JPS61252225A - Thermosetting polymer composition - Google Patents

Abstract

PURPOSE:The titled composition which can give a film excellent in adhesion, light resistance, heat resistance, scratch resistance, water resistance, solvent resistance, stain resistance and toughness and suitable for spin coating, containing a specified polymer and a polycarboxylic acid anhydride. CONSTITUTION:100pts.wt. polymer, weight-average MW (in terms of PS) of 5,000-500,000 and a MW distribution <=10, comprising 60wt% or above units derived from a compound (A) of formula I (wherein R is H or a lower alkyl and n is 1-5) and 10wt% or below units drived from other polymerizable monomers is mixed with 0.01-50pts.wt. at least one compound (B) selected from among polycarboxylic acids (anhydrides), e.g., pyromellitic anhydride and, optionally, at least one member (C) selected from among a silane coupling agent (a) of formula II (wherein X is vinyl, COOH or NCO, Y is alkylene or phenylene and R is CH3-C3H7), a titanate coupling agent (b) and a compound (c) having at least two epoxy groups by a solution mixing process.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermosetting polymer composition, and particularly to a thermosetting polymer composition that is excellent in various physical properties of a coating film as a coating film forming material.

[Conventional technology]

Conventionally, in order to prevent deterioration and damage to the substrate surface of various articles, it has been widely practiced to form a protective coating on the surface of the substrate. Such protective coatings have high adhesion to the substrate, are smooth, have high hardness and toughness, and have high scratch resistance, high heat resistance and light resistance, and do not discolor over a long period of time. Properties such as no deterioration in quality and excellent water resistance and solvent resistance are required.

Furthermore, in recent years, various liquid crystal display elements and solid-state image sensors equipped with color filters have been announced.

These color filters are formed on a transparent substrate such as glass or a solid-state image sensor through the following steps, for example. That is, it imparts photosensitivity to polyvinyl alcohol, gruel, gelatin, etc.

It is applied uniformly onto a substrate, and only the first color pattern is photocured and developed using a mask exposure method, and the other portions are removed. 1. Dyeing this pattern with a dye that has predetermined spectral characteristics.
A transparent anti-dye protection layer is then applied. The pattern portion of the second color is also dyed using the same process and coated with an anti-dye protection layer. A portion of the third color patter is also dyed using the same process, and finally a surface protective layer is formed. This anti-dyeing protective layer and surface protective layer have the performance necessary for the protective coating film,
That is, in addition to adhesion, smoothness, toughness, heat resistance, light resistance, water resistance, and solvent resistance, performance such as transparency and resistance to staining with dyes is required. Furthermore, the materials forming these layers are applied as a solution in order to form an anti-dye protection layer and a surface protection layer, but a spin coating method using a spin coater is sometimes used to form a uniform coating film. Therefore, it is required to be suitable for this coating method as well.

Thermoplastic resins such as polystyrene and polycarbonate have conventionally been known as coating film forming materials, but these coating films have the drawbacks of poor adhesion to a substrate, low heat resistance, and low solvent resistance. In addition, thermosetting polymer resins such as melamine resin and epoxy resin are known as other paint film forming materials, but these paint films are hard and brittle, and have particularly low transparency and stain resistance. It has the disadvantage that it is not suitable for spin coating. Further, thermosetting acrylic resins are known as coating film forming materials, but their coatings have the drawback of having low adhesion to substrates and being unsuitable for spin coating.

In addition, as materials for forming protective layers in the production of color filters, materials made of cyclized rubber and sensitizers, materials made of polymethyl methacrylate, etc. have been proposed (
JP-A-59-49507).

However, even if a protective layer is formed using these materials, it is not possible to obtain a protective layer that has the above-mentioned properties required for a protective layer in a well-balanced manner. However, materials made of polymethyl methacrylate have poor adhesion to dyed substrate layers and poor heat resistance, making it impossible to obtain satisfactory color filters. There is.

[Problem that the invention seeks to solve]

As described above, it is not possible to obtain a coating film that satisfies the above-mentioned required properties in a well-balanced manner using conventional coating film-forming materials. Furthermore, many of the coatings were not suitable for spin coating.

The purpose of the present invention is to solve the above-mentioned problems of the prior art, and to provide smoothness, toughness, high heat resistance and light resistance, as well as adhesion to substrates, transparency, water resistance, solvent resistance and stain resistance. An object of the present invention is to provide a thermosetting polymer composition which can form a coating film that is excellent in all respects, has high hardness, and is suitable for spin coating.

[Means for solving problems]

The present invention, as a means to solve the above problems, provides (A)
General formula (I) [In the formula, R is a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and n is 1 to
an integer of 5] A polymer containing 60% by weight or more of a monomer unit derived from a compound represented by (B) 0.01 to 50 parts by weight per 100 parts by weight of the polymer;
The present invention provides a thermosetting polymer composition containing parts by weight of a polycarboxylic anhydride and at least one compound selected from polycarboxylic acids.

The polymer that is component (A) of the composition of the present invention includes a homopolymer consisting of one type of compound of general formula (I), a copolymer consisting of two or more types of compounds of general formula (I), and a copolymer consisting of one or more compounds of general formula (I) and other polymerizable monomers.

Specific examples of the compound of general formula (I) include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and acrylic M
-3,4-epoxybutyl, 3,4-epoxybutyl methacrylate, 4,5-epoxypentyl methacrylate, 6,7-epoxypentyl acrylate, 6,7-epoxypentyl methacrylate, α- Mention may be made of 6°7-epoxypentyl ethyl acrylate.

