JP2003270421A - Photosensitive composition for color filter, color filter containing the same and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for a color filter, which has high sensitivity, demonstrates hardening property with high cross-linking density, is free from color mixing, forms a precise pattern with high resolution, has heat resistance so as not to damage color filter's properties (a shape, hue or the like), is excellent in the hue, transmittance and has an excellent yield and a color filter using the composition. <P>SOLUTION: The photosensitive composition for the color filter is characterized in that it contains a photocross-linking polymer compound with at least a photodimerizable maleimide group in a side chain and a pigment. The color filter uses the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition for a color filter suitable for forming a colored image constituting a color filter used in a liquid crystal display device or a solid-state image pickup device, and a color containing the curable composition. The present invention relates to a filter and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive composition used for producing a color filter, a polyfunctional acrylate and an optical resin are added to an acrylic resin in which a pigment is dispersed as described in JP-A-1-152449. A radical polymerization type photosensitive composition containing a polymerization initiator is known. A composition utilizing this radical polymerization is generally highly sensitive, but it is difficult to form a pattern in an oxygen atmosphere because the composition is susceptible to oxygen inhibition during exposure and the necessary radicals cannot be obtained. Therefore, in order to favorably carry out radical polymerization, it is necessary to perform exposure in a state in which it is hardly affected by oxygen such as formation of an oxygen blocking film, which is a complicated process.

As a means for eliminating the above-mentioned influence and complexity of oxygen, in JP-A-4-163552, there is disclosed a resin having a phenol which is cured by an acid, a cross-linking agent having an N-methylol structure, a photo-acid generator and a pigment. Is disclosed. This is a chemically amplified photosensitive composition utilizing an acid-catalyzed reaction, which is known to be particularly highly sensitive and high resolution, and has a feature that the obtained pattern shape is vertically vertical. Then, when forming a pattern using this photosensitive composition, the composition is applied onto a substrate, the pattern is exposed to generate an acid, the substrate after exposure is heated, and cured by an acid-catalyzed crosslinking reaction. Then, the pattern is formed by alkali development.

However, in the case of a photosensitive composition using a novolac resin or a homopolymer of p-hydroxystyrene as a resin containing phenol, the heat resistance is particularly low, and the resin yellows due to heating, or a resin layer formed. However, there is a problem that the transmittance of the Further, in the case of a photosensitive composition using a p-hydroxystyrene copolymer as a resin containing phenol, a decrease in transmittance is hardly recognized by heating at 230 ° C. for 1 hour, but at a temperature higher than that. There was a problem that the transmittance was lowered.

On the other hand, from the viewpoint of further improving heat resistance, acrylic resins having a carboxylic acid and a hydroxyl group have been studied as a resin which is cured by an acid. From the viewpoint of heat resistance, a decrease in transmittance was not observed by heating at 250 ° C. for 1 hour, but the reaction efficiency of the cross-linking agent and the resin was low, and self-crosslinking between cross-linking agents increased, resulting in a cross-linking density. In order to obtain a pattern having low chemical resistance, post-baking at 200 ° C. or higher was required immediately after alkali development at the time of forming a colored pattern of each color. However, by post-baking, cracks occur in the glass substrate on which the color filter is formed, or a sublimate from the photosensitive composition adheres to other portions on the substrate and becomes a residue. It was one of the factors that hindered the yield.

On the other hand, in recent years, a charge coupled device (CCD)
In the color filters for solid-state image pickup devices such as the above, further high definition is desired. However, in the conventional pigment dispersion system, since the pigment itself contains particles of about 1 μm, the resolution cannot be essentially improved, and there is a problem that color unevenness due to coarse particles in the pigment occurs. Therefore, it is not suitable for applications requiring a fine pattern such as a solid-state image sensor.

In order to solve this problem, Japanese Patent Laid-Open No. 6-75
No. 375 and the like propose a technique using a dye.
However, although it is useful for increasing the resolution of the pattern, since the dye essentially acts as a light absorber, it absorbs the irradiation light and absorbs the photopolymerization initiator, followed by decomposition and radical generation. As a result of suppressing the above, there is also a problem that sufficient curability cannot be obtained with a photosensitive composition utilizing radical polymerization. Therefore, this is also a factor that causes the dye to be eluted when the second and subsequent resists are applied to cause color mixing.

[0008] As a method for obtaining curability, for example, Japanese Patent Laid-Open No. Hei 6
As disclosed in JP-A-35182 and JP-A-6-195835, a method of adding a crosslinking agent has been proposed, but even if this method is adopted, the elution of the dye is completely suppressed. In order to obtain sufficient curability, it was necessary to heat for a long time after forming the pattern.
However, as described above, heating causes a change in hue and a decrease in transmittance.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. The present invention has high sensitivity, a high degree of curing with a high cross-linking density, no color mixing due to the elution of dyes, a fine pattern can be formed with high resolution, and the properties of the color filter (shape, hue, etc.) With heat resistance not impaired, hue and transmittance, and a photosensitive composition for a color filter having a good yield, and the photosensitive composition for a color filter is used, the pattern shape is excellent and the resolution is excellent, and the hue is It is an object of the present invention to provide a color filter having good transmittance and high productivity. Also, in the method for producing the color filter, the productivity of forming a pattern with high sensitivity and high curing degree by preventing the dye from being eluted without impairing the properties of the color filter such as shape and hue. An object of the present invention is to provide a method for manufacturing a color filter including the above.

