JP2001033620A - Radiation-sensitive composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a color filter excellent in pattern shape, achievable sufficient curing reaction of a radiation-sensitive composition by exposure with a small energy amount without remaining an undissolved substance when developing. SOLUTION: This radiation-sensitive composition for color filter contains (A) a coloring agent, (B) an alkali-soluble resin, (C) polyfunctional monomer, and (D) a photoradical generator essentially containing a compound represented by 2-methyl-1-(4'-methylthiophenyl)-2-morpholinopropane-1-one expressed by formula I and a compound represented by 4,4'-bis(diethylamino)benzophenone expressed by formula II. The color filter has pixels formed of the radiosensitive composition for the color filter. In the formula I, R1 and R2 are each a 1-6C alkyl group. In the formula II, R3, R4, R5 and R6 are each a 1-6C alkyl group.

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 for forming a color filter used in a transmission type or reflection type color liquid crystal display device, a color image pickup tube element or the like, and the radiation sensitivity. The present invention relates to a color filter formed from a hydrophilic composition.

[0002]

2. Description of the Related Art Conventionally, in producing a color filter using a radiation-sensitive composition, the radiation-sensitive composition is applied to a substrate or a substrate on which a light-shielding layer having a desired pattern is formed in advance and dried. Thereafter, the dried coating film is irradiated with radiation in a desired pattern (hereinafter, referred to as "exposure").
Then, by developing, pixels of each color are obtained. In the process of manufacturing such a color filter, it is necessary to perform exposure with a small amount of energy in order to increase the productivity.However, if the amount of exposure energy is reduced, a lack of pattern may occur during development due to insufficient curing reaction. And the exposed portion is eroded by the developer. As a method for solving these problems, for example, it is known to shorten the development time. However, the color filter manufactured in this manner has a problem that residues and background stain are easily generated on the unexposed portion of the substrate or the light-shielding layer at the time of development. As the concentration of the pigment contained increases, it tends to be significant, and it has been difficult to achieve a sufficient color density. Moreover,
Such problems often have an adverse effect on the pattern shape, and development of a radiation-sensitive composition for a color filter that can solve these problems has been desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and a curing reaction of a radiation-sensitive composition can be sufficiently achieved by exposure with a small amount of energy. An object of the present invention is to provide a radiation-sensitive composition for a color filter, which can form a color filter excellent in pattern shape without causing a color filter, and a color filter formed from the radiation-sensitive composition.

[0004]

According to the present invention, the above-mentioned problems are firstly solved by (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) Equation (1)
And a radiation-sensitive composition for a color filter, comprising a photo-radical generator containing a compound represented by the following formula (2) as an essential component.

[0005]

Embedded image [In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. ]

[0006]

Embedded image [In the formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ independently represent an alkyl group having 1 to 6 carbon atoms. ]

[0007] According to the present invention, the above-mentioned problem is secondly achieved.
(A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a compound represented by the formula (1) and a compound represented by the formula (2) are essential. This is achieved by a color filter having pixels formed from a radiation-sensitive composition for a color filter containing a photoradical generator as a component.

Hereinafter, the present invention will be described in detail. (A) Colorant The colorant in the present invention is not particularly limited in color tone, and is appropriately selected depending on the use of the obtained color filter, and may be any of a pigment, a dye, and a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, as the colorant in the present invention, a colorant having a high color development property and a high heat resistance, particularly a colorant having a high thermal decomposition resistance is preferable, and is usually used. And pigments, particularly preferably organic pigments. Examples of the organic pigment include a color index (CI; The Society of Dyers and Color).
Compounds classified as Pigment (published by Ists Co., Ltd.), specifically those having a color index (CI) number as shown below.

CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, C.I.
I. Pigment Yellow 15, CI Pigment Yellow 1
6, 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 61,
CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI
Pigment Yellow 95, CI Pigment Yellow 9
7, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 10
6, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 11
4, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 12
6, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 13
9, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 15
4, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 17
5, CI Pigment Yellow 180, CI Pigment Yellow 185;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, C.I.
I. Pigment Orange 17, CI Pigment Orange 2
4, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49,
CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, C.I.
I. Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 1
0, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI
Pigment Red 41, CI Pigment Red 42, C.I.
I. Pigment Red 48: 1, CI Pigment Red 4
8: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, C.I.
I. Pigment Red 49: 2, CI Pigment Red 5
0: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57:
2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63:
2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI
Pigment Red 97, CI Pigment Red 101,
CI Pigment Red 102, CI Pigment Red 1
04, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI
Pigment Red 114, CI Pigment Red 12
2, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166,
CI Pigment Red 168, CI Pigment Red 1
70, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI
Pigment Red 177, CI Pigment Red 17
8, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193,
CI Pigment Red 194, CI Pigment Red 2
02, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI
Pigment Red 216, CI Pigment Red 22
0, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255,
CI Pigment Red 264, CI Pigment Red 2
65;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, C.I.
I. Pigment Blue 15: 6, CI Pigment Blue 6
0; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7. These organic pigments can be used alone or
A mixture of more than one species can be used.

Among the organic pigments, a red organic pigment (C.
I. pigment red) is preferred, and more preferably C.I.
I. Pigment Red 177, CI Pigment Red 20
2, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220,
CI Pigment Red 224, CI Pigment Red 2
26, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI
Pigment Red 264, CI Pigment Red 265
In particular, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 254, C.I.
Pigment Red 264 and the like, and mixtures of these red organic pigments with organic pigments of other colors are preferred. The organic pigment can be purified and used by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

The inorganic pigments include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, navy blue, Chromium oxide green, cobalt green,
Amber, titanium black, synthetic iron black, carbon black and the like can be mentioned. These inorganic pigments can be used alone or in combination of two or more.

In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the surface of the pigment include polymers described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments. 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, and fluorine-based surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonylphenyl 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 the following product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products), Gafakku (produced by Dainippon Ink & Chemicals Co., Ltd.), (Sumitomo 3M Co., Ltd.) Fluorad,
Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned. 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 30 parts by weight, based on 100 parts by weight of the colorant.

(B) Alkali-Soluble Resin Next, the alkali-soluble resin in the present invention includes:
(A) When it acts as a binder for a colorant and is soluble in a developing solution used in the developing step, particularly preferably an alkali developing solution, in producing a color filter, Although not limited, a polymer having a carboxyl group, in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, simply referred to as “carboxyl group-containing unsaturated monomer”) and others. (Hereinafter, simply referred to as “copolymerizable unsaturated monomer”)
(Hereinafter, simply referred to as “carboxyl group-containing copolymer”).

Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, crotonic acid,
unsaturated monocarboxylic acids such as α-chloroacrylic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Trihydric or higher unsaturated polycarboxylic acid or its anhydride; mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2) phthalate -Acryloyloxyethyl),
2 such as mono (2-methacryloyloxyethyl) phthalate
Mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids having a valency of equal to or more than one; polymers such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate having a carboxyl group and a hydroxyl group at the terminal (Meth) acrylates and the like. These carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

Examples of the copolymerizable unsaturated monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene and p-vinyltoluene.
Chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether,
aromatic vinyl compounds such as p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene;

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, sec-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, methoxypropylene glycol methacrylate, methoxy Dipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2
-Hydroxy-3-phenoxypropyl acrylate,
Unsaturated carboxylic esters such as 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, Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; unsaturated acids such as glycidyl acrylate and glycidyl methacrylate Carboxylic acid glycidyl esters; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide Amides such as N, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; maleimide, N
Unsaturated imides such as -phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly And macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain such as n-butyl methacrylate and polysiloxane. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

As the carboxyl group-containing copolymer in the present invention, acrylic acid and / or methacrylic acid are essential, and in some cases, mono (2-acryloyloxyethyl) succinate and / or mono (2-methacrylic acid) are used. Carboxyl group-containing unsaturated monomer component further containing (loiroxyethyl), styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate , A copolymer with at least one selected from the group consisting of N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as “carboxyl group-containing copolymer (I)”) Say.) It is preferred.

