JPH11119019A - Radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a transmission color filter excellent in transparency to radiation, balance of saturation and lightness, etc., by incorporating a colorant contg. at least one specified perylene pigment, an alkali-soluble resin, etc. SOLUTION: The radiation sensitive compsn. contains a colorant contg. at least one perylene pigment selected from the group comprising compds. represented by formula I or II, an alkali-soluble resin, a multifunctional monomer and a photopolymn. initiator. In the formula I, X and Y are each 1-10C alkyl, 6-20C monovalent arom. hydrocarbon, its substd. deriv., a group having a 5- or 6-membered N-contg. heterocycle or its substd. deriv., the 1-10C alkyl is, e.g. methyl or ethyl and the 6-20C monovalent arom. hydrocarbon is, e.g. phenyl, 4-biphenyl or 1-naphthyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition for a color filter used for producing a transmission type or reflection type color filter used for a color liquid crystal display device, a color image pickup tube element and the like.

[0002]

2. Description of the Related Art A color filter used in a color liquid crystal display device, a color image pickup tube element, or the like irradiates radiation (hereinafter, referred to as "exposure") to a coating film of a photosensitive resin through a photomask to form an exposure portion. Is cured, and then subjected to a development treatment to remove a non-exposed portion of the coating film to form a pattern, and then use a dyeing method (a dyeing method) or a composition in which a colorant is dispersed in a photosensitive resin. In the same manner as described above, it is manufactured by a method such as a photolithography method in which a coating film is formed, exposed and developed, and the colorants of these color filters include, in addition to the three primary colors of red, green and blue, For image pickup tubes, combinations of complementary colors of cyan, magenta and yellow have also been used. By the way, a color filter used in a color liquid crystal display device, a color image pickup tube element, or the like is composed of two or more kinds of pixels having different color tones arranged in parallel or intersecting in a striped pixel on the surface of a transparent substrate such as glass. The rectangular pixels are arranged vertically and horizontally, and the pixel size is as fine as about several tens μm to several hundred μm. Conventionally, when manufacturing a color filter in which such fine pixels are regularly arranged, a photosensitive resin is applied onto a substrate, and the formed coating film is exposed through a photomask to cure the radiation-irradiated portion. And then develop it,
After removing the unexposed portion of the coating film to form a pattern, a dyeing method for dyeing, or using a composition in which a coloring agent (dye or pigment) is dissolved or dispersed in a photosensitive resin, to form a coating film in the same manner as described above. In addition, a method such as a photolithography method of performing patterning by performing exposure and development processing is employed. In general, in a color liquid crystal display device, in order to drive a liquid crystal, a transparent electrode made of indium oxide, tin oxide, or the like is formed on a color filter by, for example, vapor deposition or sputtering, and the liquid crystal is further formed thereon in a certain direction. An alignment film for alignment is formed, and in order to obtain a high-performance transparent electrode and an alignment film, a high temperature of generally 200 ° C. or higher, preferably 250 ° C. or higher is required when forming them. Among the color filters manufactured by the above method, a color filter using a dye has high transparency to radiation, but has insufficient heat resistance. Therefore, formation of a transparent electrode and an alignment film is performed at a temperature of less than 200 ° C. Inevitably, the performance of the transparent electrode and the alignment film cannot be sufficiently ensured. In addition, color filters using dyes also have poor light resistance, and are not suitable for outdoor use. Therefore, instead of dyes, pigments having excellent heat resistance and light resistance have come to be used, and most of currently manufactured color filters use organic pigments. The color filter is roughly divided into a light source (backlight) on the back of the device and a transmissive type that displays by the transmitted light, and a light reflection plate such as an aluminum foil attached to the back of a transparent substrate provided on the back of the device. And a reflection type in which incident light from the front of the device is reflected and displayed. In recent years, reflecting the high quality of color liquid crystal display devices and color image pickup tube elements and the expansion of applications, colorants used in color filters have excellent transparency to radiation, balance between saturation and brightness. It is required to have dispersibility in resin components, etc., and also as a radiation-sensitive composition, coating uniformity when forming a pixel array, solubility in a developer, sensitivity, pattern shape, etc. Strictly required. However, the types of colorants used in color filters are extremely diverse, and it is actually difficult to find an appropriate colorant or a combination thereof that has an excellent balance of the above-mentioned various properties.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve the uniformity of application, sensitivity, developability, and the like when forming a pixel array. Another object of the present invention is to provide a radiation-sensitive composition for a color filter capable of forming a transmission-type or reflection-type color filter which is excellent in pattern shape, transparency to radiation, balance between saturation and brightness, and the like.

[0004]

The present invention provides (A) a colorant containing at least one kind of perylene pigment selected from the group of compounds represented by the following formula (1) or (2):
The radiation-sensitive composition for a color filter, comprising (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator.

[0005]

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[In the formula (1), X and Y each independently represent an alkyl group having 1 to 10 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a substituted derivative thereof, or a 5- to 6-membered compound. And a group having a nitrogen-containing heterocyclic ring or a substituted derivative thereof. ],

[0007]

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Hereinafter, the present invention will be described in detail. (A) Colorant The colorant in the present invention is a compound represented by the formula (1) (hereinafter, referred to as “pigment (1)”) and a compound represented by the formula (2) (hereinafter, “pigment”) (2) "), at least one perylene pigment selected from the group of (2). In the pigment (1), examples of the alkyl group having 1 to 10 carbon atoms of X and Y include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and sec. -Butyl group, t-butyl group, n-pentyl group, n-hexyl group,
Examples thereof include an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group.