[0010]

The concrete means for solving the above-mentioned problems are as follows, and the above-mentioned object is achieved. (1) A photosensitive composition for a color filter comprising a photocrosslinkable polymer compound having at least one photodimerizable maleimide group in a side chain and a dye.

(2) A photocrosslinkable polymer compound having at least one photodimerizable maleimide group in its side chain,
The photosensitive composition for a color filter according to (1) above, which comprises a dye, a photopolymerization initiator, and a monomer or oligomer having at least one ethylenically unsaturated group. (3) The photosensitive composition for a color filter according to (1) or (2), which further contains a crosslinking agent.

(4) A color filter comprising the photosensitive composition for a color filter according to any one of (1) to (3) above.

(5) A step of applying the photosensitive composition for a color filter according to any one of (1) to (3) above on a support, exposing through a mask, and developing to form a negative pattern. And a method for manufacturing a color filter. In the method of manufacturing a color filter, the above steps are repeated for a desired number of hues when manufacturing a color filter having a desired hue. Moreover, an aspect having a step of curing the negative pattern by heating and / or exposure is also suitable, if necessary.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive composition for a color filter of the present invention, the color filter using the same and the method for producing the same will be described in detail below. The photosensitive composition for a color filter of the present invention may be a photocrosslinkable polymer compound having at least one photodimerizable maleimide group in its side chain (hereinafter, simply referred to as "photocrosslinkable polymer compound"). ) And a dye, and preferably also a solvent. Preferably, it comprises a monomer or oligomer having at least one ethylenically unsaturated group, a photopolymerization initiator and a photosensitizer together with a photocrosslinkable polymer compound and a dye, and optionally further comprises a crosslinking agent. .
It may also contain other components.

Each component will be described below. -Photocrosslinkable polymer compound having at least one photodimerizable maleimide group in a side chain-In the present invention, a photocrosslinking polymer having at least one photodimerizable maleimide group in a side chain as a binder component Contains a polymer compound. The photocrosslinkable polymer compound is not affected by oxygen during exposure and can greatly improve the degree of cure after curing. In addition, the heat resistance of the composition is also improved, and it is possible to prevent the deformation and discoloration of the pattern during manufacturing.

The photocrosslinkable polymer compound is preferably a compound having a maleimide group represented by the following general formula (A) in its side chain.

[0017]

[Chemical 1]

In the general formula (A), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ¹ and R ² are bonded to each other to form a 5-membered ring or a 6-membered ring. May be formed.

As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable. The halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom.

The photocrosslinkable polymer compound according to the present invention comprises, for example, at least one of the monomers represented by the following general formulas (B) to (D) in a suitable solvent using a known polymerization initiator. It can be obtained by polymerization. That is, a copolymer containing at least one divalent group derived from the monomers represented by the following general formulas (B) to (D) in its constituent unit is preferable.

[0021]

[Chemical 2]

In the above general formulas (B) to (D), R ¹ and R ²
Is the same as R ¹ and R ² in the general formula (A). n represents an integer and is preferably 1 to 6.

Further, in order to impart alkali developability, it is preferable to further have an acidic group such as a carboxylic acid, a phenolic hydroxyl group or a sulfonamide group in the side chain, and it is particularly preferable to have a carboxylic acid. Therefore, it is preferably a copolymer containing a group (constitutional unit) derived from a monomer having a carboxylic acid group. Preferred monomers having a carboxylic acid group include acrylic acid, methacrylic acid, crotonic acid, vinyl benzoic acid, caprolactone adduct of (meth) acrylic acid, and hydroxyalkyl (meth).
Examples thereof include those obtained by adding an acid anhydride such as phthalic anhydride to acrylate.

The copolymerization ratio of the group (constituent unit) derived from the above-mentioned monomer in the copolymer is preferably 5 to 60 mol%. If the copolymerization ratio is less than 5 mol%, the sensitivity may decrease, and if it exceeds 60 mol%, overdevelopment may occur and an image may not be formed.

The photocrosslinkable polymer compound according to the present invention is a monomer having a maleimide group represented by the general formula (A), for example, at least one of the monomers represented by the general formulas (B) to (D). A polymer obtained by polymerizing
More preferably, one or more of the monomers having a maleimide group represented by the general formula (A) (such as the monomers represented by the general formulas (B) to (D)) and at least one polymerizable unsaturated It is a copolymer with one or more compounds having a bond and not having a maleimide group (compounds having a polymerizable unsaturated bond).

Examples of such a compound having a polymerizable unsaturated bond include acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and Examples thereof include compounds having a polymerizable unsaturated bond, selected from crotons esters and the like.