Specific examples of the carboxyl group-containing copolymer (I) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, and (meth) acrylate. ) Acrylic acid / 2-
Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate Macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth)
Acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acryl Acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Mono (2-acryloyloxyethyl succinate) / styrene / benzyl (meth) acrylate /
Examples thereof include N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxyethyl succinate) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
５０50% by weight, preferably 10-40% by weight. In this case, if the copolymerization ratio is less than 5% by weight, the solubility of the obtained composition in an alkali developing solution tends to decrease, while if it exceeds 50% by weight, the solubility in an alkali developing solution becomes excessive, When developing with an alkali developing solution, there is a tendency that pixels fall off the substrate or the surface of the pixels becomes rough. The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of the alkali-soluble resin in the present invention measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is usually 3,000 to 300,000, preferably. Is 5,000 to 100,000. By using such an alkali-soluble resin having a specific Mw, a radiation-sensitive composition excellent in developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, and Occasionally, background contamination, film residue, and the like in a region other than a portion on which a pixel is formed on a substrate are less likely to occur. In the present invention, the alkali-soluble resins 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 1, based on 100 parts by weight of the coloring agent.
000 parts by weight, preferably 20 to 500 parts by weight.
In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, alkali developability may be reduced, or background contamination or film residue may occur in a region other than a portion where a pixel is formed on the substrate, On the other hand, when the content exceeds 1,000 parts by weight, the pigment concentration relatively decreases, and it may be difficult to achieve the color density required for the color filter.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds, and examples thereof include ethylene glycol and propylene glycol. Diacrylates or dimethacrylates of alkylene glycols such as polyethylene glycol, polypropylene glycol and the like; diacrylates or dimethacrylates of polyalkylene glycols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol; Polyacrylates or polymethacrylates of alcohols and their dicarboxylic acid modified products; oligoacrylates or oligomethacrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin And diacrylates or dimethacrylates of hydroxyl-terminated polymers such as hydroxy-poly-1,3-butadiene at both ends, hydroxy-polyisoprene at both ends, hydroxy-polycaprolactone at both ends, and tris (2-acryloyloxyethyl). ) Phosphate, tris (2-methacryloyloxyethyl) phosphate, and the like.

Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and modified dicarboxylic acids thereof are preferred.
Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol Pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, a compound represented by the following formula (3), and the like are preferable. In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate have high pixel strength, Excellent pixel surface smoothness and unexposed areas on the substrate and Scumming on the optical layer, it is unlikely to generate film residue and the like.

[0026]

Embedded image

The above-mentioned polyfunctional monomers can be used alone or in combination of two or more. In the present invention, a monofunctional monomer may be used in combination with the polyfunctional monomer as the case may be. Specific examples of such monofunctional monomers include (B) the same monomers as the carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the alkali-soluble resin, and Examples of commercially available products include M-5300 and M-5400 (trade names, manufactured by Toagosei Co., Ltd.). These monofunctional monomers can be used alone or in combination of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 0 to 50% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, the use ratio of the monofunctional monomer is 90% by weight.
If it exceeds, the strength and surface smoothness of the obtained pixels may be insufficient. The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). Department. in this case,
If the amount is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to decrease, while if it exceeds 500 parts by weight, for example, the alkali developability decreases, or the unexposed part on the substrate or light-shielding Background dirt, film residue, and the like tend to easily occur on the layer.

(D) Photo-radical generator The photo-radical generator in the present invention is a compound represented by the formula (1) (hereinafter referred to as “photo-radical generator (1)”) and the formula (2). Compound represented by the following (hereinafter,
It is called "photoradical generator (2)". ) As an essential component and has an action of generating a radical upon exposure. In the above formula (1), R ¹ and R ^{2 each} represent an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-type group.
-A butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group are preferable, and a methyl group is particularly preferable. In the above formula (1), R ³ , R ⁴ , R ⁵ and R ^{6 each} represent an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i- Propyl group, n-
A butyl group, an i-butyl group, a sec-butyl group and a t-butyl group are preferred, and an ethyl group is particularly preferred. The photo-radical generator (1) and the photo-radical generator (2) are highly sensitive to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams or X-rays, particularly radiation having a wavelength in the range of 190 to 450 nm. The radiation-sensitive composition is sensitive and can be sufficiently cured by exposure to a small amount of energy.

