material of the surface protective film. For this reason, it is possible to form a surface protective film that hardly causes shrinkage or the like of the film and has excellent characteristics such as hardness.

The composition for a color filter surface protective material (9) according to the present invention is characterized in that the reactive diluent is a cyclic ether compound in the composition for a color filter surface protective material (8). .

According to the color filter surface protective material composition (9), since the reactive diluent is a cyclic ether compound, when the film formed on the color filter is cured, the film shrinks. Can be formed, and a surface protective film excellent in the above-mentioned various properties such as hardness can be formed.

[0037]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the composition for a color filter surface protective material according to the present invention will be described. The composition for a color filter surface protective material according to the embodiment (1) is represented by the following chemical formula 1:

[0038]

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(Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5) (hereinafter referred to as compound (I)). It contains a homopolymer (hereinafter, referred to as polymer A) and a cationic curing agent.

In the above formula, examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a sec-
Examples thereof include a butyl group, a tert-butyl group, a pentyl group and the like.

Specific examples of the compound (I) include glycidyl acrylate, glycidyl methacrylate, α
-Glycidyl ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5 methacrylic acid −
Epoxy pentyl, acrylic acid-4,5-epoxy pentyl and the like can be mentioned.

The polymerization reaction of the compound (I) can be carried out by the following method. That is, in the presence or absence of a diluent, a polymerization initiator is added to the compound (I), and the polymerization is performed at 40 to 120 ° C, preferably 60 to 120 ° C.
By reacting in a temperature range of 0 ° C. for 5 to 20 hours,
A homopolymer (polymer A) of the compound (I) can be obtained.

The polymerization initiator is not particularly limited, but is conventionally known, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4
Azo compounds such as -dimethylvaleronitrile), organic peroxides such as benzoyl peroxide and acetyl peroxide, inorganic peroxides such as persulfate, hydrogen peroxide and permanganate; and the organic or inorganic peroxides. Substances and sulfites, metasulfites,
A redox initiator combining a reducing agent such as hydrosulfite and bisulfite, or a redox initiator combining the above organic or inorganic peroxide and a metal salt such as an iron salt is exemplified.

Since the amount of the polymerization initiator affects the molecular weight of the polymer A, and the molecular weight increases as the ratio of the polymerization initiator increases, it is preferable to add 0 at a predetermined ratio. The ratio of the polymerization initiator to 100 parts by weight of the compound (I) is preferably 0.1 to 10 parts by weight.

The above-mentioned polymerization reaction can be carried out under the condition where no diluent is present as described above. However, in order to obtain a high molecular weight polymer A, the viscosity is reduced by adding a diluent. It is desirable to accelerate the polymerization reaction. The diluent is not particularly limited as long as it is inert to epoxy groups and radicals, and a commonly used organic solvent (solvent type diluent) can be used. A so-called reactive diluent having reactivity with the curing agent can be used.

Examples of the solvent-type diluent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate. Acetates such as alkyl ether acetates, propylene glycol monoalkyl ether acetates and dipropylene glycol monoalkyl ether acetates; diethylene glycol dialkyl ethers such as ethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol and butyl carbitol , Triethylene glycol dialkyl ethers, propylene glycol Call dialkyl ethers, dipropylene glycol dialkyl ethers, 1,4
Dioxane, ethers such as tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone and butyrolantone; hydrocarbons such as benzene, toluene, xylene, tetramethylbenzene, tetralin, octane, and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, dimethylformamide And normal methylpyrrolidone.

Among the solvent-type diluents, preferred are diethylene glycol monoalkyl ether acetates such as carbitol acetate and the above-mentioned ketones. These solvent-type diluents can be used alone or as a mixture of two or more kinds, and are added at the time of performing a polymerization reaction or before using as a color filter surface protective material after the polymerization reaction. The amount of the solvent-type diluent is the same as that of compound (I) 10
1 to 1000 parts by weight, preferably 5 to 5 parts by weight,
500 parts by weight is more preferred.

Examples of the reactive diluent include compounds having an electron donating property and containing a vinyl group having a high electron density and heterocyclic compounds (for example, “Technical Information Association, edited by the latest UV curable compound”). Technology, September 1991,
Chapter 1, p. 29 "," Polyfile, Vol. 34 "
(1997); 397, p. 44 ").