Specifically, for example, acrylic acid esters [for example, alkyl (wherein the alkyl group has 1 to 1 carbon atoms]
0 is preferred) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, -t-octyl acrylate,
Chlorethyl acrylate, glycidyl acrylate,
Benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg phenyl acrylate etc.)];

Methacrylic acid esters [eg, alkyl (wherein the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl) Methacrylate, chlorobenzyl methacrylate, octyl methacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (for example, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.)];

Acrylamide [eg, acrylamide, N-alkylacrylamide (the alkyl group preferably has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, Octyl group, cyclohexyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (the aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, etc.), N, N-dialkylacrylamide (the alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.), N,
N-aryl acrylamide (as the aryl group,
For example, there is a phenyl group. ), N-methyl-N-phenylacrylamide, N-2-acetamidoethyl-
N-acetylacrylamide, etc.];

Methacrylamides [eg methacrylamide, N-alkylmethacrylamide (wherein the alkyl group is preferably one having 1 to 10 carbon atoms, such as methyl group, ethyl group, t-butyl group, ethylhexyl group,
Examples include hydroxyethyl group and cyclohexyl group. ), N-arylmethacrylamide (the aryl group includes a phenyl group, etc.), N, N-dialkylmethacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diarylmethacrylamide (the aryl group includes a phenyl group, etc.), N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc.];

Allyl compounds (eg, allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyl) Oxyethanol etc.];

Vinyl ethers [eg alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethylbutyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.),
Vinyl aryl ether (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.)];

Vinyl esters [eg vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.];

Styrenes [eg styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene,
Trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene,
Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-tri Fluoromethylstyrene etc.)];

Crotonic acid esters [eg, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.)]; dialkyl itaconates (eg, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.) ; Maleic acid or fumaric acid dialkyls (eg, dimethyl maleate, dibutyl fumarate, etc.); Acronitrile,
There are methacrylonitrile and the like.

Of these compounds having a polymerizable unsaturated bond, methacrylic acid esters, acrylic acid esters, methacrylamides, acrylamides, acrylotolyl and methacrylonitrile are preferably used. These may be used alone or in combination of one or more, and the copolymerization ratio of these compounds in the copolymer is 0.
-80 mol% is preferable, and 30-80 mol% is particularly preferable.

One or more of these compounds having a polymerizable unsaturated bond and a monomer having a maleimide group represented by the general formula (A) (monomers represented by the general formulas (B) to (D), etc.) The copolymer with one or more of) may be any of block, random, graft and the like.

Examples of the solvent used for synthesizing the above copolymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,
N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate,
Examples thereof include methyl lactate and ethyl lactate. The said solvent is used individually or in mixture of 2 or more types.

The molecular weight of the photocrosslinkable polymer compound according to the present invention is preferably 2,000 or more on the mass average and 1,000 or more on the number average. More preferably, the mass average is in the range of 5,000 to 300,000, and the number average is in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10.

The photocrosslinkable polymer compound according to the present invention may contain unreacted monomers. In this case, the proportion of unreacted monomer in the resin is preferably 15% by mass or less.

-Dyes-Dyes and pigments can be used as dyes, and dyes or the like which have a desirable spectrum as a color filter and can be dissolved in a solvent that dissolves the binder resin as it is or in a modified form are used. Can be used. Among them, dyes are preferable from the viewpoint of high definition and high resolution.

Examples of the dye include oil-soluble dyes,
A disperse dye, a reactive dye, an acid dye or the like, or a direct dye or the like can be used. Specific examples of these dyes include, for example, Nippon Kayaku Co. or Orient Chemical Co.'s Varifast dye, Ciba Geigy's Orazole dye, BASF's Neozapon dye, or Sumitomo Chemical's Sumiplast. (Sumiplast) or oleosol dye, and the like.

In consideration of solubility, spectral characteristics, heat resistance, and light resistance, the yellow dye has a Valifast Ye content.
low 1108, same 3108, same 3120, same 412
0, 1151, 3150, Oil Yellow1
29, for red dye, Valifast Red130
6, Same 1308, Same 1360, Same 3304, Same 331
1, 2230, 3305, 3320, Valif
ast Pink2310N (all are manufactured by Orient Chemical Industry, Nippon Kayaku Co., Ltd.), PCRed136P, and blue dyes are Valifast Blue 2610 and 160.
Preferable examples thereof include No. 3, No. 1605, No. 2620 and No. 2606 (all manufactured by Nippon Kayaku Co., Ltd.).

Among them, Valifast Yellow
1108, 3120, 1151, Valifast
Red 1360, same 3304, same 3311, Vali
fast Pink2310N, PCRed136P,
Valifast Blue 2610, the same 2620, the same 2606, etc. are more preferable, and the Valifast Ye
low 3120, same 1151, Valifast R
ed1360, same 3304, same 3311, Valifa
st Pink2310N, ValifastBlue
2610, 2620, 2606, etc. are particularly preferable.