In the present invention, the photo-radical generator (1)
The photoradical generator (2) can be used alone or in combination of two or more. The usage ratio of the photo radical generator (1) to the photo radical generator (2) in the present invention is usually 10; 90 to 99;
Preferably from 30:70 to 95: 5, particularly preferably 5
0:50 to 95: 5. In this case, when the use ratio is less than 10:90, the pixel pattern tends to be enlarged and the resolution tends to be reduced. On the other hand, when it exceeds 99: 1, the curing reaction becomes insufficient, and the pixel pattern lacks during development. Or the exposed portion may be eroded during development.

In the present invention, another photoradical generator can be used together with the photoradical generator (1) and the photoradical generator (2). Examples of the other photo radical generator include, for example, imidazole compounds, benzoin compounds, acetophenone compounds, α
-Diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds and the like.

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 (2,4-dichlorophenyl) -4,4', 5,5 '
-Tetrakis (4-ethoxycarbonylphenyl)-
1,2′-biimidazole, 2,2′-bis (2,4,
6-trichlorophenyl) -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-dibromophenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4',
5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-chlorophenyl)-
4,4 ′, 5,5′-tetraphenyl-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 −
Bromophenyl) -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 and the like can be mentioned.

Further, specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, methyl 2-benzoylbenzoate and the like. Specific examples of the acetophenone-based compound include 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-benzyl-2-dimethylamino-1- (4'-morpholinophenyl) butane-1
-One, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-
1-one and the like can be mentioned. Specific examples of the α-diketone compound include diacetyl, dibenzoyl,
Methylbenzoyl formate and the like can be mentioned.
Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1,4-naphthoquinone. Specific examples of the xanthone-based compound include xanthone, thioxanthone, and 2-chlorothioxanthone.

Specific examples of the triazine-based compound include 1,3,5-tris (trichloromethyl) -s-triazine and 1,3-bis (trichloromethyl) -5.
(2′-chlorophenyl) -s-triazine, 1,3-
Bis (trichloromethyl) -5- (4'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-methoxyphenyl) -s-triazine, 1,3-bis (trichloro Methyl) -5- (4'-
Methoxyphenyl) -s-triazine, 2- (2′-furylethylidene) -4,6-bis (trichloromethyl)
-S-triazine, 2- (4'-methoxystyryl)-
4,6-bis (trichloromethyl) -s-triazine,
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 (trichloromethyl)-
Examples thereof include s-triazine, 2- (2′-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine, and a compound represented by the following formula (4).

[0035]

Embedded image

Of these other photoradical generators,
2,2′-bis (2-chlorophenyl) -4,4 ′,
5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl)-
4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2-benzyl-2-dimethylamino-1-
(4′-morpholinophenyl) butan-1-one, 1
-Hydroxycyclohexyl phenyl ketone is preferred. The other photo radical generators can be used alone or in combination of two or more.

The proportion of the other photo-radical generator used is usually 80% by weight or less based on the total of the photo-radical generator (1), the photo-radical generator (2) and the other photo-radical generator. It is preferably at most 60% by weight, more preferably at most 40% by weight. In this case, if the use ratio of the other photoradical generator exceeds 80% by weight, the intended effect of the present invention may be impaired. The total amount of the photoradical generator used in the present invention is (C) a polyfunctional monomer 10
0 to 100 parts by weight, usually 0.01 to 200 parts by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight.
Parts by weight. In this case, if the total amount of the photoradical generator is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 200 parts by weight, the formed pixels may easily fall off the substrate during development, or the background may become liable to be soiled or a film remaining on the unexposed portion of the substrate or the light-shielding layer. is there. Further, in the present invention, one or more of a sensitizer, a curing accelerator and a polymer photocrosslinking / sensitizer may be used together with the photoradical generator, if necessary.

Additives The radiation-sensitive composition for a color filter of the present invention can contain various additives, if necessary. Examples of the additive include an organic acid having an action of further improving the solubility of the radiation-sensitive composition for a color filter in an alkali developing solution and further 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. Examples of the aliphatic carboxylic acid 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, and amber 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,
Dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid; tricarballylic acid, aconitic acid, Examples thereof include tricarboxylic acids such as 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. Examples include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; trimellitic acid, trimesic acid, and melophanic acid , Triphenyl or higher aromatic polycarboxylic acids such as pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidenic acid, coumaric acid, umbellic acid And the like.