Examples of the compound containing a vinyl group include:
For example, triethylene glycol divinyl ether, dodecyl vinyl ether, cyclohexane dimethanol divinyl ether, propenyl ether propylene carbonate, aliphatic vinyl ether such as hydroxybutyl vinyl ether, aromatic vinyl ether obtained by reaction of chloroethyl vinyl ether and various phenols, Urethane vinyl ethers obtained by the reaction of isocyanate compounds with hydroxy vinyl ethers and the like, ester vinyl ethers obtained by the reaction of hydroxy vinyl ethers and the like with polycarboxylic acid derivatives,
Examples include various styrene derivatives.

Examples of the heterocyclic compound include monofunctional or polyfunctional bisphenol-based, novolak-based, alicyclic, aliphatic, and amine-based epoxy resins.
3-methyl-3-hydroxymethyloxetane, 1,4
The above-mentioned cyclic ring containing oxetane compounds such as -bis ((3-ethyl-3-oxetanylmethoxy) methyl) benzene, 3-ethyl-3-hydroxymethyloxetane and oxetane oligomers, carbonate compounds such as ethylene and propylene, dioxolane and trioxane; Other examples include ether compounds, and spiro compounds such as oxazoline.

Among the reactive diluents described above, the epoxy resin, the oxetane compound, the carbonate compound, cyclic ether compounds such as dioxolan and trioxane are preferable. These reactive diluents can be used alone or as a mixture of two or more kinds, and are added to the reaction solution when performing the polymerization reaction or before using as a color filter surface protective material after the polymerization reaction. .

The polymer A obtained by the above polymerization reaction is
It is necessary that the polymer A has excellent properties such as heat resistance, chemical resistance, and hardness. For this reason, it is desirable that the polymer A be a polymer having a molecular weight of a certain level or more, and that a sufficient crosslinking reaction takes place during the curing reaction. Is desirable. From such a viewpoint, the molecular weight of the polymer A is preferably 2500 or more,
00 or more is more preferable. The epoxy equivalent is 2000
Or less, more preferably 1000 or less.

After the above-mentioned polymerization reaction, conventionally known polymerization inhibitors such as hydroquinone and p-methoxyphenol are usually added to stabilize the reaction solution. After the addition of the polymerization inhibitor, one or more compounds having at least one double bond in the molecule may be added as a post-addition type diluent for adjusting the viscosity and the like.
Specific examples of the post-addition type diluent include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl acrylate, methacrylic acid Unsaturated fatty acid esters such as phenyl, (meth) acrylamide, (meth) acrylonitrile, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, nitrogen-containing monomers such as diethylaminoethyl (meth) acrylamide, vinyl chloride And aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and vinylnaphthalene; and diene compounds such as butadiene, isoprene, chloroprene, and pentadiene.

Examples of the cationic curing agent contained in the composition for a color filter surface protective material include conventionally known various onium salts such as diazonium salts, iodonium salts and sulfonium salts. Specific examples of the cationic curing agent include, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyl-
4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4′-bis [bis (2-hydroxyethoxyphenyl) sulfonio] phenylsulfidebishexafluorophosphate, diphenyliodonium hexafluoroantimonate, and the like.

These cationic curing agents can be used alone or as a mixture of two or more, and are added to the reaction solution after the completion of the polymerization reaction. The amount of the cationic curing agent is 0.5 to 20 with respect to 100 parts by weight of the polymer A.
It is preferably 1 part by weight, more preferably 1 to 10 parts by weight.

The composition for a color filter surface protective material containing the polymer A, the cationic curing agent, and the solvent-type diluent, the reactive diluent, and the post-addition type diluent which are added as necessary, is used. , Vinyl trichlorosilane,
Vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinylsilane such as vinyltrimethoxysilane, acrylic silane such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane,
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. A silane coupling agent such as aminosilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane, and a leveling agent.