The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms for X and Y includes, for example, phenyl group, 4
-Biphenyl group, 1-naphthyl group, 2-naphthyl group, 1
-Anthranyl group, 2-anthranyl group, 9-anthranyl group, 9-phenanthryl group and the like. The substituted derivatives of the aromatic hydrocarbon group include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, -OR ^1, -COR ^2, -C
OOR ³ , -N (R ⁴ ) (R ⁵ ), -SO ₃ R ⁶ , -SO ₂ R ⁷ , -OCO
R ⁸ , -N = NR ⁹ (where R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms) Indicates that R ⁷
R ⁸ independently represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms, and R ⁹ represents a monovalent aromatic having 6 to 20 carbon atoms. Shows a hydrocarbon group. ) And the like. X and Y
Specific examples of the substituted derivative of a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a p-chlorophenyl group, 3,5-
Dichlorophenyl, p-nitrophenyl group, 3,5-dinitrophenyl group, p-cyanophenyl group, 3,5-dicyanophenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, 3, 5-dimethylphenyl group, p-ethylphenyl group, 3,5-diethylphenyl group, o-hydroxyphenyl group, m-hydroxyphenyl group, p-hydroxyphenyl group, 3,5-dihydroxyphenyl group, o-methoxyphenyl Group, m-
Methoxyphenyl group, p-methoxyphenyl group, 3,5
-Dimethoxyphenyl group, p-ethoxyphenyl group,
3,5-diethoxyphenyl group, p-formylphenyl group, 3,5-diformylphenyl group, p-methylcarbonylphenyl group, 3,5-dimethylcarbonylphenyl group, p-carboxyphenyl group, 3,5- Dicarboxyphenyl group, p-methoxycarbonylphenyl group, 3,
5-dimethoxycarbonylphenyl group, p-ethoxycarbonylphenyl group, 3,5-diethoxycarbonylphenyl group, p-aminophenyl group, 3,5-diaminophenyl group, p-dimethylaminophenyl group, 3,5-bis (Dimethylamino) phenyl group, p-sulfophenyl group, 3,5-disulfophenyl group, p-methylsulfophenyl group, 3,5-dimethylsulfophenyl group, p-methylsulfonylphenyl group, 3,5-dimethyl A substituted phenyl group such as a sulfonylphenyl group, a p-methylcarbonyloxyphenyl group, a 3,5-dimethylcarbonyloxyphenyl group, a group represented by the following formula (3),

[0010]

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4'-chloro-4-biphenyl group, 4'-
Nitro-4-biphenyl group, 4'-cyano-4-biphenyl group, 4'-methyl-4-biphenyl group, 4'-hydroxy-4-biphenyl group, 4'-methoxy-4-biphenyl group, 4'- Formyl-4-biphenyl group, 4'-
Methylcarbonyl-4-biphenyl group, 4'-carboxy-4-biphenyl group, 4'-methoxycarbonyl-4
-Biphenyl group, 4'-amino-4-biphenyl group,
4'-dimethylamino-4-biphenyl group, 4'-sulfo-4-biphenyl group, 4'-methylsulfo-4-biphenyl group, 4'-methylsulfonyl-4-biphenyl group, 4'-methylcarbonyloxy-4 -Biphenyl group, a substituted 4-biphenyl group such as a group represented by the following formula (4),

[0012]

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4-chloro-1-naphthyl group, 4-nitro-1-naphthyl group, 4-cyano-1-naphthyl group, 4-
Methyl-1-naphthyl group, 4-hydroxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-formyl-
1-naphthyl group, 4-methylcarbonyl-1-naphthyl group, 4-carboxy-1-naphthyl group, 4-methoxycarbonyl-1-naphthyl group, 4-amino-1-naphthyl group, 4-dimethylamino-1- Naphthyl group, 4-sulfo-1-naphthyl group, 4-methylsulfo-1-naphthyl group, 4-methylsulfonyl-1-naphthyl group, 4-methylcarbonyloxy-1-naphthyl group, represented by the following formula (5) Substituted 1-naphthyl group such as

[0014]

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And the like.

Examples of the group having a 5- or 6-membered nitrogen-containing heterocyclic ring of X and Y include a 1-pyrrolyl group,
-Pyrrolyl group, 3-pyrrolyl group, 1-pyrazolyl group, 3
-Pyrazolyl group, 4-pyrazolyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 1-triazolyl group, 4-triazolyl group, 5-triazolyl group, 2-pyridinyl group, 3-pyridinyl group, 4 -Pyridinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5
-Pyrimidinyl group, 6-pyrimidinyl group, 2-pyrazinyl group, 3-pyrazinyl group, s-triazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isooxazolyl group, 4-isoxazolyl group, 5 -Isoxazolyl group, 2-thiazolyl group, 4-
Examples thereof include a thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, and a 5-isothiazolyl group. Among the substituents in the substituted derivative of the group having a nitrogen-containing heterocyclic ring, examples of the substituent for the nitrogen atom in the group having a nitrogen-containing heterocyclic ring include an alkyl group having 1 to 5 carbon atoms and a carbon atom having 6 to 5 carbon atoms. Examples thereof include an aryl group having 12 carbon atoms and an aralkyl group having 7 to 13 carbon atoms. Examples of the substituent for a carbon atom in the group having a nitrogen-containing heterocyclic ring include an alkyl group having 1 to 5 carbon atoms, In addition to the aryl group having 6 to 12 carbon atoms and the aralkyl group having 7 to 13 carbon atoms, the same groups as the substituents (excluding the alkyl group) in the substituted derivatives of the aromatic hydrocarbon group can be exemplified. .

Specific examples of substituted derivatives of a group having a 5- or 6-membered nitrogen-containing heterocyclic ring of X and Y include 2-methyl-
1-pyrrolyl group, 3-methyl-1-pyrrolyl group, 1-methyl-2-pyrrolyl group, 3-methyl-1-pyrazolyl group, 4-methyl-1-pyrazolyl group, 1-methyl-3-
Pyrazolyl group, 2-methyl-1-imidazolyl group, 4-
Methyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 4-methyl-2-imidazolyl group, 4-methyl-1-triazolyl group, 1-methyl-4-triazolyl group, 4-methyl-2-pyridinyl Group, 2-methyl-4
-Pyridinyl group, 4-methyl-2-pyrimidinyl group, 2
-Methyl-4-pyrimidinyl group, 3-methyl-2-pyrazinyl group, 2-methyl-3-pyrazinyl group, methyl-s
Alkyl-substituted derivatives such as -triazinyl group, dimethyl-s-triazinyl group; 2-phenyl-1-pyrrolyl group;
3-phenyl-1-pyrrolyl group, 1-phenyl-2-pyrrolyl group, 3-phenyl-1-pyrazolyl group, 4-phenyl-1-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 2-phenyl-1 -Imidazolyl group, 4-phenyl-1-imidazolyl group, 1-phenyl-2-imidazolyl group, 4-phenyl-2-imidazolyl group, 4-phenyl-1-triazolyl group, 1-phenyl-4-triazolyl group, 4 -Phenyl-2-pyridinyl group, 2-phenyl-4-pyridinyl group, 4-phenyl-2-pyrimidinyl group, 2-phenyl-4-pyrimidinyl group, 3-phenyl-2-pyrazinyl group, 2-phenyl-3- Pyrazinyl group, phenyl-s-triazinyl group, diphenyl-s
Phenyl-substituted derivatives such as -triazinyl group; 2-benzyl-1-pyrrolyl group, 3-phenyl-1-pyrrolyl group,
1-benzyl-2-pyrrolyl group, 3-benzyl-1-pyrazolyl group, 4-benzyl-1-pyrazolyl group, 1-benzyl-3-pyrazolyl group, 2-benzyl-1-imidazolyl group, 4-benzyl-1 -Imidazolyl group, 1-benzyl-2-imidazolyl group, 4-benzyl-2-imidazolyl group, 4-benzyl-1-triazolyl group, 1-
Benzyl-4-triazolyl group, 4-benzyl-2-pyridinyl group, 2-benzyl-4-pyridinyl group, 4-benzyl-2-pyrimidinyl group, 2-benzyl-4-pyrimidinyl group, 3-benzyl-2-pyrazinyl And benzyl-substituted derivatives such as a 2-benzyl-3-pyrazinyl group, a benzyl-s-triazinyl group and a dibenzyl-s-triazinyl group.