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 are alkali-soluble, This is preferred from the viewpoints of solubility in GaN, prevention of background contamination and film residue on the unexposed portion of the substrate and the light-shielding layer. 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 5% by weight or less, based on the whole radiation-sensitive composition.
More preferably, it is 1% by weight or less. 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. High molecular compounds such as ethers and poly (fluoroalkyl acrylates); nonionic, cationic,
Surfactants such as 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);
Antioxidants such as 6-di-t-butylphenol; 2-
UV absorbers such as (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; aggregation inhibitors such as sodium polyacrylate; epoxy compounds and melamine compounds And a thermal crosslinking agent such as a bisazide compound.

Solvent The radiation-sensitive composition for a color filter of the present invention contains the above-mentioned components (A) to (D) as essential components and optionally contains the above-mentioned additive components. And prepared as a liquid composition. As the solvent, a component which disperses or dissolves the components (A) to (D) and the additives constituting the radiation-sensitive composition, does not react with these components, and has appropriate volatility. 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 mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-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-butyl ether,
(Poly) alkylenes such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether Glycol monoalkyl ethers; (poly) alkylene glycol mono such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Alkyl A Le acetates; diethylene glycol dimethyl ether, other ethers such as diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methylethylketone, cyclohexanone, 2-heptanone, 3-
Ketones such as heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate; methyl 3-methoxypropionate;
Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-
Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-acetic acid
-Propyl, n-butyl acetate, i-butyl acetate, n-formic acid
-Amyl, i-amyl acetate, n-butyl propionate,
Ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, 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-methylpyrrolidone ,
Examples thereof include amides such as N-dimethylacetamide.

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, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxy Butyl propionate, 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. The solvents may be used alone or in combination of two or more.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, High boiling solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be used in combination.
Of these high-boiling solvents, γ-butyrolactone and the like are preferred. The high boiling point solvents can be used alone or in combination of two or more. The total amount of the solvent used is not particularly limited, but from the viewpoint of the applicability of the obtained radiation-sensitive composition, stability, etc., the total concentration of each component excluding the solvent of the composition is usually , 5 to 50% by weight, preferably 10 to 40% by weight.

Method for Forming Color Filter Next, a method for forming a color filter using the radiation-sensitive composition for a color filter of the present invention will be described. First, on the surface of the substrate, if necessary, a light-shielding layer is formed so as to partition a portion where a pixel is formed, and a liquid composition of a radiation-sensitive composition in which, for example, a red pigment is dispersed, is formed on the substrate. After applying the object, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, after this coating film is exposed through a photomask, it is developed using an alkali developing solution to dissolve and remove the unexposed portions of the coating film, and then post-baked, so that a red pixel pattern is formed. To form a pixel array arranged in the above arrangement. Thereafter, using a liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, in the same manner as described above, coating, pre-baking, exposing and developing each liquid composition, and then performing post-baking Then, by sequentially forming the green pixel array and the blue pixel array on the same substrate, a color filter in which the three primary color pixel arrays of red, green, and blue are arranged on the substrate is obtained. Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, norbornene-based ring-opening polymer, and hydrogenated products thereof. . These substrates may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired. When applying the liquid composition of the radiation-sensitive composition to the 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
It is 10 μm, preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 3.0 μm. As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-rays and the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. . Exposure energy of radiation is usually
100 to 200 mJ / cm ² , but 50 to 100 mJ / cm ²
Even if it falls to the range of J / cm ^2, the radiation-sensitive composition can be sufficiently cured. Further, as the alkali developer, for example, sodium carbonate, sodium hydroxide,
Potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.
4.0] -7-undecene, 1,5-diazabicyclo-
An aqueous solution such as [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 developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method, or the like can be applied.
0 seconds is preferred. The color filter of the present invention thus formed is extremely useful for, for example, a transmission type or reflection type color liquid crystal display device, a color image pickup tube element, a color sensor and the like.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color filter of the present invention contains the above components (A) to (D) as essential components. And (a) to (f) below. (A) A radiation-sensitive composition for a color filter, wherein (B) the alkali-soluble resin contains a carboxyl group-containing copolymer (I). (B) (C) the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate
Radiation-sensitive composition for color filters. (C) (D) The photoradical generator (1) in the photoradical generator contains 2-methyl-1- (4′-methylthiophenyl) -2-morpholinopropan-1-one,
The radiation-sensitive composition for a color filter according to the above (a) or (b), wherein the photoradical generator (2) contains 4,4'-bis (diethylamino) benzophenone. (D) (A) wherein the colorant contains an organic pigment;
The radiation-sensitive composition for a color filter according to (b) or (c). (E) The radiation-sensitive composition for a color filter according to the above (d), wherein the organic pigment contains a red organic pigment. (F) Red organic pigments are more preferably CI Pigment Red 177, CI Pigment Red 202, C.I.
I. Pigment Red 206, CI Pigment Red 20
7, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226,
CI Pigment Red 242, CI Pigment Red 2
43, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, and at least one selected from the group of CI Pigment Red 265, particularly preferably CI Pigment Red 177, CI Pigment Red 224, The radiation-sensitive composition for a color filter according to (e), comprising at least one selected from the group consisting of CI Pigment Red 254 and CI Pigment Red 264, and a mixture of these red organic pigments and organic pigments of other colors. Further, preferred color filters of the present invention include: (g) the above (a), (b), (c), (d), (e)
Or (f) a color filter having pixels formed from the 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 the following examples.