The composition for a color filter surface protective material having the above composition can be cured by light and / or heating at 120 ° C. or lower. Therefore, the composition for a color filter surface protective material, for example, spray method, roll coating method,
After spraying or applying to the surface of the color filter by a method such as spin coating and drying, the ultraviolet light is irradiated with 100 to 5 UV rays.
Irradiate with an intensity of about 00 mJ / cm ² or 120
℃ or less, preferably at a temperature of about 80 to 120 ℃
By heating for 120 minutes, the crosslinking reaction of the epoxy group using the cationic curing agent as a catalyst proceeds and cures, and a surface protective film having a thickness of about several μm can be formed on the surface of the color filter. In particular, when the spin coating method is applied, the color filter surface protective material composition is dropped while rotating the color filter at a predetermined speed, so that the surface protective film having a desired thickness can be easily formed on the color filter surface. Can be formed.

As described above, by using the composition for a color filter surface protective material according to the embodiment (1), a surface protective film can be formed on the color filter surface with high productivity.

Next, the composition for a color filter surface protective material according to the embodiment (2) will be described. The composition for a color filter surface protective material according to the embodiment (2) has the following formula 1:

[0060]

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(Wherein R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5) (compound (I)) and a compound other than the compound (I). It contains a copolymer of a compound having a polymerizable double bond (hereinafter, referred to as compound (III)) (hereinafter, referred to as polymer B) and a cationic curing agent.

The same cationic curing agent as that described in the above embodiment (1) is used.

Examples of the compound (III) include unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride;
Unsaturated fatty acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl acrylate, phenyl methacrylate, and (meth) acrylamide , (Meth) acrylonitrile, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and other nitrogen-containing monomers, vinyl chloride, propene, butene, and other aliphatic vinyls, and styrene , Aromatic vinyl compounds such as α-methylstyrene, p-methylstyrene and vinylnaphthalene; diene compounds such as butadiene, isoprene, chloroprene and pentadiene; ethylene glycol di (meth) acrylate; diethylene glycol Distearate (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Pentaerythritol diacrylate monostearate, fatty acid-modified dipentaerythritol polyacrylate, polyester acrylate,
A reaction product of a dibasic acid anhydride and an alcohol having at least one or more unsaturated groups in one molecule includes a compound having three or more polymerizable groups in one molecule.

The polymerization reaction between the compound (I) and the compound (III) is carried out in the same manner as in the embodiment (1) using the polymerization initiator described in the embodiment (1).
The ratio of the polymerization initiator to 100 parts by weight of the compound (I) and the compound (III) is preferably 0.1 to 10 parts by weight.

Further, the compound (I) and the compound (II)
When performing the polymerization reaction with I) or after the polymerization reaction, the solvent-type diluent, the reactive diluent, the post-addition type diluent, or the like used in the above-described embodiment (1) may be added. After the polymerization reaction, the silane coupling agent or the leveling agent may be added.

The molecular weight of the polymer B obtained by the above polymerization reaction is preferably 2500 or more, more preferably 3500 or more. The epoxy equivalent is preferably 2000 or less,
1000 or less is more preferable.

The composition for a color filter surface protective material according to the embodiment (2), which contains a copolymer (polymer B) of the compound (I) and the compound (III) and a cationic curing agent, is also provided. Curing by light and / or heating at 120 ° C. or less is possible, and a surface protective film having a predetermined thickness can be formed on the surface of the color filter with high productivity by the method described in Embodiment (1).

Next, the composition for a color filter surface protective material according to the embodiment (3) will be described. The composition for a color filter surface protective material according to the embodiment (3) has the following formula 2:

[0069]

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Wherein R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4 (hereinafter, referred to as compound (II)). It contains a polymer (hereinafter, referred to as polymer C) and a cationic curing agent.

As the cationic curing agent, the same compound as the cationic curing agent described in the embodiment (1) can be used.

In the above formula, as the alkyl group represented by R ² , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-
Examples thereof include a butyl group, a tert-butyl group, a pentyl group and the like.

Examples of the compound (II) include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 1- (3,4-epoxycyclohexylmethyl) 6-acrylate. Hexanoate, 6-methacrylic acid-1- (3,4
-Epoxycyclohexylmethyl) hexanoate, α
-Ethylacrylic acid-1- (3,4-epoxycyclohexylmethyl) hexanoate, α-n-propylacrylic acid-1- (3,4-epoxycyclohexylmethyl) hexanoate, α-n-butylacrylic acid-1-
(3,4-epoxycyclohexylmethyl) hexanoate and the like.