X and Y in the pigment (1) are as follows:
Methyl group, ethyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, Preferred are a 3,5-dimethoxyphenyl group, a p-ethoxyphenyl group, a 3,5-diethoxyphenyl group, a group represented by the above formula (3), and more preferably a methyl group, 3,5-dimethylphenyl Group, p-ethoxyphenyl group, the formula (3)
And the like. Specific examples of the pigment (1) are described in Color Index (CI; The Society of Dyers and Colou).
Published by rists. The same applies hereinafter. ), CI Pigment Red 123 (X and Y are p-ethoxyphenyl groups), CI Pigment Red 149 (X and Y are 3,
5-dimethylphenyl group), CI Pigment Red 17
8 (X and Y are groups represented by the formula (3)), CI Pigment Red 179 (X and Y are methyl groups), and the like. As the perylene pigment in the invention, pigment (2) is particularly preferred. Pigment (2) corresponds to CI Pigment Red 224 by a color index number. In the present invention, the perylene pigments can be used alone or in combination of two or more.

In the present invention, other coloring agents can be used in combination with the pigment (1) as the case may be. The other colorant is not particularly limited in color tone,
Further, an organic colorant or an inorganic colorant may be used. Examples of the organic colorant include dyes, organic pigments, and natural pigments. Examples of the inorganic colorant include, in addition to inorganic pigments, inorganic salts called extenders, and the like. As the other colorant in the above, a colorant having a high coloring property and a high heat resistance, particularly a colorant having a high thermal decomposition resistance is preferable, and an organic colorant is usually used, and an organic pigment is particularly preferable. As specific examples of the organic pigment, the following can be given by color index number.
CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24,
CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI
Pigment Yellow 83, CI Pigment Yellow 9
3, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, C.I.
I. Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, C.I.
Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, C.I.
CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, C.I.
CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, C.I.
Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, C.I.
CI Pigment Yellow 168, CI Pigment Yellow 175; CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 71, C.I.
I. Pigment Orange 73; CI Pigment Red 9,
CI Pigment Red 97, CI Pigment Red 12
2, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 202,
CI Pigment Red 209, CI Pigment Red 2
15, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 265; CI Pigment Violet 19,
CI Pigment Violet 23, CI Pigment Violet 29; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4,
CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

The inorganic colorant includes, for example,
Titanium oxide, barium sulfate, calcium carbonate, zinc white,
Lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (II
I)), cadmium red, ultramarine blue, navy blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In the present invention,
Other coloring agents can be used alone or in combination of two or more. The proportion of other colorants used is usually 99% by weight or less, preferably 90% by weight, based on all the colorants.
It is as follows. In this case, if the use ratio of the other colorant exceeds 99% by weight, it tends to be difficult to secure good coatability, sensitivity, developability, and the like while maintaining a balance between chroma and lightness.

The colorant in the present invention can be used together with a dispersant, if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants. As the surfactant, for example,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether;
Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters;
Tertiary amine-modified polyurethanes: In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals) Chemical Industry), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (above, manufactured by Asahi Glass) and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant to be used is generally 50 parts by weight or less, preferably 0 to 40 parts by weight, based on 100 parts by weight of the colorant.

(B) Alkali-Soluble Resin As the alkali-soluble resin in the present invention, (A) acts as a binder for a colorant and is soluble in an alkali developing solution used in a developing step in the production of a color filter. Any suitable resin can be used as long as the resin is used. Examples of such an alkali-soluble resin include a resin containing an acidic functional group such as a carboxyl group and a phenolic hydroxyl group. Among the alkali-soluble resins, the carboxyl group-containing alkali-soluble resin includes, for example, (co) -weight of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, simply referred to as “carboxyl group-containing unsaturated monomer”). Coalescence can be mentioned. Examples of the (co) polymer of the carboxyl group-containing unsaturated monomer include a carboxyl group-containing unsaturated monomer and another copolymerizable ethylenically unsaturated monomer (hereinafter, simply referred to as “other unsaturated monomer”). (Hereinafter simply referred to as “carboxyl group-containing copolymer (b)”) is preferred. Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid. Unsaturated dicarboxylic acids (anhydrides) such as, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides); succinic acid mono (2 -Acryloyloxyethyl), mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate,
2 such as mono (2-methacryloyloxyethyl) phthalate
Mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids having a valency of at least 1, mono- (meth) acrylate of carboxy polymer at both terminals such as ω-carboxy-polycaprolactone monomethacrylate and ω-carboxy-polycaprolactone monomethacrylate And the like. These carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

The other unsaturated monomers include:
For example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o
-Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, indene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzylmethyl Aromatic vinyl compounds such as ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate I-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, s c- butyl acrylate, sec
-Butyl methacrylate, t-butyl acrylate, t
-Butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl Methacrylate, 3-hydroxybutyl acrylate, 3-
Hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
Phenyl acrylate, phenyl methacrylate, 2-
Methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-
Phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate,
Methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3- Unsaturated carboxylic esters such as phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate; 2
-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2
-Dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate Aminoalkyl esters of unsaturated carboxylic acids such as methacrylic acid and 3-dimethylaminopropyl methacrylate; Glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Vinyl esters; unsaturated esters such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; Ethers; acrylonitrile, methacrylonitrile, alpha-chloro acrylonitrile, vinyl cyanide compounds such as vinylidene cyanide; acrylamide, methacrylamide, alpha-chloro acrylamide,
N- (2-hydroxyethyl) acrylamide, N-
Unsaturated amides such as (2-hydroxyethyl) methacrylamide; maleimide, N-cyclohexylmaleimide,
Unsaturated imides such as N-phenylmaleimide; 1,3-
Aliphatic conjugated dienes such as butadiene, isoprene and chloroprene; monoacryloyl groups or the like at the terminal of polymer molecular chains such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and polysilicone. Examples thereof include macromonomers having a monomethacryloyl group. These other unsaturated monomers can be used alone or in combination of two or more.