The concentration of the coloring matter (particularly dye) in all the solid components of the photosensitive coloring composition varies depending on the coloring matter (dye), but is preferably 0.5 to 80% by mass, and 0.5
-60 mass% is more preferable, and 0.5-50 mass% is especially preferable.

-Solvent- A solvent is generally used when preparing the photosensitive coloring composition of the present invention. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coating property of the photosensitive coloring composition,
In particular, it is preferably selected in consideration of the solubility of the dye and the binder resin, the coating property, and the safety. As the solvent,
Esters such as ethyl acetate, -n-butyl acetate,
Isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-Oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, etc .; 2-Oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, for example, methyl 2-methoxypropionate, 2 -Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2 -Methoxy-2-me Methyl Rupuropion acid, 2
Ethyl ethoxy-2-methylpropionate, etc .; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

Ketones such as methyl ethyl ketone,
Cyclohexanone, 2-heptanone, 3-heptanone,
Etc .; aromatic hydrocarbons such as toluene, xylene,
Etc. are preferred.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

-Photosensitizer-In the invention, it is also suitable to contain a photosensitizer. The photosensitizer is preferably a triplet sensitizer having a maximum absorption that allows sufficient light absorption in a wavelength range of 300 nm or more. Examples of such sensitizers include thioxane and thioxanthone derivatives such as 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, and 5-nitroacenaphthene. In addition, 1,2-dicyanobenzene, chloranil, and 2,3-described in JP-A-59-206425.
Electron accepting compounds such as dichloro-5,6-dicyanobenzoquinone are also effective. Furthermore, benzothiazole dyes,
A naphthothiazole dye, for example, a dye represented by the following formula is also useful.

[0052]

[Chemical 3]

In the above formula, R ³ represents an unsubstituted or optionally substituted alkyl group, and R ⁴ and R ⁵ are
Each independently represents a hydrogen atom, an aryl group, or a heterocyclic group, which may have a substituent or a substituent.

The amount of the photosensitizer added is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total solid content of the photosensitive composition for color filters.

-Other Components-In the photosensitive composition for a color filter of the present invention, if necessary, various additives, for example, a monomer or oligomer having at least one ethylenically unsaturated group, a photopolymerization initiator, A crosslinking agent, a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an agglomeration inhibitor and the like can be added.

<Monomer or oligomer having at least one ethylenically unsaturated group> The monomer or oligomer having at least one ethylenically unsaturated group is usually a monomer or oligomer having at least one addition-polymerizable ethylenic double bond. A compound having a boiling point of 100 ° C. or higher under pressure is preferable. The colored photosensitive composition of the present invention can be formed into a negative type by containing it together with a photopolymerization initiator described later.

Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth).
Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate,
Neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, after addition of ethylene oxide or propylene oxide to (meth) acrylate What was done, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 5
No. 0-6034, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Examples thereof include polyfunctional acrylates and methacrylates such as the polyester acrylates described and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. Furthermore, the Journal of Japan Adhesion Association, Vol. 20, No. 7, 30
Examples thereof include those introduced as photocurable monomers and oligomers on pages 0 to 308.

<Photopolymerization Initiator> Next, the photopolymerization initiator will be described. The photopolymerization initiator is contained together with the (D) monomer and the like. Examples of the photopolymerization initiator include (D)
It is not particularly limited as long as it can polymerize a monomer or an oligomer, but it is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost and the like.

For example, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and their derivatives, Examples include cyclopentadiene-benzene-iron complex and salts thereof, oxime-based compounds, and the like.

Examples of the active halogen compound which is a halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4 described in JP-B-57-6096.
-Oxadiazole compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-
Trichloromethyl-5- (p-cyanostyryl) -1,
3,4-oxadiazole, 2-trichloromethyl-5
-(P-methoxystyryl) -1,3,4-oxadiazole and the like can be mentioned.

As an active halogen compound which is a halomethyl-s-triazine compound, Japanese Patent Publication No. 59-1281 is available.
Vinyl-halomethyl-s-triazine compounds described in JP-A No. 53-133428,
(Naphth-1-yl) -4,6-bis-halomethyl-s
-Triazine compound and 4- (p-aminophenyl)-
2,6-di-halomethyl-s-triazine compounds and the like.

Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,6-bis (trichloromethyl) -4- (3.
4-Methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-
Methoxyphenyl) -1,3,5-triazine, 2,4
-Bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2 -(Naft-1-
Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,
6-bis-trichloromethyl-s-triazine, 2-
(4-Ethoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1- Il] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s
-Triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-
s-Triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4 , 6-Bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6
-Bis-trichloromethyl-s-triazine, 2- (5
-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s- Triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-
Triazine, 2- (4,5-dimethoxy-naphth-1-
Yl) -4,6-bis-trichloromethyl-s-triazine,

4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N -Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s
-Triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl)
-S-triazine, 4- [p-N, N-di (phenyl)
Aminophenyl] -2,6-di (trichloromethyl)-
s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)
-S-triazine,

4- [p-N- (p-methoxyphenyl)
Carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-
Di (trichloromethyl) -s-triazine, 4- [m-
Bromo-p-N, N-di (ethoxycarbonylmethyl)
Aminophenyl] -2,6-di (trichloromethyl)-
s-triazine, 4- [m-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
[M-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N
-Di (ethoxycarbonylmethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine, 4
-[O-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [o-fluoro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-p-N , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N
-Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p-N, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-N)
-Ethoxycarbonylmethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (m
-Chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-
Ethoxycarbonylmethylaminophenyl) -2,6-
Di (trichloromethyl) -s-triazine, 4- (o-
Chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine,

4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-
N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-
p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Bromo-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-(O-chloro-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine and the like.