Among these compounds, in general formula (I), R is preferably a hydrogen atom, a methyl group or an ethyl group, and n is preferably 1 or 2.

General formula (I) of the polymer which is component (A) of the composition of the present invention
) is the monomer unit content derived from the compound.

It needs to be 60% by weight or more, preferably 80% by weight or more, and particularly preferably 100% by weight.

If the monomer unit content is less than 60% by weight, the adhesion of the composition to the substrate is insufficient and the intended purpose cannot be achieved. Compositions with this content of 80% by weight or more exhibit particularly good adhesion to various substrates.

In the polymer of component (A), other polymerizable monomers that can be used together with the compound of general formula (I) to form a copolymer include 1, for example, methyl acrylate, methyl methacrylate, acrylic Acrylic acid or methacrylic acid esters such as ethyl acid, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl acrylate, phenyl methacrylate: styrene, α-methylstyrene, p-methylstyrene , vinyl aromatic compounds such as vinylnaphthalene. Among these polymerizable monomers, it is particularly preferable to use esters of acrylic acid or methacrylic acid in terms of forming a tougher and more transparent coating film.

In addition, monopolymerizable monomers include acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxypropyl acrylate.
-Functional acrylic compounds such as hydroxybutyl and 2-hydroxybutyl methacrylate; diene compounds such as butadiene, isoprene, piperylene, dimethylbutadiene, etc. can also be used, but the content of monomer units derived from these compounds It is desirable that the content of the component (A) does not exceed 10% by weight; if the content exceeds 10% by weight, the adhesive strength to the substrate will decrease.

The copolymerization form of the copolymer of the above polymerizable monomer and the compound of general formula <1> is not particularly limited, and may be a random copolymer, a block copolymer, etc. by addition polymerization, or a copolymer The method may be either a solution polymerization method or an emulsion polymerization method, but a solution radical polymerization method using dioxane, tetrahydrofuran, ethylene glycol monoethyl ether acetate, etc. as a solvent is particularly preferred.

The molecular weight of the polymer of component (A) is not particularly limited as long as the composition of the present invention can be applied to a substrate as a uniform film, but usually the weight average molecular weight in terms of polystyrene is s
, ooo~soo, ooo, preferably 10,000~
200,000, and can be appropriately selected depending on the purpose and conditions of coating film formation, such as the thickness of the coating film to be formed and the coating method.

In addition, the molecular weight distribution (weight average molecular weight/number average molecular weight) of the polymer of component (A) is the storage stability when made into a solution,
For reasons such as filterability, it is preferably 10 or less.

The composition of the present invention contains a polycarboxylic anhydride or a polycarboxylic acid as component (B). Specific examples of polycarboxylic anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citracone anhydride, dodecenylsuccinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, and methyl anhydride. Aliphatic dicarboxylic acid anhydrides such as tetrahydrophthalic acid and hymic anhydride; 1.2,3.4-butanetetracarboxylic dianhydride;
Aliphatic polycarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride; aromatic polycarboxylic acid anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ethylene glycol bistrimellitic anhydride Examples thereof include ester group-containing acid anhydrides such as Tito, glycerol tristrimeritite, etc., and aromatic polycarboxylic acid anhydrides are particularly preferred.

Furthermore, as the carboxylic acid anhydride, a commercially available epoxy resin curing agent consisting of a colorless acid anhydride can also be suitably used, and a specific example is Adeka Hardener EH-700 (
Product name (same hereinafter), manufactured by Kadenka Kogyo Co., Ltd.), Rikajid-HH1 MH-700 (manufactured by Shin Nihon Rika Co., Ltd.), Epiki:, 7126. Same YH-306, Same DX-126 (
(manufactured by Yuka Shell Epoxy Co., Ltd.).

Specific examples of polycarboxylic acids used in the present invention include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid; Alicyclic polycarboxylic acids such as 1,2-cyclohexanecarboxylic acid, 1,2゜4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-tricarboxyl Benzene, 1
, 2.3-tricarboxyl-4-methylbenzene, 1
, 2.3-tricarboxyl-5-methylbenzene,
1,2.3-tricarboxyl-4-phenylbenzene, 1,2.3-tricarboxyl-5-phenylbenzene, 1,2.4-tricarboxylbenzene (i.e. trimellitic acid),! , 2.4-tricarboxyl-3-methylbenzene, 1,2.4-tricarboxyl-3-phenylbenzene, 1,2.4-tricarboxyl-5-methylbenzene, 1,2.4-tricarboxyl- 5-phenylbenzene, 1,2.4-tricarboxy)E/-6-methylbenzene, 1,2.
4-tricarboxyl-6-phenylbenzene, 1
,2,3.4~tetracarboxylbenzene,1,2,
3.4-tetracarboxyl-5-methylbenzene,
1,2,3.4-tetracarboxyl-5-phenylbenzene, 1,2,3.5-tetracarboxylbenzene, 1,2,3.5-tetracarboxyl-4-methylbenzene, 1,2,3. Benzene derivatives such as 5-tetracarboxyl-4-phenylbenzene, 1,2,4.5-tetracarboxylbenzene (i.e., pyromellitic acid); 1,2,3. - Tricarboxylnaphthalene, 1,2.4-tricarboxylnaphthalene, 1.2
．． 5-)-Licarboxylnaphthalene, 1,2.6-
Tricarboxylnaphthalene, 1,2.7-tricarboxylnaphthalene, 1,2,8-tricarboxylnaphthalene, 1,2,3.4-tetracarboxylnaphthalene, 1°2.3.5-tetracarboxylnaphthalene, 1, 2,3.6-tetracarboxylnaphthalene, 1
, 2,3.7-tetracarboxylnaphthalene, 1,3
, 5.6-tetracarboxylnaphthalene, 1,3,5
．． 7-tetracarboxylnaphthalene, 1,4,5.6
-Tetracarboxylnaphthalene, 1,4,5.7-
Naphthalene derivatives such as tetracarboxylnaphthalene and 1,4,5,8-tetracarboxylnaphthalene; 2
,2',3-) Ricarboxylbenzophenone, 2,
3.3'-tricarboxylbenzophenone, 2,3
．． 4'-tricarboxylbenzophenone.