The polymerization reaction of the compound (II) is carried out in the same manner as in the above embodiment (1) using the polymerization initiator described in the above embodiment (1). The ratio of the polymerization initiator to 100 parts by weight of the compound (II) is preferably 0.1 to 10 parts by weight.

When the polymerization reaction of the compound (II) is carried out or after the polymerization reaction, the solvent-type diluent, the reactive diluent, and the post-addition type diluent used in the above embodiment (1) are used. Or the like, or the silane coupling agent or the leveling agent may be added after the polymerization reaction.

The molecular weight of the polymer C obtained by the above polymerization reaction is preferably 2500 or more, more preferably 3500 or more. The epoxy equivalent is preferably 2000 or less,
1000 or less is more preferable.

The composition for a color filter surface protective material according to the embodiment (3) containing the homopolymer of the compound (II) (Polymer C), a cationic curing agent, and the like, is also light and / or 120 ° C. or lower. Can be cured by heating, and a surface protective film having a predetermined thickness can be formed on the surface of the color filter with good productivity by the method described in Embodiment (1).

Next, the composition for a color filter surface protective material according to the embodiment (4) will be described. The composition for a color filter surface protective material according to the embodiment (4) is represented by the following chemical formula 2:

[0079]

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Wherein R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4 (compound (II)) and a polymer other than the compound (II). It contains a copolymer of a compound having an acidic double bond (hereinafter, referred to as polymer D) and a cationic curing agent.

As the cationic curing agent, the same compound as the cationic curing agent described in the embodiment (1) can be used.

As the compound having a polymerizable double bond other than the compound (II), the same compound as the compound (III) described in the embodiment (2) can be used.
The polymerization reaction between the compound (II) and the compound (III) is carried out in the same manner as in the above embodiment (1) using the polymerization initiator described in the above embodiment (1). Compound (II)
The ratio of the polymerization initiator to 100 parts by weight of the compound (III) is preferably 0.1 to 10 parts by weight.

The compound (II) and the compound (III)
When performing the polymerization reaction with or after the polymerization reaction, the solvent-type diluent, the reactive diluent, the post-addition type diluent, or the like used in the above embodiment (1) may be added. After the reaction, the silane coupling agent or the leveling agent may be added.

The molecular weight of the polymer D obtained by the above polymerization reaction is preferably 2500 or more, more preferably 3500 or more. The epoxy equivalent is preferably 2000 or less,
1000 or less is more preferable.

The composition for a color filter surface protective material according to the embodiment (4), which contains a copolymer (polymer D) of the compound (II) and the compound (III) and a cationic curing agent, is also provided. Curing by light and / or heating at 120 ° C. or less is possible, and a surface protective film having a predetermined thickness can be formed on the surface of the color filter with high productivity by the method described in Embodiment (1).

Next, the composition for a color filter surface protective material according to the embodiment (5) will be described. The composition for a color filter surface protective material according to the embodiment (5) has the following formula 1:

[0087]

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Wherein R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5 (compound (I)). formula:

[0089]

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(Wherein, R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4) (hereinafter, referred to as a compound (II)). , Polymer E
) And a cationic curing agent.

As the cationic curing agent, the same compound as the cationic curing agent described in the embodiment (1) can be used.

The polymerization reaction between the compound (I) and the compound (II) is carried out in the same manner as in the embodiment (1) using the polymerization initiator described in the embodiment (1). The ratio of the polymerization initiator to 100 parts by weight of the compounds (I) and (II) is preferably from 0.1 to 10 parts by weight.

Further, the compound (I) and the compound (II)
When performing the polymerization reaction with or after the polymerization reaction, the solvent-type diluent, the reactive diluent, the post-addition type diluent, or the like used in the above embodiment (1) may be added. After the reaction, the silane coupling agent or the leveling agent may be added.

The molecular weight of the polymer E obtained by the above polymerization reaction is preferably 2500 or more, more preferably 3500 or more. The epoxy equivalent is preferably 2000 or less,
1000 or less is more preferable.

The composition for a color filter surface protective material according to the embodiment (5), which contains a copolymer (polymer E) of the compound (I) and the compound (II) and a cationic curing agent, is also provided. Curing by light and / or heating at 120 ° C. or less is possible, and a surface protective film having a predetermined thickness can be formed on the surface of the color filter with high productivity by the method described in Embodiment (1).