In addition, TAZ series manufactured by Midori Kagaku Co. (for example, TAZ-107, TAZ-110, TAZ-10
4, TAZ-109, TAZ-140, TAZ-20
4, TAZ-113, TAZ-123), PANCHI
M series T series (for example, T-OMS, T-BM
P, T-R, T-B), Ciba-Geigy Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 100).
0, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1-
[4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-Chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2-
(O-Methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- ( Also useful are p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone and 2-bromo-.
9-anthrone, 2-ethyl-9-anthrone, 9,1
0-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone,
2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4
-Diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenyl styryl ketone,
p- (Dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, etc.
Examples thereof include benzothiazole compounds described in JP-A 1-448516, Tinuvin 1130, and 400.

In the colored photosensitive composition of the present invention, other known initiators can be used in addition to the above-mentioned photopolymerizable initiator. Specifically, US Pat. No. 2,367,660
Disclosed in US Pat. No. 2,367,661 and US Pat. No. 2,367,670, .alpha.-carbonyl compounds disclosed in US Pat. Acyloin ethers disclosed in US Pat. No. 2,448,828.
.Alpha.-hydrocarbon substituted aromatic acyloin compounds disclosed in U.S. Pat. No. 3,722,512.
Polynuclear quinone compounds disclosed in 046,127 and 2,951,758, US Pat. No. 3,54
A combination of triallyl imidazole dimer / p-aminophenyl ketones disclosed in 9,367,
Examples thereof include benzothiazole-based compounds / trihalomethyl-s-triazine-based compounds disclosed in JP-B-51-48516.

The total amount of the photopolymerization initiator (and known initiator) used is based on the solid content (mass) of the monomer.
0.01% by mass to 50% by mass is preferable, and 1% by mass to 3%
0 mass% is more preferable, and 1 mass% to 20 mass% is particularly preferable. If the amount used is less than 0.01% by mass, the polymerization may be difficult to proceed, and if it exceeds 50% by mass,
Although the polymerization rate increases, the molecular weight may decrease and the film strength may decrease.

<Crosslinking Agent> It is also possible to obtain a more highly cured film by supplementarily using a crosslinking agent. The cross-linking agent used in the present invention is not particularly limited as long as it can cure the film by a cross-linking reaction, and includes, for example, (a) epoxy resin, (b) methylol group, alkoxymethyl group, and acyloxymethyl group. Substituted with at least one substituent selected, melamine compounds, guanamine compounds,
Substituted with at least one substituent selected from glycoluril compounds or urea compounds, (c) methylol group, alkoxymethyl group, and acyloxymethyl group,
Phenolic compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Among them, the multi-sensitive epoxy resin is preferable.

The above-mentioned (a) epoxy resin may be any as long as it has an epoxy group and is crosslinkable, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether,
Butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, phthalic acid diglycidyl ester,
Divalent glycidyl group-containing low molecular weight compounds such as N, N-diglycidylaniline, as well as trivalent typified by trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether and TrisP-PA triglycidyl ether. Glycidyl group-containing low molecular weight compounds, likewise pentaerythritol tetraglycidyl ether, tetramethylol bisphenol A tetraglycidyl ether, and other tetravalent glycidyl group-containing low molecular weight compounds, likewise dipentaerythritol pentaglycidyl ether, dipenta Low molecular weight compounds containing polyvalent glycidyl groups such as erythritol hexaglycidyl ether, polyglycidyl (meth) acrylate, 2,2
1,2-bis (hydroxymethyl) -1-butanol
-Glycidyl group-containing polymer compounds represented by epoxy-4- (2-oxiranyl) cyclohexane adduct and the like,
Etc.

The number of methylol groups, alkoxymethyl groups and acyloxymethyl groups contained in the cross-linking agent (b) is 2 to 6 for melamine compounds, glycoluril compounds, guanamine compounds and urea compounds. In the case of a melamine compound, it is 5 to 6, and in the case of a glycoluril compound, a guanamine compound, and a urea compound, it is 3 to 4. Hereinafter, the melamine compound, the guanamine compound, the glycoluril compound and the urea compound (b) are collectively referred to as the compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) according to (b).

The compound containing a methylol group according to (b) is obtained by heating the compound containing an alkoxymethyl group according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid. To be (B)
The acyloxymethyl group-containing compound according to (2) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with an acyl chloride in the presence of a basic catalyst.

Specific examples of the compound (b) having the above substituent will be given below. Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 5 of the methylol groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or a mixture thereof.

Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine. , Tetramethylol guanamine 1
Examples thereof include compounds obtained by acyloxymethylating 3 to 3 methylol groups, or a mixture thereof.

Examples of the glycoluril compound include tetramethylolglycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 of the methylol groups of tetramethylolglycoluril, or a mixture thereof, tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 methylol groups are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolurea or a mixture thereof, tetramethoxyethylurea, and the like. These compounds according to (b) may be used alone or in combination.

The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, is Similar to the case of the agent (b), it is intended to suppress the intermixing with the overcoat photoresist by thermal crosslinking and further increase the film strength. Hereinafter, these compounds may be collectively referred to as a compound containing a methylol group, an alkoxymethyl group or an acyloxymethyl group according to (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the cross-linking agent (c) must be at least two per molecule, and from the viewpoint of thermal cross-linkability and storage stability, the skeleton A compound in which the 2-position and 4-position of the phenol compound to be The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent. In addition, the naphthol compound and the hydroxyanthracene compound, which are the skeletons, are
A compound in which all ortho positions and para positions of the H group are substituted is preferable. The naphthol compound may be unsubstituted or may have a substituent except the ortho position of the OH group.

The compound containing a methylol group according to the above (c) uses as a raw material a compound in which the 2- or 4-position of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, ammonia or tetraalkyl. It is obtained by reacting with formalin in the presence of a basic catalyst such as ammonium hydroxide. The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid. The acyloxymethyl group-containing compound according to (c) above can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

Examples of the skeletal compound in the cross-linking agent (c) include phenol compounds, naphthols and hydroxyanthracene compounds in which the ortho or para position of the phenolic OH group is not substituted, and examples thereof include isomers of phenol and cresol. Bisphenols such as body, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol-A,
4,4'-bishydroxybiphenyl, TrisP-P
A (manufactured by Honshu Chemical Industry Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

Specific examples of the cross-linking agent (c) include phenol compounds such as trimethylolphenol, tri (methoxymethyl) phenol, and a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, and a diamine such as 2,6-dimethylol-4-cresol. Methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl -4,4'-Bishydroxybiphenyl, hexamethylol form of TrisP-PA, Tri
Hexamethoxymethyl form of sP-PA, TrisP-P
Examples thereof include a compound in which 1 to 5 methylol groups of the hexamethylol compound of A are methoxymethylated, bishydroxymethylnaphthalenediol, and the like.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include the methylol group of the above-mentioned methylol group-containing compound. Examples thereof include compounds partially or wholly acyloxymethylated.

Of these compounds, preferred are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, hexamethylol form of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.), or their forms. Phenol compounds in which a methylol group is substituted with an alkoxymethyl group and both a methylol group and an alkoxymethyl group are mentioned. These compounds according to (c) may be used alone or in combination.

The total content of the cross-linking agents (a) to (c) in the colored photosensitive composition of the present invention varies depending on the material, but is based on the solid content (mass) of the curable composition.
1 to 70 mass% is preferable, 5 to 50 mass% is more preferable, and 7 to 30 mass% is particularly preferable.

When the colored photosensitive composition of the present invention is formed in a negative type, it is preferable to further add a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol,
t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,
2'-Methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate; nonion. -Based, cationic, anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-
Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 Adhesion promoters such as -chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6- Antioxidants such as di-t-butylphenol; 2- (3-t-butyl-
Examples thereof include UV absorbers such as 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

In order to promote the alkali solubility in the unirradiated area and further improve the developability of the photosensitive composition for a color filter of the present invention, an organic carboxylic acid, preferably a molecular weight, is added to the composition. It is possible to add a low molecular weight organic carboxylic acid of 1000 or less. Specifically, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, aliphatic monocarboxylic acids such as caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Tricarballylic acid, aconitic acid,
Aliphatic tricarboxylic acids such as camphorone acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melophanoic acid,
Aromatic polycarboxylic acids such as pyromellitic acid; phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid,
Other carboxylic acids such as phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umbellic acid and the like can be mentioned.

In the method for producing a color filter of the present invention, the above-mentioned photosensitive composition for a color filter is applied to a support by a coating method such as spin coating, cast coating or roll coating to obtain radiation sensitivity. A negative type colored pattern is formed by forming a composition layer, exposing the layer through a predetermined mask pattern, and developing the layer with a developing solution (image forming step). Further, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure may be included. In the production of the color filter, the image forming step (and the step of curing if necessary) is repeated for a desired number of hues to produce a color filter having a desired hue. Ultraviolet rays such as g-rays, h-rays and i-rays are preferably used as the radiation used in this case.

Examples of the support include soda glass, Pyrex (R) glass, quartz glass used in liquid crystal display elements and the like, those obtained by attaching a transparent conductive film thereto, and photoelectric conversion used in image pickup elements and the like. Element substrates such as silicon substrates and complementary metal oxide semiconductors (CM
OS) and the like. These substrates may be formed with black stripes that separate each pixel.
If necessary, an undercoat layer may be provided on these supports for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the substrate surface.