2', 3.4-tricarboxylbenzophenone, 3.
3'.

4-tricarboxylbenzophenone, 3,4.4'-
Tricarboxylbenzophenone, 2,3.4-tricarboxylbenzophenone, 2,3.6-tricarboxylbenzophenone, 2,3,4.5-tetracarboxylbenzophenone, 2,3,5.6-tetracarboxylbenzophenone, 2. 2',3.3'-tetracarboxylbenzophenone, 2,3.3',5-tetracarboxylbenzophenone, 3.3',4.4'-
Tetracarboxylbenzophenone, 3.3'4.5'
Examples include aromatic polycarboxylic acids such as benzophenone derivatives such as -tetracarboxylbenzophenone, and aromatic polycarboxylic acids are preferred.

Particularly preferred among the polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids are trivalent or tetravalent aromatic polyvalent carboxylic acids and their anhydrides.

The above polyvalent carboxylic acid anhydride and polyvalent carboxylic acid are
They can be used alone or in combination of two or more.

The amount of component (B) in the composition of the present invention is (A)
The amount ranges from o, oi to 50 parts by weight, preferably from 1 to 50 parts by weight, per 100 parts by weight of the component polymer.

If the amount of component (B) is less than 0.01 part by weight, curing will be insufficient and a strong coating film cannot be formed, and if it exceeds 50 parts by weight, the coating film will not adhere to the substrate. Not only does adhesiveness deteriorate, but it is also difficult to form a uniform and smooth coating film by spin coating.

The composition of the present invention essentially includes the above-mentioned component (A) and component (B), and further includes a third component.

At least one selected from a silane coupling agent, a titanate coupling agent, and a compound having two or more epoxy groups can be blended.

As the silane coupling agent that can be used as the third component, a silane compound having a reactive substituent represented by the following formula (A) can be exemplified.

X-Y-3i(OR)a −
(A) [In the formula, or a vinyl group, a carboxyl group, an isocyanate group, or an epoxy group, Y represents an alkylene group or a phenylene group, and R represents a methyl group, an ethyl group, or a propyl group] ) Specific examples of compounds include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Examples include silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Among them, γ-glucidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)
Silane coupling agents with epoxy groups such as ethyltrimethoxysilane.

These silane coupling agents are preferred because they exhibit particularly excellent smoothness, adhesion, water resistance, and solvent resistance as coating films on various substrates, and these silane coupling agents can be used alone or in combination of two or more. can.

Furthermore, examples of the titanate coupling agent include the following titanate compounds.

(a) General formula; % formula % () [In the formula, R represents an alkyl group, preferably an alkyl group of 1 to 4 carbon atoms; R1 is a vinyl group, an α-alkyl substituted vinyl group, or a carbon atom of 6 or more, preferably C1G"C20 represents a substituted or unsubstituted alkyl group or aryl group; R2 has 6 or more carbon atoms, preferably CIO""
C20 represents a substituted or unsubstituted alkyl group or aryl group; R3 represents a hydrogen atom or a group represented by R2; two R1s are not hydrogen atoms at the same time; n represents an integer of 1 to 3; Specific examples of the compound of general formula (i) include isopropyltriisostearoyl titanate, isopropyltrilauroyl titanate, isopropyl trimyristoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, Isopropyl isostearoyl diacryloyl titanate, isopropyl trimethacryloyl titanate, isopropyl triacryloyl titanate, isopropyl trioctanoyl titanate, ethyl triisostearoyl titanate, butyl triisostearoyl titanate, diisopropyl dilauroyl titanate, diisopropyl lauroyl myristoyl titanate, diisopropyl distearoyl titanate, Diisopropyl stearoyl methacryloyl titanate, diisopropyl diacryloyl titanate, diisopropyl isostearoyl-4-aminobenzoyl titanate,
Triisopropyl acryloyl titanate, triethyl methacryloyl titanate, triisopropyl myristoyl titanate, triisopropyl stearoyl titanate, triisopropyl isostearoyl titanate, etc. can be mentioned, and specific examples of the compound of general formula (it) include isopropyl tricumylphenyl titanate, Isopropyl tris (N-aminoethyl aminoethyl) titanate, bis (triethanolamine) diisopropyl titanate, bis (triethanolamine) dibutyl titanate, bis (triethanolamine) diethyl titanate, bis (triethanolamine) dimethyl titanate, bis (triethanolamine) diethyl titanate, bis(triethanolamine) dipropyl titanate, bis(triethanolamine) diisopropyl titanate, etc. Specific examples of the compound of general formula (iii) include isopropyl tris( Dodecylbenzenesulfonyl) titanate, diisopropylbis(dodecylbenzenesulfonyl)
Titanate, tributyl dodecylbenzenesulfonyl titanate, isopropyl-tris(toluenesulfonyl)titanate, diisopropyl-bis(toluenesulfonyl)titanate.