Example 1 [Preparation of Liquid Composition] (A) 90 parts by weight of CI Pigment Red 177 as a coloring agent, and (B) methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer as an alkali-soluble resin ( (C copolymer weight ratio = 15/15/70, Mw = 28,000) 60 parts by weight, (C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-parts as a photo radical generator. 30 parts by weight of methyl-1- (4'-methylthiophenyl) -2-morpholinopropan-1-one and 3 parts by weight of 4,4'-bis (diethylamino) benzophenone, and ethyl 3-ethoxypropionate 1 as a solvent 000 parts by weight were mixed to prepare a liquid composition of the radiation-sensitive composition. This liquid composition is referred to as composition (R1). [Preparation of Pixel Array] Using the composition (R1), a red pixel array was prepared on a transparent substrate as follows. On a surface of a soda glass substrate on which a silica (SiO ₂ ) film for preventing sodium ions from being eluted was formed, a light-shielding layer was provided so as to partition a portion where a pixel was formed, and the light-shielding layer was formed. After applying the composition (R1) on the surface of the substrate using a spin coater,
Pre-bake in a clean oven for 10 minutes,
A coating film having a thickness of 2 μm was formed. Then, after cooling the substrate to room temperature, the coating film was applied to a coating film of 365 nm, 405 nm and 43 nm using a high pressure mercury lamp and a photomask.
Ultraviolet rays containing each wavelength of 6 nm were exposed at an exposure amount of 80 mJ / cm ² . Thereafter, the substrate was immersed in a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C. for 1 minute to perform a developing treatment, and then washed with ultrapure water and dried. Thereafter, post-baking was performed in a clean oven at 180 ° C. for 30 minutes to prepare a pixel array in which red pixel patterns each having a size of 20 μm × 20 μm were arranged. [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that no undissolved matter remained on the substrate and no scum was observed at the edge of the pixel pattern. The residual film ratio of the pixel array was as good as 90%. Further, the cross section of the pixel pattern is scanned with a scanning electron microscope (SEM).
As a result, no undercut was observed.

Example 2 [Preparation of Liquid Composition] (A) 45 parts by weight of CI Pigment Red 177 and 45 parts by weight of CI Pigment Red 224 as coloring agents, and (B) methacrylic acid / 2-hydroxyethyl methacrylate as an alkali-soluble resin / Benzyl methacrylate copolymer (copolymer weight ratio = 1
5/15/70, Mw = 28,000) 60 parts by weight,
(C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-methyl-1- (4'-methylthiophenyl) as a photoradical generator
30 parts by weight of 2-morpholinopropan-1-one and 4,4′-bis (diethylamino) benzophenone 1
5 parts by weight, 3 parts by weight of citraconic acid as an additive, and 1,000 parts of ethyl 3-ethoxypropionate as a solvent
The liquid parts of the radiation-sensitive composition were prepared by mixing parts by weight. This liquid composition is referred to as composition (R2). [Preparation of Pixel Array] A red pixel array was prepared in the same manner as in Example 1 except that the composition (R2) was used instead of the composition (R1). [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that no undissolved matter remained on the substrate and no scum was observed at the edge of the pixel pattern. Further, the residual film ratio of the pixel array was as good as 92%. Further, the cross section of the pixel pattern is scanned with a scanning electron microscope (SEM).
As a result, no undercut was observed.