As the developer, any developer can be used as long as it has a composition that dissolves the unexposed portion of the photosensitive composition for a color filter of the present invention, but does not dissolve the exposed portion. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when the photosensitive composition for a color filter of the present invention is prepared.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.
[0] -7-undecene and other alkaline compounds are preferably dissolved in the solution to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. When a developer made of such an alkaline aqueous solution is used, it is generally washed with water after development.

The color filter of the present invention is particularly suitable for a high resolution CCD device, CMOS or the like having over 1 million pixels. The color filter of the present invention is, for example, C
It can be used as a color filter arranged between the light receiving portion of each pixel forming a CD and a microlens for collecting light.

[0099]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, "part" is based on mass unless otherwise specified. In this example, "a photocrosslinkable polymer compound having at least one photodimerizable maleimide group in its side chain" was simply referred to as "photocrosslinkable polymer compound".
Called.

(Example 1) 1) Synthesis of photocrosslinkable polymer compound (a) In a 500 ml three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel, 36.6 g of N- (3-hydroxypropyl) dimethylmaleimide ( 0.20 mole), 22.3 g (0.22 mole) of triethylamine, and 200 ml of diethyl ether were added, and the mixture was stirred in an ice water bath. 22.0 g (0.21 mo) of methacrylic acid chloride was added to this mixture.
le) was added dropwise with a dropping funnel over about 1 hour. After completion of dropping, the ice-water bath was removed and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the precipitate was filtered off and placed in a separating funnel. The ether solution was washed with a hydrochloric acid aqueous solution, a sodium carbonate aqueous solution, and water in this order, and dehydrated with sodium sulfate. The sodium sulfate was filtered off and then concentrated under reduced pressure to obtain 39 g of N- (3-methacryloxypropyl) dimethylmaleimide.

Subsequently, 300 m equipped with a stirrer and a cooling pipe
In a 3-necked flask, 35.2 g (0.14 mol) of N- (3-methacryloxypropyl) dimethylmaleimide
e), methacrylic acid 5.2 g (0.06 mole), 1
-Methoxy-2-propanol 95 g, and 2,2'-azobis (isobutyric acid) dimethyl (V
-601) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.461 g (0.0
02 mole) was added, and the mixture was stirred for 5 hours while heating to 75 ° C. in an oil bath under a N ₂ stream. After completion of the reaction, the mixture was poured into 1 L of water with stirring, and the precipitate was filtered and dried to obtain 38 g of a white solid (polymer compound). The weight average molecular weight (polystyrene standard) of the obtained polymer compound was measured by gel permeation chromatography and found to be 38,000 (photocrosslinkable polymer compound (a);
See Table 1 below).

[0102]

[Table 1]

[0103] 2) Preparation of resist solution   ・ Propylene glycol monomethyl ether acetate ... 19.20 parts     (PGMEA)   ・ Ethyl lactate ... 36.67 parts   ・ Benzyl methacrylate / methacrylic acid copolymer ... 30.51 parts     (Molar ratio: 75/25) 36% PGMEA solution   ・ Dipentaerythritol hexaacrylate ... 12.20 parts   ・ Polymerization inhibitor (p-methoxyphenol) ... 0.0061 parts   ・ Fluorosurfactant ... 0.83 parts   Photoinitiator TAZ-107 (Midori Kagaku Co., Ltd.) ... 0.586 parts Were mixed and dissolved to prepare a resist solution.

3) Preparation of Glass Substrate with Undercoat Layer The glass substrate (Corning 1737) was ultrasonically washed with 1% NaOH water, then washed with water and dehydrated and baked (200 ° C./30).
Minutes). Then, the resist solution of the above 2) is applied onto the glass substrate after washing so as to have a film thickness of 2 μm using a spin coater, and dried by heating at 220 ° C. for 1 hour,
A cured film (undercoat layer) was formed.

4) Preparation of Dye Resist Solution The compounds having the following compositions were mixed and dissolved to obtain a dye resist solution (photosensitive coloring composition). -Ethyl lactate ... 80 parts-Photocrosslinkable polymer compound obtained above (a; see Table 2 below) ... 17.50 parts-Photosensitizer represented by the following structural formula ... 1.00 parts-Red dye (Dye) ... 1.00 part (Valifast Red 1360, manufactured by Orient Chemical Co., Ltd.) * 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol ... 0 .50 copies

[0106]

[Chemical 4]

5) Exposure / Development of Dye Resist (Image Forming Step) The dye resist solution obtained in 4) above is applied onto the undercoat layer of the glass substrate with an undercoat layer obtained in 3) to form a film having a thickness of 1
Apply using a spin coater so that
Prebaked at 0 ° C. for 90 seconds. Then, using an exposure device, the coating film was irradiated with light having a wavelength of 365 nm through a 20 μm mask at each exposure amount of 100 mJ / cm ² . After irradiation, it was developed for 60 seconds at 26 ° C. using a 12.5% CD-2000 (manufactured by Fuji Film Arch) developer. Then, after rinsing with running water for 20 seconds, it was spray-dried to obtain a red pattern image.