As the carboxyl group-containing copolymer (b), acrylic acid and / or methacrylic acid, styrene, methyl acrylate, methyl methacrylate,
Co-polymerization with at least one selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer Coalescence is preferred.

Specific examples of preferred carboxyl group-containing copolymer (b) include acrylic acid / benzyl acrylate copolymer, acrylic acid / styrene / methyl acrylate copolymer, acrylic acid / styrene / benzyl acrylate copolymer, Acrylic acid / methyl acrylate /
Polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl acrylate /
Polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate copolymer, acrylic acid / styrene / methyl methacrylate copolymer, acrylic acid / styrene / benzyl methacrylate copolymer Polymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid /
Methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl Methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-
Acrylic acid copolymers such as hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer;

Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / styrene / methyl acrylate copolymer, methacrylic acid / styrene / benzyl acrylate copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / Methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate /
Polystyrene macromonomer copolymer, methacrylic acid /
Benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / styrene / methyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / polystyrene Macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic Acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / - hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers,

Methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide / polystyrene macro Monomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
Methacrylic acid / styrene / phenyl methacrylate / N
-Phenylmaleimide / polystyrene macromonomer copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenyl Maleimide / polystyrene macromonomer copolymer, methacrylic acid / styrene / 2-
Hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, methacrylic acid / Styrene / 2-
Examples thereof include methacrylic acid copolymers such as hydroxyethyl methacrylate / phenyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer.

Among these carboxyl group-containing copolymers (b), methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / styrene / methyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate copolymer, Methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2- Mud methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers, methacrylic acid / styrene /
Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid /
Styrene / benzyl methacrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenyl Maleimide / polystyrene macromonomer copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide /
Polystyrene macromonomer copolymer, methacrylic acid /
Styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / N-phenylmaleimide /
Polystyrene macromonomer copolymer, methacrylic acid /
Styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer is preferred.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer (b) is as follows:
Usually, it is 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease. During development with a developer, the formed pixels tend to fall off the substrate and the surface of the pixels becomes rough. In particular, the carboxyl group-containing copolymer (b) containing the carboxyl group-containing unsaturated monomer at the specific copolymerization ratio has excellent solubility in an alkali developer, and the copolymer is used as a binder. The radiation-sensitive composition used as the non-dissolved material is very unlikely to remain after development with an alkaline developer, and it is difficult to cause background fouling, film residue, and the like in a region other than a portion where a pixel is formed on a substrate, Moreover, the pixel obtained from the composition does not dissolve excessively in the alkali developing solution, has excellent adhesion to the substrate, and does not have a risk of falling off the substrate. The carboxyl group-containing copolymer (b) preferably has a weight average molecular weight in terms of polystyrene (hereinafter, simply referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC; elution solvent: tetrahydrofuran) of preferably 3,000 or more. 300,000, more preferably 5,0
00 to 100,000.

Further, an alkali-soluble polyester resin can be used as the alkali-soluble resin.
As such a polyester resin, polylactic acid having a relatively low molecular weight is particularly preferable. The weight average molecular weight of the polylactic acid is usually from 3,000 to 300,000, preferably from 5,000 to 100,000. Further, as the phenolic hydroxyl group-containing alkali-soluble resin, for example,
Examples thereof include a (co) polymer of a phenolic hydroxyl group-containing vinyl aromatic compound and a phenol novolak resin. Examples of the phenolic hydroxyl group-containing vinyl aromatic compound include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy -Α-methylstyrene and the like. These phenolic hydroxyl group-containing vinyl aromatic compounds can be used alone or in combination of two or more. The phenolic hydroxyl group-containing vinyl aromatic compound may optionally be one or more other copolymerizable ethylenically unsaturated monomers, such as the other unsaturated monomers exemplified for the carboxyl group-containing copolymer (b). And can be copolymerized. Examples of the phenol used in the phenol novolak resin include o-cresol, m-cresol, and p-cresol.
-Cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol And the like, and as the aldehydes, for example,
Examples include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. These phenols and aldehydes can be used alone or in combination of two or more. The weight average molecular weight of the (co) polymer of the phenolic hydroxyl group-containing vinyl aromatic compound is preferably from 1,000 to 150,000.
0, more preferably 3,000 to 100,000. The weight average molecular weight of the phenol novolak resin is preferably from 1,000 to 150,000, and more preferably from 1,500 to 80,000.