Next, the composition for a color filter surface protective material according to the embodiment (6) will be described. The composition for a color filter surface protective material according to the embodiment (6) is represented by the following chemical formula 1:

[0097]

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Wherein R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 5 (compound (I)). formula:

[0099]

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Wherein R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4 (compound (II)); And a copolymer of a compound having a polymerizable double bond other than the compound represented by the above formula (hereinafter, referred to as polymer F) and a cationic curing agent.

As the cationic curing agent, the same compound as the cationic curing agent described in the embodiment (1) can be used.

As the compound having a polymerizable double bond other than the compounds (I) and (II), the same compound as the compound (III) described in the above embodiment (2) can be used. The polymerization reaction of the compound (I), the compound (II) and the compound (III) is carried out in the same manner as in the above embodiment (1) by using the polymerization initiator described in the above embodiment (1). Do with. Compound (I), compound
The ratio of the polymerization initiator to 100 parts by weight of (II) and the compound (III) is preferably from 0.1 to 10 parts by weight.

The compound (I) and the compound (II)
When the polymerization reaction of the compound (III) is performed or after the polymerization reaction, the solvent-type diluent, the reactive diluent, the post-addition type diluent, and the like used in the above embodiment (1) are added. Alternatively, the silane coupling agent or the leveling agent may be added after the polymerization reaction.

The molecular weight of the polymer F obtained by the above polymerization reaction is preferably 2500 or more, more preferably 3500 or more. The epoxy equivalent is preferably 2000 or less,
1000 or less is more preferable.

The color filter surface protective material according to the embodiment (6), comprising the compound (I), a copolymer of the compound (II) and the compound (III) (polymer F), a cationic curing agent and the like. The composition for use can also be cured by light and / or heating at 120 ° C. or lower, and form a surface protective film of a predetermined thickness with good productivity on the color filter surface by the method described in Embodiment (1). be able to. The surface protective film formed on the surface of the color filter in the above embodiments (1) to (6) is excellent in light transmittance and hue, and has heat resistance, chemical resistance, surface smoothness, insulation, base material. Excellent in various properties such as adhesion to steel and hardness.

[0106]

EXAMPLES Examples of the composition for a surface protective material for a color filter according to the present invention will be described below.

Example 1 Glycidyl methacrylate (molecular weight 1) was added to a 200 ml four-necked kolben equipped with a stirrer and a curler.
42, 0.1 mol), 14.2 g of methyl methacrylate (molecular weight: 100.1, 0.2 mol), 20.0 g, and 136.8 g of carbitol acetate (solids content: 20) were charged under a nitrogen stream at 85%. ℃, and then 2.2 '
-Add 0.3 g of azobisisobutyronitrile and add 10 g
The polymerization reaction was carried out with stirring for an hour. Thereafter, the reaction solution was filtered through a filter having an opening of 0.2 μm, and used as a cationic curing agent, San-Aid SI80 (Sanshin Chemical Industry Co., Ltd.)
Was added so as to be 3 PHR to obtain a composition 1 for a color filter surface protective material.

Next, the molecular weight of the polymer contained in the composition 1 for color filter surface protective material was measured by GPC (gel permeation chromatography). As a result, the weight average molecular weight of the polymer was 5,100. The epoxy equivalent of the polymer was 342.

Example 2 Glycidyl methacrylate (molecular weight: 1) was added to a 200 ml four-necked kolben equipped with a stirrer and a curler.
42, 0.1 mol) 14.2 g, benzyl methacrylate (molecular weight 176.2, 0.2 mol) 35.2 g, Epikote 828 (epoxy resin, manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 186) 3 g and methyl ethyl ketone 1
15.3 g (solid content: 30) was charged, and the mixture was cooled to 8 under a nitrogen stream.
The temperature was raised to 5 ° C., 0.2 g of benzoyl peroxide was further added, and the polymerization reaction was carried out with stirring for 12 hours. afterwards,
The reaction solution was filtered through a filter having an opening of 0.2 μm, and as a cationic curing agent, San Aid SI100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was added to 2 PHR to obtain a composition 2 for a color filter surface protective material. I got

Example 3 Glycidyl methacrylate (molecular weight: 1) was added to a 200 ml four-necked kolben equipped with a stirrer and a curler.
42, 0.3 mol) 42.6 g, celloxide 2021
6.6 g of P (epoxy resin, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 131) and dimethyldiglycol 9
9.4 g (solid content 30) was charged, and 85
The temperature was raised to 0 ° C., and 0.2 g of benzoyl peroxide was further added to carry out a polymerization reaction with stirring for 10 hours. Thereafter, the reaction solution was filtered through a filter having an opening of 0.2 μm, and Adeka Optomer SP170 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added as a cationic curing agent so as to obtain 4 PHR. Composition 3 was obtained.