Examples include triisopropyltoluenesulfonyl titanate.

Specific examples of the compound of general formula (iv) include isopropyl tris(diisooctylphosphato)titanate, isopropyl tri(dioctylphosphato)titanate, isopropyl tri(dioctylpyrophosphato)titanate, etc. .

(b) A compound formed by a phosphite ester being coordinately bonded to a tetraalkyl titanate; A specific example is tetraisopropyl bis(dioctyl phosphite)
Titanate (CHa-CHCH-0)4Ti・CP(-0-C1
187) 20H) 2-tetraoctyl bis(ditridecylphosphite) titanate (CsTo70-)4Ti・CP(-0-C13H27
)20H)2+tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate and the like.

(c) Titanate compound having a chelate ring: Specific examples include bis(dioctylpyrophosphato) oxyacetate titanate, dicumylphenyl oxyacetate titanate, bis(dioctylpyrophosphato)ethylene titanate, diiso Examples include stearoyl ethylene titanate.

The titanate coupling agents exemplified above can be used singly or in combination of two or more.

Further, specific examples of compounds having two or more epoxy groups that can be used as the third component include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol. diglycidyl ether, 1,6-hexanethiol diglycidyl ether,
Jepoxy compounds such as dibromoneopentyl glycol diglycidyl ether, 0-phthalic acid diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A-propylene oxide adduct diglycidyl ether, 0-cresol, novolak type epoxy resin,
Examples include glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. These compounds are available from Nagase Chemical Co., Ltd. as "
It is commercially available under the trade name "Bunacol".

These compounds having two or more epoxy groups can be used alone or in combination of two or more.

The amount of the above-mentioned silane coupling agent, titanate coupling agent, and compound having two or more epoxy groups, which are used as the third component as necessary, is preferably per 100 parts by weight of the polymer of component (A). The range is from 0.1 to 30 parts by weight, particularly preferably from 0.5 to 20 parts by weight.

By blending these compounds in such ranges, the coating film formed will have further improved smoothness, adhesion to the substrate, water resistance, solvent resistance, and hardness.

In addition to the above-mentioned essential components (A) and (B), the composition of the present invention may optionally contain stabilizers such as anti-aging agents and ultraviolet absorbers to an extent that does not impair transparency. Can be added. Note that if transparency is not required due to the purpose of the coating film, pigments, paints, fillers, etc. may be added, but other properties will not be impaired in any way.

The composition of the present invention can be obtained by uniformly mixing the above components. There are 9 ways to mix these ingredients.
Usually, a solution mixing method is preferred, in which these components are mixed by dissolving them in a suitable solvent.The solvent used for solution mixing may be any solvent, especially one that dissolves each of the above components and does not react with these components. Without limitation, various solvents can be used, specific examples include:
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n -Ketone solvents such as propyl ketone, diisobutyl ketone, cyclohexanone, and holon; ethers such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, and tetrahydrofuran; System solvents: ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate.

Examples include ester solvents such as ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.

When preparing the composition of the present invention by solution mixing, the mixing order is not particularly limited. For example, a solution of the composition of the present invention may be prepared by dissolving all components in a solvent at the same time, or as necessary. Depending on the situation, each component may be dissolved separately in the same or different solvents to form two or more solutions, and these solutions may be mixed to prepare a solution of the composition of the present invention. In addition, the long-term storage stability of each component can be improved by mixing them in the desired ratio immediately before use, and the coating performance can be easily changed depending on the purpose by simply changing the mixing ratio of the two types of solutions. is also possible.

The solution concentration of the composition of the present invention is not particularly limited, and is generally used at about 5 to 50% by weight, but in order to form a better coating film, it is preferably 5 to 10% by weight.
Octps (EL-D rotary gas viscometer manufactured by Tokyo Keiki Co., Ltd., 25°C).

The solution of the composition of the present invention prepared as described above can be applied to the surface of a substrate and cured by heating to obtain a desired coating film.

The method of applying the solution of the composition of the present invention to the substrate surface is not particularly limited, and various methods such as a spray method, roll coating method, and spin coating method can be used. One of the features of the present invention is that it is suitable for゛The heat curing conditions for the composition of the present invention are appropriately selected depending on the specific types and blending ratios of each component of the composition, but are usually at 80 to 250°C for about 15 minutes to 10 hours.

One of the applications for which the composition of the present invention is useful is color filters for liquid crystal display elements and solid-state image sensors, and the color filters are manufactured by the following steps. That is, the manufacturing method includes (i) a step of forming a photosensitive dyed substrate layer on a substrate, (5X) a step of selectively exposing and developing a patterned portion of the first color of the substrate layer, and (fit) the above-mentioned step. After development, the first color pattern is formed by a step of dyeing the pattern portion of the first color with a dye having predetermined spectral characteristics, and (iv) a step of forming a protective layer on the entire surface of the substrate after the dyeing, and then This is a method of forming a required number of hue patterns in a laminated state by repeating the steps (i) to (iv) for the required number of colors using the protective layer formed in the step as a base.