In the present invention, the alkali-soluble resin is
They can be used alone or in combination of two or more. The amount of the alkali-soluble resin used in the present invention is
(A) Usually 10 to 10 parts by weight based on 100 parts by weight of the colorant.
00 parts by weight, preferably 20 to 500 parts by weight. In this case, if the use amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may be reduced, and background contamination or film residue may occur in a region other than a portion where a pixel is formed. If the amount exceeds 1,000 parts by weight, the concentration of the colorant relatively decreases, so that it may be difficult to achieve the desired color density as a thin film.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention comprises a monomer having two or more polymerizable ethylenically unsaturated bonds. Examples of such polyfunctional monomers include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates and dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as methylolpropane, pentaerythritol and dipentaerythritol; polyesters, epoxy resins,
Oligoacrylates or oligomethacrylates such as urethane resins, alkyd resins, silicone resins, and spirane resins; both ends hydroxypoly-1,3-butadiene;
Diacrylate or dimethacrylates of hydroxyl-terminated polymers such as hydroxyl-terminated hydroxypolyisoprene and hydroxyl-terminated hydroxypolycaprolactone, and tris (2
-Acryloyloxyethyl) phosphate, tris (2-methacryloyloxyethyl) phosphate, and the like.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols are preferred. Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Particularly, trimethylolpropane Triacrylate, pentaerythritol triacrylate, dipentaerythr Penta acrylate, dipentaerythritol hexaacrylate, high pixel intensities, excellent smoothness of the pixel surface and scumming in the region other than a portion where pixels are formed, are unlikely to generate film residue and the like. In the present invention, the polyfunctional monomers can be used alone or in combination of two or more. The amount of the polyfunctional monomer used in the present invention is usually 5 to 50 parts by weight per 100 parts by weight of the alkali-soluble resin (B).
0 parts by weight, preferably 20 to 300 parts by weight. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight,
If the pixel strength or the smoothness of the pixel surface tends to be insufficient, on the other hand, if it exceeds 500 parts by weight, for example, the alkali developability is reduced, and background contamination or film in a region other than the portion where the pixel is formed is reduced. The remainder tends to occur easily.

(D) Photopolymerization Initiator The photopolymerization initiator of the present invention is obtained by exposing the above (C) polyfunctional monomer to light by exposing it to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray. It consists of a compound capable of generating an active species capable of initiating polymerization. Examples of such a photopolymerization initiator include a biimidazole compound having at least one main skeleton represented by the following formula (6), formula (7) or formula (8), a benzoin compound,
Acetophenone compound, benzophenone compound, α
-Diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, triazine compounds and the like can be mentioned, and among them, biimidazole compounds are preferable.

[0035]

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Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4 -Phenoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4
-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl)
-4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,
2'-bis (2,4,6-trichlorophenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4',
5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxy Carbonylphenyl) -1,2'-
Biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 '
-Tetrakis (4-phenoxycarbonylphenyl)-
1,2′-biimidazole, 2,2′-bis (2,4,
6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'
-Biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, , 2'-bis (2-cyanophenyl)
-4,4 ', 5.5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,
2'-bis (2-cyanophenyl) -4,4 ', 5
5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2
-Methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-methylphenyl)-
4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2-methylphenyl) -4,4 ', 5,5'-
Tetrakis (4-phenoxycarbonylphenyl)-
1,2'-biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-
Methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-ethylphenyl) -4,
4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-phenoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2-phenylphenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-phenylphenyl) -4,4', 5,5'-tetrakis ( 4-phenoxycarbonylphenyl) -1,
2'-biimidazole,

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'
-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 ,
4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dicyanophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4', 5,5'-tetraphenyl- 1,
2′-biimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 ,
4,6-trimethylphenyl) -4,4 ', 5,5'-
Tetraphenyl-1,2'-biimidazole, 2,2 '
-Bis (2,4-diethylphenyl) -4,4 ', 5
5′-tetraphenyl-1,2′-biimidazole,
2,2'-bis (2,4,6-triethylphenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-diphenylphenyl) -4,4', 5,5'-tetraphenyl-1 ,
2′-biimidazole, 2,2′-bis (2,4,6-
(Triphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Of these biimidazole compounds,
In particular, 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2,4,
6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 '
-Tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl)-
4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole is preferred. The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, and has high sensitivity. Since the curing reaction is high and no curing reaction occurs in the unexposed area, the coated film after exposure is clearly divided into a cured area insoluble in the developer and an uncured area having a high solubility in the developer. It is possible to form an excellent color filter which is divided and has no pattern missing, missing or undercut.

The benzoin-based compound includes
For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, methyl-2-benzoylbenzoate and the like can be mentioned. Examples of the acetophenone-based compound include, for example, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-
(4-i-propylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl- (4- Methylthiophenyl) -2-morpholino-1-propane-1-
On, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-azidoacetophenone, 4-azidobenzalacetophenone and the like. Examples of the benzophenone-based compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 3,3-dimethyl-4-methoxybenzophenone, and the like. . The α-
Examples of the diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate and the like. As the polynuclear quinone compound, for example,
Anthraquinone, 2-ethylanthraquinone, 2-t-
Butyl anthraquinone, 1,4-naphthoquinone and the like can be mentioned. Examples of the xanthone-based compound include xanthone, thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. As the diazo compound, for example,
4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like can be mentioned. Examples of the triazine-based compound include 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine and 2- (3 ′, 4′-dimethoxystyryl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-bromo-4'-methylphenyl) -4,6-bis (tric 15
Methyl) -s-triazine, 2- (2′-thiophenylethylidene) -4,6-bis (trichloromethyl) -s
-Triazine and the like. Further, as other photopolymerization initiators, 4-azidobenzaldehyde, azidopyrene, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, N-phenylthioacridone, triphenylpyridone Lium perchlorate can also be used.

In the present invention, the photopolymerization initiators can be used alone or in combination of two or more. The amount of the photopolymerization initiator used in the invention is usually 0.01 to 200 parts by weight based on 100 parts by weight of the polyfunctional monomer (C).
It is preferably 1 to 120 parts by weight, particularly preferably 1 to 50 parts by weight. In this case, if the amount of the photopolymerization initiator is less than 0.01 part by weight, curing by radiation irradiation becomes insufficient, and there is a possibility that a pattern may be missing, chipped or undercut, while if it exceeds 200 parts by weight,
The formed pattern easily falls off the substrate during development,
In addition, background contamination, film residue, and the like are likely to occur in a region other than the portion where the pattern is formed.

Further, in the present invention, a sensitizer, a curing accelerator, a polymer photocrosslinking / sensitizer and the like can be used together with the photopolymerization initiator. Examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, and 2,5-bis (4 ′ -Diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin,
4- (diethylamino) chalcone and the like can be mentioned. These sensitizers can be used alone or in combination of two or more. Examples of the curing accelerator include 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
Chain transfer agents such as mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-4,6-dimethylaminopyridine can be exemplified. These curing accelerators can be used alone or in combination of two or more. In addition, the polymer photocrosslinking / sensitizer has at least one functional group capable of acting as a crosslinking agent and / or a sensitizer upon irradiation with a radiation having a main chain and / or a functional group.
Or a high molecular compound having in a side chain, examples of which include a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, a condensate of 4-azidobenzaldehyde and a phenol novolak resin, and 4-acryloylphenylcinnamoyl ester Homopolymer or copolymer, 1,4-polybutadiene, 1,2-polybutadiene and the like can be mentioned. These polymer photocrosslinking / sensitizers can be used alone or in combination of two or more. The total used amount of the sensitizer, the curing accelerator and the polymer photocrosslinking / sensitizer in the present invention is 100 photopolymerization initiators.
It is usually 300 parts by weight or less, preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to parts by weight.