Example 4 In a 200 ml four-necked kolben equipped with a stirrer and a curler, 3,4-epoxycyclohexylmethyl acrylate (molecular weight: 182, 0.1 mol)
2 g, methyl methacrylate (molecular weight 100.1, 0.2
Mol) 20.0 g and carbitol acetate 15
2.8 g (solid content: 20) were charged, and 85
C., and 0.15 g of 2,2'-azobisisobutyronitrile was further added, and a polymerization reaction was carried out with stirring for 8 hours. Thereafter, the reaction solution was filtered through a filter having a mesh size of 0.2 μm, and used as a cationic curing agent, San Aid SI.
100 (manufactured by Sanshin Chemical Industry Co., Ltd.) is 2PHR, and Adeka Optomer SP170 (manufactured by Asahi Denka Kogyo Co., Ltd.) is 2PHR.
To obtain a composition 4 for a color filter surface protective material.

Next, the molecular weight of the polymer contained in this composition 4 for color filter surface protective material was measured by GPC (gel permeation chromatography), and the weight average molecular weight of the polymer was 5,800. The epoxy equivalent of the polymer was 382.

Example 5 Glycidyl methacrylate (molecular weight 1) was added to a 200 ml four-necked kolben equipped with a stirrer and a curler.
42, 0.1 mol) 14.2 g, acrylic acid-3,4-
Epoxycyclohexylmethyl (molecular weight 182, 0.2
Mol) 36.4 g, and dimethyldiglycol 118.
1 g (solid matter 30) was charged, the temperature was raised to 80 ° C. under a nitrogen stream, 0.2 g of 2,2′-azobisisobutyronitrile was further added, and the polymerization reaction was carried out with stirring for 12 hours. . Thereafter, the reaction solution was filtered through a filter having a mesh size of 0.2 μm, and used as a cation curing agent.
0 (manufactured by Sanshin Chemical Industry Co., Ltd.) so as to obtain 3 PHR to obtain a composition 5 for a color filter surface protective material.

Next, the molecular weight of the polymer contained in the composition for color filter surface protective material 5 was measured by GPC (gel permeation chromatography), and the weight average molecular weight of the polymer was 7,200. The epoxy equivalent of the polymer was 169.

Example 6 In a 200 ml four-necked kolben equipped with a stirrer and a queuer, 3,4 epoxycyclohexylmethyl acrylate (molecular weight: 182, 0.2 mol) 36.4
g, and 109.2 g of dimethyldiglycol (solid content: 25), heated to 80 ° C. under a nitrogen stream, and further added with 0.1 g of 2,2′-azobisisobutyronitrile for 12 hours. The polymerization reaction was performed while stirring. afterwards,
The reaction solution was filtered through a filter having a mesh size of 0.2 μm, and as a cationic curing agent, San Aid SI100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was added to 3 PHR. I got

Next, when the molecular weight of the polymer contained in the composition 6 for color filter surface protective material was measured by GPC (gel permission chromatography), the weight average molecular weight of the polymer was 8,800. The epoxy equivalent of the polymer was 182.

Test Example 1 One stripe having a width of 20 μm and a height of 0.4 μm
While rotating a PES (polyethersulfone) or glass substrate formed at a pitch of 10 μm, the composition for a color filter surface protective material 1 to 6 manufactured in the above Examples 1 to 6 was dropped, and the substrate was dried. Films of compositions 1 to 6 for a color filter surface protective material were formed on the surface.

Next, the coatings of the compositions 1 and 2 for the color filter surface protecting material were pre-dried at 80 ° C. for 5 minutes, and then heated at 120 ° C. for 30 minutes to cure the coatings and to protect the surface. A film was formed.