The substrate used in the step (i) is, for example, a transparent substrate such as glass or plastic, or a solid-state imaging device.For the formation of the photosensitive dyed substrate layer, a photosensitive polymer compound solution is applied by roller coating, dipping, etc. This can be done by uniformly applying the coating onto the substrate using a spinner or the like and drying it. Specific examples of polymer compounds that will become the photosensitive dye substrate layer include water-soluble natural polymer compounds such as gelatin, casein, fish glue, and egg white, and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylonitrile. The compound contains photosensitizers, such as ammonium dichromate, sodium dichromate,
Dichromate salts such as potassium dichromate, p-diazophenylamine, 1-diazo-4-dimethylaminobenzene hydrofluoroborate, 1-diazo-3-methyl-4
-dimethylaniline sulfate, 1-diazo-3-
Diazonium salts such as monoethylnaphthylamine and their paraformaldehyde condensates, 4,4'-diazidostilbene-2,2-disulfonic acid and its salts,
2,6-bis(4-azidobenzal-2-sulfonic acid)
Azidosulfonic acid compounds such as cyclohexanone and its salts have solubility in solvents such as water, and when activated by active light such as ultraviolet rays, -Cool, -NO3, -
Examples include compositions in which compounds capable of coordinate bonding with groups having non-coexisting electron pairs such as 0FI, -CONH2, and >CO are mixed. The amount of the photosensitizer added is usually 1 to 50%, preferably 10 to 30% by weight based on the polymer.
Set to %. The thickness of the photosensitive dyed substrate layer thus formed is preferably in the range of 0.3 to 2 μm.

(...) Selective exposure in the process can be performed according to a known method, and can be performed by irradiating through a mask with a desired pattern using a mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, etc. as a light source. After the required pattern portions are cured by exposure, unnecessary portions are removed by developing with a developer such as warm water.

The dye used in step (iii) is usually a water-soluble dye, and any acidic, direct or basic water-soluble dye can be used. Specific examples of dyes that can be used include the following.

(I) Red dyes include Suminol Milling Scarlet G (Sumiman Chemical Co., Ltd.), Cibacron Scarlet G-P (Ciba Geigy Co., Ltd.), Cibacron Pronto Scarlet (Ciba Geigy Co., Ltd.), Suminol.
Fast Red G (Cabinet Chemical), Sumilite Splat Red 4BL (Cabinet Chemical), Aminyl Red
E-28L (Sumai Chemical) 1, Aminyl Red E-3
BL (resident chemistry), Azido Scarlet 901 (resident chemistry), Suminol Milling Scarlet FG
(Suminol Chemical), Suminol Milling Orange SG
(Resident Chemistry), Suminol Fast Orange P○
(Sumai Chemical), Maxilon Red GRL (Ciba・
Geigy), Eriosin Scarlet RE (Ciba Geigy), Mikawan Brilliant Red 8
BS (Mitsubishi Chemical), and light scarlet
Examples include GL130% (Mitsubishi Chemical) and Kayanol Milling Red R8125 (Mitsubishi Chemical).

(2) Green dyes include Suminol Milling Brilliant Green 5G (Suminor Chemical), Acid Brilliant Milling Green G (Suminant Chemical), and Acid Brilliant Milling Green B (Suminant Chemical).
, Mikation Olive Green 3GS (Ciba・
Geigy), Kayanor Milling Green 5GW
(Nippon Kayaku), Sooriidazole Green P-GG
(Hoechst), Paper Fast Green 5G (
/<inyl), etc.

(3) Blue dyes include Sumilite, Supra, Turquoise Blue, G (Sumai Kagaku), Cibacron Blue,
3G-A (Ciba Geigy), Cytochlorane Blue 8G (Ciba Geigy), Prodione Turquoise
H-A (CIC), Kayathion Turquoise P-
A (Nippon Kayaku), Kayathion Turquoise P-NGF
(Nippon Kayaku), Sumikalon Blue E-FBL (Sumikaron Chemical), Sumikalon Brilliant Blue 5-BL
(Jinja Chemical), Suminol Leveling Sky Blue R Extra Conc (Jinja Chemical), Orazol Blue GN (Ciba Geigy), Makizion Blue 3GS (Mitsubishi Chemical), Makizion Blue 2G
S (Mitsubishi Chemical), Kayanol Milling Blue G
Examples include W (Nippon Kayaku), Kayasil Sky Blue R (Nippon Kayaku), and the like.

The formation of the protective layer in step (iv) is performed by applying a solution of the composition of the present invention and curing it by heating.

The coating method is not particularly limited, but spin coating, spray coating, roll coating, dipping, printing, etc. are preferred, and the thickness of the protective layer formed is 0.1 μm = 1
A range of 0μ is desirable. In the color filter manufactured in this way, the protective layer provided between the patterns of each hue mainly functions as a resist-dyeing protective layer for the purpose of resisting each other, and the finally formed protective layer covers the surface of the color filter. It acts as a surface protective layer to prevent it from being damaged by scratches, etc.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these Examples.

Example 1 Polyglycidyl methacrylate obtained by solution radical polymerization using dioxane as a solvent (polystyrene equivalent weight average molecular weight approximately go, ooo, molecular weight distribution 65.000)
6 g into 49 g of ethylene glycol monoethyl ether acetate in a glass container.