In the present invention, as the photopolymerization initiator,
In particular, it is preferable to use a combination of a biimidazole-based compound and a benzophenone-based compound and / or a thiazole-based curing accelerator, since the formed pixels are less likely to fall off the substrate during development, and the pixel strength and sensitivity are high. In the present invention, when a biimidazole compound and another component are used in combination as the photopolymerization initiator, the amount of the other component used is preferably 80% by weight or less based on the entire photopolymerization initiator. Particularly preferred photopolymerization initiators in the present invention are shown below as combinations of the components. That is, 2,2′-bis (2-
(Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone, 2,2'-bis (2- Chlorophenyl)-
4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'
-Bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5, 5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone, 2,
2'-bis (2-chlorophenyl) -4,4 ', 5
5'-tetrakis (4-ethoxycarbonylphenyl)
-1,2'-biimidazole / 4,4'-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole, 2,2'-bis (2,4-dichlorophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone, 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5,5'-Tetraphenyl-1,2 '
-Biimidazole / 4,4'-bis (diethylamino)
Benzophenone / 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) butan-1-one,
2,2′-bis (2,4-dichlorophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butan-1-one / 2-mercaptobenzothiazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi Imidazole / 4,4'-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-
1-one, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′
-Biimidazole / 4,4'-bis (diethylamino)
Benzophenone / 1-hydroxycyclohexyl phenyl ketone, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,
2′-biimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole.

Additives The radiation-sensitive composition for a color filter of the present invention may contain a solvent. The solvent may dissolve or disperse the components (A), (B), (C) and (D), and the additive component, if desired, and may not react with these components. As long as it has volatility, it can be appropriately selected and used. Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether,
Ethylene glycol monoalkyl ethers such as ethylene glycol mono-n-butyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono- Polyethylene glycol monoalkyl ethers such as n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-
n-propyl ether, propylene glycol mono-n
Propylene glycol monoalkyl ethers such as -butyl ether; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahi Other ethers such as Rofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone,
Ketones such as 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate; methyl 3-methoxypropionate;
Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n-butyl, methyl pyruvate, ethyl pyruvate,
Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N ,
Examples thereof include amides such as N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

Further, benzyl ethyl ether, dihexyl ether, acetonylacetone,
Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate , Etc., can be used in combination. These high-boiling solvents can be used alone or in combination of two or more.

Among these solvents, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, from the viewpoints of solubility, pigment dispersibility, coatability and the like.
Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, n-butyl acetate, i-butyl acetate,
Preferred are n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like, and as the high boiling solvent, γ-butyrolactone and the like preferable. The amount of the solvent used in the present invention is usually 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B).

Further, the radiation-sensitive composition for a color filter of the present invention may contain various additives other than the solvent, if necessary. Examples of the additive include an organic acid having a function of further improving the solubility of the radiation-sensitive composition in an alkali developer and suppressing the remaining of undissolved material after development. As such an organic acid, an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having a molecular weight of 1,000 or less is preferable. Specific examples of the aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itacone acid,
Examples thereof include dicarboxylic acids such as citraconic acid, maleic acid, fumaric acid, and mesaconic acid; and tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid. Examples of the phenyl group-containing carboxylic acid include an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain. Specific examples include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelitic acid, and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; trimellitic acid, trimesic acid, and melophane Trivalent or higher aromatic polycarboxylic acids such as acid and pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidenic acid, coumaric acid, umbel Acids and the like can be mentioned. Among these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid have alkali solubility, solubility in a solvent, This is preferable from the viewpoint of preventing background contamination and film residue in a region other than the portion where the upper pixel is formed. The organic acids can be used alone or in combination of two or more. The amount of the organic acid used is usually 10% by weight or less, preferably 0.0% by weight, based on the whole radiation-sensitive composition.
It is from 0.01 to 10% by weight, more preferably from 0.01 to 1% by weight. In this case, if the amount of the organic acid used exceeds 10% by weight, the adhesion of the formed pixel to the substrate tends to decrease.

Examples of additives other than the organic acids include dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives; fillers such as glass and alumina; polyvinyl alcohol and polyethylene glycol monoalkyl ether. And high molecular compounds such as poly (fluoroalkyl acrylate); nonionic, cationic and 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-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and other adhesion promoters; 2,2-thiobis (4-methyl-6-t-butylphenol), 6-di-t-
Antioxidants such as butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; aggregation inhibitors such as sodium polyacrylate Can be mentioned.

Method for Forming Color Filter Next, a method for forming a transmission color filter and a reflection color filter using the radiation-sensitive composition for a color filter of the present invention will be described. First, a light-shielding layer is formed so as to partition a portion where a pixel pattern is to be formed on the surface of a transparent substrate, and for example, a composition in which a colorant (A) is dispersed is applied onto the substrate, and then prebaking is performed. To evaporate the solvent to form a coating film. Next, after this coating film is exposed through a photomask, development processing is performed with an alkali developing solution to dissolve and remove unexposed portions of the coating film, and preferably by performing post-baking, whereby the colored pixels are formed. A pixel array arranged in a predetermined pattern is formed. Thereafter, if necessary, using each composition in which a colorant of another color (for example, red, green or blue) is dispersed, coating, pre-baking, exposure and development treatment of each composition in the same manner as described above. , And preferably post-baking to form a pixel array of each color sequentially on the same substrate to obtain a color filter. Examples of the transparent substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. On these transparent substrates, if desired,
Appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, a gas phase reaction method, or vacuum deposition can also be performed. When applying the radiation-sensitive composition for a color filter of the present invention to a transparent substrate, an appropriate coating method such as spin coating, casting coating, and roll coating can be adopted. The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 1.5 μm, as a film thickness after drying. As the radiation used for forming the color filter, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-ray, or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. The irradiation energy amount of the radiation is preferably 1
１０００1000 mJ / cm ² . Examples of the alkali developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8, and the like.
-Diazabicyclo- [5.4.0] -7-undecene,
An aqueous solution such as 1,5-diazabicyclo- [4.3.0] -5-nonene is preferred. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkali developer. After the alkali development, the film is usually washed with water. As the alkali developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method, and the like can be applied.
The development condition is preferably at room temperature for 5 to 300 seconds. The transmission type color filter and the reflection type color filter thus formed are particularly suitably used for a color image pickup tube element, and are also useful for a color liquid crystal display device, a color sensor and the like.