6) Post-baking and measurement, etc. The pattern image after development was heated at 180 ° C. for 10 minutes.
After heating, the pattern shape of the obtained pattern image was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

7) Evaluation, etc. The following evaluation was performed on the obtained pattern image. The evaluation results are shown in Table 2 below. Heat resistance 6) The pattern image after post baking is further heated to 200 ° C.
Heated for 1 hour at 400n of pattern image before and after heating
The change in transmittance at m was visually evaluated and used as an index for heat resistance evaluation. Chemical resistance, pattern shape The pattern image after post-baking was immersed in acetone for 10 minutes, and the change of the pattern shape, the film loss, and the change of the spectral characteristics were visually observed.

Color Mixability The red dye used in the dye resist solution of the above 4) was replaced with a yellow dye (Valifast Yellow 1108 (manufactured by Orient Chemical Co.)), and a second color was applied on the same substrate on which a red pattern image was formed. Then, the dye elution and color mixing during the coating were evaluated by the change in absorbance before and after the second color image formation. In addition, the chromaticity, transmission spectrum, and absorbance of the pattern image were measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). As a result, the hue of the pattern image was good, and no hue change was observed before and after heating at 200 ° C.

(Examples 2 to 3) In the same manner as the synthesis of the photocrosslinkable polymer compound (a) in Example 1, the photocrosslinkable polymer compounds (b) and (c) shown in Table 1 were synthesized. did. The molecular weights of the photocrosslinkable polymer compounds (b) and (c) were 45,000 and 42,000, respectively.

Next, 4) the photocrosslinkable polymer compound (a) used in the preparation of the dye resist solution in Example 1 was replaced with the photocrosslinkable polymer compound (b) or (c) shown in Table 1 above.
The same procedure as in Example 1 was repeated except that
Furthermore, the same measurement and evaluation as in Example 1 were performed on the obtained pattern image. The results are shown in Table 2 below together with Example 1.
Shown in.

Comparative Example 1 Instead of the 4) dye resist solution prepared in Example 1, 99 parts of the resist solution obtained in “2) Preparation of resist solution” in Example 1 and a red dye (colorant; Valifast) were used. Example 1 was repeated, except that 1.0 part of Red1360, manufactured by Orient Chemical Co., Ltd.) was mixed and dissolved to obtain a resist solution (radical polymerization system). Furthermore, the same measurement and evaluation as in Example 1 were performed on the obtained pattern image. The results are shown in Table 2 below together with Example 1.

(Comparative Example 2) The same procedure as in Example 1 was carried out except that a dye resist solution (chemical amplification system) having the following composition was used in place of the dye resist solution 4) prepared in Example 1. Furthermore, the same measurement and evaluation as in Example 1 were performed on the obtained pattern image. The results are shown in Table 2 below together with Example 1.

[0115] 〔composition〕   ・ Ethyl lactate ... 80 parts   1: 1 copolymer of vinylphenol and methyl methacrylate ... 13.5 parts     (LYNCUR-CMM, manufactured by Maruzen Petrochemical Co., Ltd.)   -Hexamethoxymethylmelamine ... 4.0 parts     (Cymel 300, manufactured by Mitsui Cyanamit Co., Ltd.)   ・ The following photoacid generators: 1.5 parts

[0116]

[Chemical 5]

[0117]

[Table 2]

As is clear from the results shown in Table 2, the use of the photocrosslinkable polymer compound having a photodimerizable maleimide group as the binder component exerts sufficient curability and heat resistance, and It was possible to form various patterns with high sensitivity and high resolution, and the formed color filter was excellent in its pattern shape and hue. In addition, without containing a cross-linking agent, the dye elution at the time of applying the second color was significantly improved, and no color mixing occurred in each pixel of the color filter.

[0119]

EFFECTS OF THE INVENTION According to the present invention, high sensitivity, a high degree of curing with a high cross-linking density, no color mixing due to dye elution, a fine pattern can be formed with high resolution, and the properties of the color filter can be obtained. The heat-resistant composition does not impair (shape, hue, etc.), the hue and transmittance, and the yield are good, and the photosensitive composition for a color filter and the photosensitive composition for a color filter are used, and the pattern shape is good. Thus, it is possible to provide a color filter having excellent resolution, excellent hue and transmittance, and high productivity. Further, according to the present invention, in the method for producing a color filter of the present invention, the deterioration of the dye is prevented without impairing the properties of the color filter such as shape and hue, and the degree of cure with high sensitivity and resolution. It is possible to provide a method for manufacturing a color filter having a productivity capable of forming a high-quality pattern.

Claims (3)

[Claims] 1. A photosensitive composition for a color filter comprising a photocrosslinkable polymer compound having at least one photodimerizable maleimide group in a side chain and a dye. 2. A color filter comprising the photosensitive composition for a color filter according to claim 1. 3. The photosensitive composition for a color filter according to claim 1 is applied on a support and then exposed through a mask,
A method of manufacturing a color filter, comprising a step of developing to form a negative pattern.