Stir at room temperature until completely dissolved. Add ADEKA Hardener EHX-7000, 6 g (
M Denka Kogyo Co., Ltd.) and 0.3 g of γ-glycidoxypropyltrimethoxysilane were added and stirred until uniformly mixed. The solution thus obtained (I8cps,
25℃) through a filter with a pore size of 0.2μ, and then coated on a glass plate with a spin coater at a rotation speed of 3000.
The coating was applied by spinning at rpm. After coating, the glass plate was heat treated in a constant temperature bath at 150° C. for 1 hour to cure the coating film. The surface of the resulting coating film was extremely smooth, and no film roughness was observed. The film thickness measured by dual-light interference microscopy was 0.39 μm, and the above tests were conducted on the coating film prepared as described above. First, the absorption spectrum of a glass plate coated with the above coating was measured using the same glass plate as a control. The light transmittance was 95% or more in the entire range from 350 nm to 800 nm.

Next, in order to examine the adhesion of the coating film applied and cured to this glass plate, a cross-cut test (JISK-54
00) was carried out. As a result, no peeling was observed. In addition, this glass plate was placed in boiling water and allowed to stand for 5 hours, and then a burlap test was conducted in the same manner, but no peeling was observed in this case as well. Further, the glass plate with the above-mentioned coating film was placed in toluene, heated under reflux for 5 hours, and then subjected to a cross-cut test, but no peeling was observed in this case as well. In addition, a glass plate with a coating film prepared in the same manner as above was placed in a gear oven at 200°C for 200 min.
As a result of the time heat treatment, no cracks appeared in the coating film, and no change in the absorption spectrum was observed.

Furthermore, a glass plate with a coating film prepared in the same manner as above was placed in a dyeing bath with the composition shown below and left at 100°C for 30 minutes, and then the glass plate was taken out, thoroughly washed with water, dried, and then the condition of the coating film was observed. Visual inspection revealed no abnormalities such as cracks or film roughness, and the coating remained colorless and transparent with no staining at all.

From the above results, it is clear that the coating film of the composition of the present invention is smooth and has excellent transparency, adhesion, water resistance, solvent resistance, heat resistance, and dye resistance.

1 Day acidic dye (Brilliant Blue FCF)...
2g glacial acetic acid 3
g Distilled water ・・・・・・10
0g Example 2 5.5g of polyglycidyl methacrylate used in Example 1
45. of cyclohexanone in a glass container. It was dissolved in To the solution thus obtained was added 1.7 g of pyromellitic anhydride.
and 0.28 g of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were added and mixed until a homogeneous solution was obtained.Next, a composition solution (I5cps, 25°C) was prepared in the same manner as in Example 1. After that, the solution was spin-coated onto a glass plate and cured at 180°C for 2 hours, resulting in a film thickness of 0 after curing.
．． A coating of 41 μm tumor was formed. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1. In addition, a glass plate on which a coating film was formed in the same manner as above was placed in a dyeraku with the following composition and left at 100°C for 5 hours, then the glass plate was taken out, thoroughly washed with water, dried, and the condition of the coating film was visually observed. When inspected, no abnormalities such as cracks or film roughness were observed, and the coating remained colorless and transparent with no dyeing at all.

Kurumuan acid dye (Sminol Milling Red RS manufactured by Sumitomo Chemical Co., Ltd.) 2g glacial acetic acid
・・・・・・ 3g distilled water
......100g Example 3 Copolymer of glycidyl acrylate and methyl methacrylate obtained by solution radical polymerization using tetrahydrofuran as a solvent (weight average molecular weight in terms of polystyrene: about 95,
000, molecular weight distribution 2.5. 6 g of monomer unit content derived from glycidyl acrylate (80% by weight determined by NMR spectrum) was dissolved in 49 g of cyclohexanone, and 1 g of trimellitic anhydride and β-(3,4-epoxycyclohexyl) were dissolved in 49 g of cyclohexanone. ) 0.4 g of ethyltrimethoxysilane was mixed with force until a homogeneous solution was obtained.Then, the composition solution (
After preparing a solution (23 eps, 25° C.), the solution was spin-coated onto a glass plate and cured at 180° C. for 2 hours to form a coating film with a film thickness of 0 and a weight of 45 μm after curing. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1. In addition, a glass plate with a coating film prepared in the same manner as above was operated in the same manner as in Example 4 using the same dyeing bath, but no abnormalities such as cracks or film roughness were observed.
Moreover, the coating film remained colorless and transparent and was not dyed at all.

Example 4 6 g of polyglycidyl methacrylate used in Example 1 was mixed with 49 g of ethylene glycol monoethyl ether acetate.
To the solution obtained by dissolving 1.g of Himic anhydride, add 1.
2g and 0.5g of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were added and mixed until a homogeneous solution was obtained.6 Then, a composition solution (I8cps, 25°C) was prepared in the same manner as in Example 1. Thereafter, the solution was spin-coated onto a glass plate and cured at 180° C. for 2 hours to form a coating film with a cured film thickness o of 42 μm. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1.

Example 5 A composition solution (20 cps, 25
℃) and cured on a glass plate with a film thickness of 0.35 μm.
A coating film was formed. The test results of the obtained coating film were as shown in Table 1. Note that the surface of the coating film was very smooth.

Example 6 1.7 g of benzophenone tetracarboxylic dianhydride was used instead of pyromellitic anhydride in Example 2, and the composition solution (22 eps, 25°C) was otherwise the same as in Example 2.
was prepared, and a coating film was formed on a glass plate in the same manner as in Example 4. The thickness of the coating film after curing was 0.46 μm, and the test results of the coating film were as shown in Table 1. Note that the surface of the coating film was very smooth.