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color filter of the present invention essentially comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. Although it is contained as a component, the following (a) to (下 記) are specific examples of particularly preferred compositions. (A) The component (B) is composed of a carboxyl group-containing copolymer (b), and the component (D) is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4)
-Ethoxycarbonylphenyl) -1,2'-biimidazole and 2,2'-bis (2-bromophenyl)-
A radiation-sensitive composition for a color filter, comprising at least one member selected from the group consisting of 4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole. (B) The component (B) is composed of the carboxyl group-containing copolymer (b), and the component (D) is 2,2′-bis (2,4).
-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetraphenyl-
A radiation-sensitive composition for a color filter, comprising at least one member selected from the group consisting of 1,2'-biimidazole. (C) The component (D) wherein the component (D) further contains one or more components selected from the group of other photopolymerization initiators, sensitizers, curing accelerators, and polymer photocrosslinking / sensitizers. B) The radiation-sensitive composition for a color filter. (D) The carboxyl group-containing copolymer (b) as the component (B) is a methacrylic acid / benzyl methacrylate copolymer, a methacrylic acid / styrene / methyl methacrylate copolymer, or a methacrylic acid / styrene / benzyl methacrylate copolymer. , Methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl Methacrylate macromonomer copolymer, methacrylic acid / 2-
Hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer Methacrylic acid / styrene / phenyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenylmale Mido / polystyrene macromonomer copolymer, methacrylic acid / styrene / phenyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide / Polystyrene macromonomer copolymer, methacrylic acid / styrene /
2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / N-phenylmaleimide / polystyrene macromonomer copolymer and methacryl The color of (a), (b) or (c), which is at least one selected from the group consisting of acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer. Radiation-sensitive composition for filters. (E) The component (C) is composed of at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, (A), (B), and (B). The radiation-sensitive composition for a color filter according to (c) or (d). (F) The above (a), (b), wherein the component (A) contains the pigment (1) and / or the pigment (2) and another colorant.
(C) The radiation-sensitive composition for a color filter according to (d) or (e). (G) The radiation-sensitive composition for color filters as described in (f) above, wherein the other colorant contains CI Pigment Yellow 150. (H) The radiation-sensitive composition for a color filter according to the above (F) or (G), wherein the other colorant contains CI Pigment Yellow 155. (I) The radiation-sensitive composition for a color filter according to the above (f), (g) or (h), wherein the other coloring agent comprises CI Pigment Red 254. (N) The radiation-sensitive composition for a color filter according to the above (F), (G), (H) or (H), wherein the other colorant contains CI Pigment Red 177. (R) The radiation-sensitive composition for a color filter according to the above (F), (G), (H), (H), or (H), wherein the other colorant contains CI Pigment Yellow 83. (ヲ) The above (f), (g), (h), (li), (nu) in which the other colorant contains CI Pigment Yellow 139
Or (11) a radiation-sensitive composition for a color filter.

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. Comparative Example 1 100 parts by weight of an 80/20 (weight ratio) mixture of CI Pigment Red 177 and CI Pigment Yellow 139 as the component (A), and methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer as the component (B) Copolymer weight ratio = 25/65/10, weight average molecular weight = 55,000) 50 parts by weight, dipentaerythritol pentaacrylate as component (C) 40 parts by weight,
Component (D) is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′
A mixture of 10 parts by weight of biimidazole, 10 parts by weight of 4,4'-bis (diethylamino) benzophenone, 5 parts by weight of malonic acid as an organic acid, and 800 parts by weight of ethylene glycol monoethyl ether acetate as a solvent; A composition was prepared. Next, on a surface of a transparent substrate made of soda glass on which a silica (SiO ₂ ) film that prevents elution of sodium ions on the surface is formed, a light-shielding layer is provided so as to partition a portion where a pixel pattern is formed,
The radiation-sensitive composition was applied using a spin coater, and prebaked at 90 ° C. for 2 minutes to form a film having a thickness of 2.0
A μm coating film was formed. After cooling the board,
Using a high-pressure mercury lamp, the coating film was exposed to ultraviolet light of 100 mJ / cm ² including light of wavelengths of 365 nm, 405 nm and 436 nm through a photomask. Next, the substrate is immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to perform a development process.
After washing with ultrapure water and air-drying,
20 minutes post-baking for each side 20μm × 20μm
The pixel array in which the red pixel pattern of the size of was formed. At this time, when the substrate after prebaking was visually observed, a swell was observed at the center of the substrate, and the coating uniformity was insufficient. In addition, when the obtained pixel array was observed with an optical microscope, it was found that undissolved matter remained in a region on the substrate where no pattern was formed. Further, a color analyzer (TC-18 manufactured by Tokyo Denshoku Co., Ltd.) is used as an index of the transparency of the pixel array to radiation.
00M), the Y value in the CIE color system was measured with a C light source and a 2 degree field of view, and it was a low value of Y = 20.

Comparative Example 2 100 parts by weight of a 75/25 (weight ratio) mixture of CI Pigment Red 177 and CI Pigment Yellow 83 was used as the component (A), and methacrylic acid / benzyl methacrylate / polystyrene macromonomer was used as the component (B). 50 parts by weight of a polymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 55,000), 40 parts by weight of dipentaerythritol pentaacrylate as the component (C),
Component (D) is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′
A mixture of 10 parts by weight of biimidazole, 10 parts by weight of 4,4'-bis (diethylamino) benzophenone, 5 parts by weight of citraconic acid as an organic acid, and 800 parts by weight of ethylene glycol monoethyl ether acetate as a solvent; A composition was prepared. Next, a light-shielding layer is provided on the surface of a transparent substrate made of soda glass on which a silica (SiO ₂ ) film for preventing elution of sodium ions from being formed is formed so as to partition a portion where a pixel pattern is formed. The radiation-sensitive composition was applied using a coater, and prebaked at 90 ° C. for 2 minutes to form a film having a thickness of 2.
A 0 μm coating was formed. After cooling the substrate, the coating film was exposed to ultraviolet light of 100 mJ / cm ² including light of wavelengths of 365 nm, 405 nm and 436 nm using a high-pressure mercury lamp through a photomask. Next, the substrate is immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to perform a development treatment, washed with ultrapure water, air-dried, and further dried at 180 ° C.
And post-bake for 30 minutes at each side, 20 μm × 2
A pixel array in which a red pixel pattern having a size of 0 μm was formed. At this time, when the substrate after prebaking was visually observed, a swell was observed at the center of the substrate, and the coating uniformity was insufficient. In addition, when the obtained pixel array was observed with an optical microscope, it was found that undissolved matter remained in a region on the substrate where no pattern was formed. Further, a color analyzer (TC-TC manufactured by Tokyo Denshoku Co., Ltd.)
1800M), the Y value in the CIE color system was measured with a C light source and a 2 degree visual field, and it was a low value of Y = 21.