The coatings of the compositions 3 to 6 for the surface protective material for color filters were first preliminarily dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays of 365 nm at 200 mJ /.
Irradiated under the condition of cm ² and further heated at 120 ° C. for 10 minutes to cure the coating, thereby forming a surface protective film.

Next, the surface protective film formed by the above method was evaluated by the following method.

(1) Flattening ability: The unevenness of the surface protective film (difference between the highest part and the lowest part) was measured, and the value was gradually reduced by the height (0.4 μm) of the substrate before forming the surface protective film. Was defined as a flattening ability.

(2) Adhesion to substrate, etc. (bending): PES substrate is bent for 1 minute to a diameter of 6 mm with the side on which the surface protective film is formed facing outward, and then the surface protective film is bent. Was visually observed and observed with a microscope, and no crack or peeling was observed.

(3) Surface smoothness (center line average roughness (R
a)): Measured by a contact type film thickness meter. (4) Solvent resistance: NM on the surface protective film heated to 85 ° C
P (N-methylpyrrolidone) and γ-butyrolactone were added dropwise, and the state after 2 minutes was observed, and it was determined that no dissolution or erosion was observed in the surface protective film.

(5) Chemical resistance (alkali): 5 wt% N
immersing the substrate having the surface protective film in an aOH aqueous solution,
The surface protective film was found to have no dissolution or erosion.

(6) Chemical resistance (acid): A solution obtained by mixing 35 wt% of hydrochloric acid, ferric chloride and water at a ratio of 1: 1: 2 and heated to 40 ° C. A substrate having a film was immersed so that no dissolution or erosion was observed in the surface protective film. (7) Hardness: The hardness was measured according to JIS6301.

(8) Heat resistance: After forming the surface protective film on a glass substrate, heat treatment was performed at 200 ° C. for 60 minutes to observe a change in film thickness. did. The results are shown in Table 1 below.

[0127]

[Table 1]

As is clear from the results shown in Table 1 above, the composition 1 for a color filter surface protective material according to the example was prepared.
By using ~ 6, a surface protective film can be formed with good productivity on a substrate to be a color filter, and the formed surface protective film has excellent flattening ability and heat resistance,
Excellent in various properties such as chemical resistance, surface smoothness, adhesion to substrates, and hardness. Therefore, the compositions 1 to 6 for the color filter surface protective material are most suitable as materials for forming the surface protective film of the color filter.

Claims (9)

[Claims] (1) The following formula (1): (Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5), and a cation curing agent. , Light and / or
Alternatively, a composition for a color filter surface protective material, which can be cured by heating at 120 ° C. or lower. 2. The following formula (1): (Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5) and a compound other than the compound having a polymerizable double bond. A copolymer comprising a copolymer and a cationic curing agent;
A composition for a color filter surface protective material, which is capable of being cured by heating at a temperature of 20 ° C. or less. 3. The following formula (2): (Wherein, R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4), and a homopolymer of a compound represented by the formula: A composition for a color filter surface protective material, which can be cured by light and / or heating at 120 ° C. or lower. 4. The following formula (2): (Wherein, R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4), and a compound having a polymerizable double bond other than the compound. A composition for a color filter surface protective material comprising a polymer and a cationic curing agent, wherein the composition can be cured by light and / or heating at 120 ° C. or lower. 5. The following formula (1): (Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5) and a compound represented by the following formula: (Wherein, R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4), and a cationic curing agent; Light and / or
Alternatively, a composition for a color filter surface protective material, which can be cured by heating at 120 ° C. or lower. 6. The following formula (1): (Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5), a compound represented by the following formula: (Wherein, R ² represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4).
And a copolymer of a compound having a polymerizable double bond other than the compound represented by Formula 1 and a compound having a polymerizable double bond, and a cationic curing agent, wherein light and / or 1
A composition for a color filter surface protective material, which is capable of being cured by heating at a temperature of 20 ° C. or less. 7. The composition for a color filter surface protective material according to claim 1, wherein the epoxy equivalent of the polymer is 2000 or less and the weight average molecular weight is 2500 or more. 8. The method according to claim 1, further comprising a reactive diluent having reactivity to the cationic curing agent.
Item 8. The composition for a color filter surface protective material according to any one of Items 7 to 7. 9. The composition for a color filter surface protective material according to claim 8, wherein the reactive diluent is a cyclic ether compound.