In addition, a glass plate with a coating film prepared in the same manner as above was operated in the same manner as in Example 2 using the same dyeing bath, but no abnormalities such as cracks or film roughness were observed, and the coating film was colorless and transparent. It was completely unstained.

Example 7 ADEKA Hardener E) IX-700 in Example 1
Instead, Rikajid-)IN (manufactured by New Japan Chemical Co., Ltd.)
A composition solution (I9cps, 25°C) prepared in the same manner as in Example 1 using 1.8g was spin-coated onto a glass plate, and cured at 180°C for 1 hour to give a film thickness of 0.52μ.
A coating film (2) was obtained. The surface of the coating film was very smooth. The test results of this coating film were as shown in Table 1.

Example 8 A composition solution prepared in the same manner as in Example 1, except that 1.8 g of Rikazid MH-700 (manufactured by New Japan Chemical Co., Ltd.) was used in place of ADEKA Hardener EHX-700 in Example 1. (20cps, 25℃) was spin-coated onto a glass plate, and cured at 180℃ for 2 hours, resulting in a film thickness of 0.47.
A coating film was obtained at the foot of μ. The surface of the coating film was very smooth.

The test results of this coating film were as shown in Table 1.

Example 9 Instead of Adeka Hardener EHX-700 in Example 1, 0.8 g of terephthalic acid was used, and the rest were as in Example 1.
A composition solution prepared in the same manner as (I8cps, 25°C
) was spin-coated onto a glass plate and cured at 180° C. for 1 hour to obtain a coating film with a thickness of 0.44 μm. The surface of the coating film was very smooth. The test results of this coating film were as shown in Table 1.

Example 10 A composition solution (I8 cps, 25
C) was spin-coated onto a glass plate, and then cured at 150° C. for 1 hour to obtain a coating film with a thickness of 0.40 μm. The surface of the coating film was very smooth. The test results of this coating film were as shown in Table 1.

Example 11 In place of the polyglycidyl methacrylate of Example 1, polyglycidyl acrylate (weight average molecular weight in terms of polystyrene,
000, molecular weight distribution 2.2) A composition solution (I6cps, 25°C) was prepared in the same manner as in Example 1 except for the following: After curing, a coating film with a thickness of 0.51 μm was obtained. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1.

Example 12 Glycidyl methacrylate and methyl methacrylate/L/17) copolymer (polystyrene) obtained by solution radical polymerization using ethylene glycol monoethyl ether acetate as a solvent instead of the polyglycidyl methacrylate of Example 1. Converted weight average molecular weight 84.000, molecular weight distribution 2.3. Monomer unit content derived from glycidyl methacrylate determined from NMR spectrum 72% by weight)
A composition solution (I5 cps, 25° C.) was obtained in the same manner as in Example 1 except that 5.8 g was used.Then, in the same manner as in Example 1, it was spin-coated onto a glass plate and cured to a thickness of 0.8 g. 37μ
A coating film of - was obtained. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1.

Example 13 In place of the polyglycidyl methacrylate in Example 1, a copolymer of glycidyl methacrylate and n-butyl methacrylate obtained by solution radical polymerization using ethylene glycol monoethyl ether acetate as a solvent (
Polystyrene equivalent weight average molecular weight 120,000, molecular weight distribution 2.2, monomer unit content derived from glycidyl methacrylate determined from NMR spectrum 63% by weight
) 6g, and ADEKA Hardener EHX-700
A composition solution (I5 cps, 25° C.) was obtained in the same manner as in Example 1 except that 0.6 g of trimellitic acid was used instead. Then, in the same manner as in Example 1, it was spin-coated onto a glass plate and cured to obtain a coating film with a thickness of 0.35 μm. The resulting coating film was very smooth, and the test results for this coating film are shown in Table 1.
It was as shown in

Example 14 In place of the polyglycidyl methacrylate in Example 1, a copolymer of glycidyl methacrylate and isobutyl methacrylate obtained by solution radical polymerization using tetrahydrofuran as a solvent (polystyrene equivalent weight average molecular weight 125,000, molecular weight distribution Example 1
In place of ADEKA Hardener EHX-700,
A composition solution (I8 cps, 25°C) was prepared in the same manner as in Example 1 except that 0.63 g of terephthalic acid was used. A coating film was formed. The test results for this coating are shown in Table 1.
Example 15 In place of the polyglycidyl methacrylate in Example 1, a copolymer of glycidyl methacrylate and tert-butyl methacrylate obtained by solution radical polymerization using ethylene glycol monoethyl ether acetate as a solvent was used. Coalescence (polystyrene equivalent weight average molecular weight 150,000, molecular weight distribution 2.0. Monomer unit content derived from glycidyl methacrylate determined from NMRX/<cutol 62.5
Weight%) 6.0g was used.

In addition, ADEKA Hardener EHX-70 in Example 1
A composition solution (I7 cps, 25°C) was prepared in the same manner as in Example 1 except that 0.6 g of trimellitic acid was used instead of 0. A coating film was formed. The test results for this coating were as shown in Table 1.

Example 16 In place of the polyglycidyl methacrylate in Example 1, a copolymer of glycidyl acrylate and tert-butyl acrylate obtained by a solution radical polymerization method using ethylene glycol monoethyl ether acetate as a solvent (polystyrene equivalent weight Average molecular weight 1,450,000, molecular weight distribution 2.1, monomer unit content derived from glycidyl acrylate determined from NMR spectrum 60% by weight)
6.0g was used, and the other conditions were the same as in Example 1, so that the thickness was 0.
．． A coating film of 35 μm was formed. The test results for this coating were as shown in Table 1.