[0052]

【Example】

Example 1 CI Pigment Red 224, CI Pigment Red 177 and CI Pigment Yellow 1 as the components (A)
80 parts by weight of a 47/49/4 (weight ratio) mixture of 39
As the component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 550,000)
0) 50 parts by weight, 40 parts by weight of dipentaerythritol pentaacrylate as the component (C), and 2,2′-bis (2-chlorophenyl) -4,4 ′, as the component (D).
10,5 parts by weight of 5,5′-tetraphenyl-1,2′-biimidazole, 10 parts by weight of 4,4′-bis (diethylamino) benzophenone, 5 parts by weight of malonic acid as an organic acid,
Then, 800 parts by weight of ethylene glycol monoethyl ether acetate was mixed as a solvent to prepare a radiation-sensitive composition. Next, a light-shielding layer is provided on the surface of a transparent substrate made of soda glass on which a silica (SiO ₂ ) film for preventing elution of sodium ions from being formed is formed so as to partition a portion where a pixel pattern is formed. The radiation-sensitive composition was applied using a coater, and prebaked at 90 ° C. for 2 minutes to form a coating film. Then, after cooling the substrate, the wavelengths of 365 nm, 405 nm and 43
It was exposed to ultraviolet light of 100 mJ / cm ² including light of 6 nm. Next, the substrate is immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to perform development processing, washed with ultrapure water, air-dried, and further post-baked at 180 ° C. for 30 minutes. Line up, each side 20
A pixel array in which a red pixel pattern having a size of μm × 20 μm was formed. However, in Example 1, the film thickness was adjusted so as to obtain the same chromaticity (x and y values in the CIE color system) as in Comparative Example 1. At this time, when the substrate after prebaking was visually observed, there was no swelling at the center of the substrate and the coating uniformity was excellent. In addition, when the obtained pixel array was observed with an optical microscope, no undissolved matter remained in the region where the pattern was not formed on the substrate, and the pixel array was excellent in developability and the pattern shape was good. Was. Furthermore, a color analyzer (Tokyo Denshoku Co., Ltd.) is used as an index of the transparency of the pixel array against radiation.
TC-1800M), using a C light source and a 2 degree visual field,
When the Y value in the CIE color system was measured, Y = 24
And high values were obtained. Further, the obtained pixel array had a good balance between saturation and lightness.

Example 2 CI Pigment Red 224 was used as the component (A) in 100 parts.
Parts by weight, as component (B), methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 5)
5,000) 50 parts by weight, dipentaerythritol pentaacrylate 40 parts by weight as the component (C), and 2,2′-bis (2-chlorophenyl) -4,
10 parts by weight of 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 4,4'-bis (diethylamino)
A radiation-sensitive composition was prepared by mixing 10 parts by weight of benzophenone, 5 parts by weight of citraconic acid as an organic acid, and 800 parts by weight of ethylene glycol monoethyl ether acetate as a solvent. Next, a light-shielding layer is provided on the surface of a transparent substrate made of soda glass on which a silica (SiO ₂ ) film for preventing elution of sodium ions from being formed is formed so as to partition a portion where a pixel pattern is formed, and then a spin-coat is performed. Apply the radiation-sensitive composition using a coater,
For 2 minutes to form a coating film. Then, after cooling the substrate, the wavelength of 365 nm and 405 nm was applied to the coating film through a photomask using a high pressure mercury lamp.
And 100 mJ / cm ² of ultraviolet light including light of 436 nm. Next, the substrate is immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to perform development processing, washed with ultrapure water, air-dried, and further post-baked at 180 ° C. for 30 minutes. Then, a pixel array in which a red pixel pattern having a size of 20 μm × 20 μm on each side was formed. However, in Example 2, the film thickness was adjusted so that the same chromaticity (x and y values in the CIE color system) as in Comparative Example 2 was obtained. At this time,
When the substrate after prebaking was visually observed, there was no swelling at the center of the substrate and the coating uniformity was excellent. In addition, when the obtained pixel array was observed with an optical microscope, no undissolved matter remained in the region where the pattern was not formed on the substrate, and the pixel array was excellent in developability and the pattern shape was good. Was. Further, a color analyzer (TC-1800M manufactured by Tokyo Denshoku Co., Ltd.) was used as an index of transparency of the pixel array against radiation, and a C light source and a C light source were used.
When the Y value in the CIE color system was measured in a degree visual field, a high value of Y = 27 was obtained. Further, the obtained pixel array had a good balance between saturation and lightness.

[0054]

The radiation-sensitive composition for a color filter of the present invention has excellent coating uniformity, developability, sensitivity and the like when forming a pixel array, and has a pattern shape, transparency to radiation, and chroma. And a pixel array having an excellent balance of brightness and the like.

Embedded image

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/028 G03F 7/028 // C08F 2/50 C08F 2/50 C08L 101/00 C08L 101/00 (72) Inventor Iijima Takahiro 2-11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] (A) a colorant containing at least one perylene pigment selected from the group of compounds represented by the following formula (1) or (2): (B) an alkali-soluble resin,
A radiation-sensitive composition for a color filter, comprising (C) a polyfunctional monomer and (D) a photopolymerization initiator. Embedded image [In the formula (1), X and Y each independently represent an alkyl group having 1 to 10 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a substituted derivative thereof, or a 5- to 6-membered ring. A group having a nitrogen heterocycle or a substituted derivative thereof is shown. [Chemical formula 2]