Comparative Example 1 A composition solution was prepared in the same manner as in Example 2 except that 5.5 g of polymethyl methacrylate was used instead of polyglycidyl methacrylate.

The film thickness after curing was 0.5 on a glass plate in the same manner as in Example 2.
A coating film of 5 μm was obtained. The test results of the obtained coating film were as shown in Table 2.

Comparative Example 2 In place of the polyglycidyl methacrylate of Example 1, a copolymer of glycidyl methacrylate and methyl methacrylate (
Polystyrene equivalent weight average molecular weight 83.000. N.M.
A composition solution was obtained in the same manner as in Example 1 except that 6 g of the monomer unit content derived from glycidyl methacrylate (45% determined from the R spectrum) was used. Next, it was spin-coated onto a glass plate in the same manner as in Example 1, and cured to a thickness of 0.
A coating film of 31 μm was obtained. The test results of the obtained coating film are shown in Table 2.
It was as shown in

Example 17 1 g of polyglycidyl methacrylate I used in Example 1
Adeka Hardener EHX was dissolved in 89 g of ethyl cellosolve acetate in a glass container.
-7002.8 g, 0.6 g of γ-crisitoxyfuropyltrimethoxysilane, and 0.6 g of trimellitic acid were added and mixed until a homogeneous solution was obtained.

The obtained composition solution (I6cps, 25°C) was used in Example 1.
It was spin-coated onto a glass plate in the same manner as above and cured at 150° C. for 1 hour to form a coating film having a thickness of 0.4 μm after curing. The obtained coating film is colorless and transparent, and has a wavelength of 350 to 800 nm.
It had a light transmittance of 95% or more in the entire area, and its surface was very smooth. Further, as a result of conducting a cross-cut test on the cured coating film and the coating film left in boiling water for 5 hours, no peeling was observed. Furthermore, even after heat-treating the glass plate on which the coating film was formed at 200° C. for 200 hours in a gear oven, no abnormalities such as cracks or roughness were observed in the coating film, and no change was observed in the absorption spectrum.

In addition, a glass plate with a coating film prepared in the same manner as above was operated in the same manner as in Example 2 using the same dyeing bath, but no abnormalities such as cracks or film roughness were observed, and the coating film was colorless and transparent. It was completely unstained.

On the other hand, a solution of commercially available gelatin dissolved in water (solid content 20%) was spin-coated on a glass plate to form a gelatin film with a thickness of 1.52μ, and then the same composition solution as above was applied. The coating was spin-coated under the following conditions, and then cured at 150° C. for 1 hour to form a coating film. The coating film thus obtained was firmly adhered to the gelatin layer, and no peeling was observed.

Example 18 The surface hardness of the coating films formed in Examples 2.7 and 9 to 11 was evaluated by the pencil hardness method (JIS K-5400). The results were as shown in Table 3.

Example 19 Instead of 0.3 g of γ-glycidoxyprobyltrimethoxysilane used in Example 10, 0.5 g of isopropyl triisostearoyl titanate was used.

Otherwise, a homogeneous solution was prepared in the same manner as in Example 1.

Next, 1 composition solution (31 ep) was prepared in the same manner as in Example 10.
s, 25° C.) was spin-coated onto a glass plate and cured at 180° C. for 2 hours to form a coating film with a thickness of 0.54 μm after curing. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1.

Example 20 A homogeneous solution was prepared in the same manner as in Example 1 except that 0.4 g of trimethylolpropane polyglycidyl ether was used in place of 0.3 g of γ-glycidoxypropyltrimethoxysilane used in Example 1. Prepared.

Next, in the same manner as in Example 1, a composition solution (40 cps,
25 DEG C.) was spin-coated onto a glass plate and cured at 150 DEG C. for 2 hours to form a coating having a cured film thickness of 0.73 .mu.m. The surface of the coating film was very smooth. The test results of the obtained coating film were as shown in Table 1.

Table 2 Table 3 [Effects of the Invention] Since the composition of the present invention has excellent stability at room temperature, it is advantageous for producing it as a single-wave type thermosetting resin composition.

The coating film obtained by curing the composition of the present invention has high light transmittance in a wide range of wavelengths from ultraviolet to visible regions, and has excellent transparency. Shows excellent adhesion to substrates made of various materials.

In addition, this coating has high smoothness, high hardness, and toughness, making it highly scratch resistant, and has excellent light and heat resistance, and will not undergo discoloration or other deterioration even after long-term use. It has excellent water resistance, solvent resistance, and stain resistance, and is highly hard. Due to these characteristics, the coating film formed by the composition of the present invention is not only useful as a protective coating film on the substrate surface of various articles, but also as a dye-resistant protective layer of color separation filters, a surface protective layer, etc. Extremely suitable, with excellent color clarity and brightness.

A highly reliable color separation filter can be obtained.

A major feature of the coating film obtained using the composition of the present invention is that, as described above, the required properties are well-balanced and all of them are good.

Claims (1)

[Claims] 1. (A) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R is a hydrogen atom or a lower alkyl group, and n
is an integer of 1 to 5] A polymer containing 60% by weight or more of monomer units derived from the compound represented by (B) 0.01 to 50 parts by weight per 100 parts by weight of the polymer; A thermosetting polymer composition containing at least one compound selected from polycarboxylic anhydrides and polycarboxylic acids.