Example 3 [Preparation of liquid composition] (A) 110 parts by weight of CI Pigment Red 177 as a coloring agent, and (B) methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer) as an alkali-soluble resin Polymerization weight ratio = 15/15/70, Mw = 28,000) 60 parts by weight, (C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-methyl as a photoradical generator 30 parts by weight of 1- (4'-methylthiophenyl) -2-morpholinopropan-1-one, 15 parts by weight of 4,4'-bis (diethylamino) benzophenone, 2,2'-bis (2-chlorophenyl)-
5,4 parts by weight of 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 5 parts by weight of 2-mercaptobenzothiazole, 3 parts by weight of citraconic acid as an additive, and 3-ethoxypropionic acid as a solvent Ethyl 1,0
By mixing 00 parts by weight, a liquid composition of the radiation-sensitive composition was prepared. This liquid composition is referred to as composition (R3). [Preparation of Pixel Array] A red pixel array was prepared in the same manner as in Example 1, except that the composition (R3) was used instead of the composition (R1). [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that no undissolved matter remained on the substrate and no scum was observed at the edge of the pixel pattern. The residual film ratio of the pixel array was as good as 90%. Further, the cross section of the pixel pattern is scanned with a scanning electron microscope (SEM).
As a result, no undercut was observed.

Example 4 [Preparation of Liquid Composition] (A) 90 parts by weight of CI Pigment Red 254 and 10 parts by weight of CI Pigment Yellow 139 as colorants, and (B) methacrylic acid / 2-hydroxyethyl methacrylate as an alkali-soluble resin / Benzyl methacrylate copolymer (copolymerization weight ratio =
15/15/70, Mw = 28,000) 60 parts by weight,
(C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-methyl-1- (4'-methylthiophenyl) as a photoradical generator
30 parts by weight of 2-morpholinopropan-1-one and 4,4′-bis (diethylamino) benzophenone 1
A liquid composition of a radiation-sensitive composition was prepared by mixing 5 parts by weight, 3 parts by weight of malonic acid as an additive, and 1,000 parts by weight of ethyl 3-ethoxypropionate as a solvent. This liquid composition is referred to as composition (R4). [Preparation of Pixel Array] A red pixel array was prepared in the same manner as in Example 1, except that the composition (R4) was used instead of the composition (R1). [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that no undissolved matter remained on the substrate and no scum was observed at the edge of the pixel pattern. Further, the residual film ratio of the pixel array was as good as 92%. Further, the cross section of the pixel pattern is scanned with a scanning electron microscope (SEM).
As a result, no undercut was observed.

Example 5 [Preparation of liquid composition] (A) 90 parts by weight of CI Pigment Red 254 as a coloring agent, and (B) methacrylic acid / benzyl methacrylate / N- as an alkali-soluble resin
Phenylmaleimide / styrene copolymer (copolymerization weight ratio = 30/20/30/20, Mw = 13,000) 60
Parts by weight, (C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-methyl-1- (4'-methylthiophenyl) -2-morpholinopropane as a photoradical generator. 30 parts by weight of 1-one and 15 parts by weight of 4,4'-bis (diethylamino) benzophenone, 3 parts by weight of malonic acid as an additive, and ethyl 1,3-ethoxypropionate 1,0 as a solvent
By mixing 00 parts by weight, a liquid composition of the radiation-sensitive composition was prepared. This liquid composition is referred to as composition (R5). [Preparation of Pixel Array] A red pixel array was prepared in the same manner as in Example 1, except that the composition (R5) was used instead of the composition (R1). [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that no undissolved matter remained on the substrate and no scum was observed at the edge of the pixel pattern. The residual film ratio of the pixel array was as good as 90%. Further, the cross section of the pixel pattern is scanned with a scanning electron microscope (SEM).
As a result, no undercut was observed.

Comparative Example 1 [Preparation of Liquid Composition] (A) 90 parts by weight of CI Pigment Red 177 as a coloring agent, and (B) methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer) as an alkali-soluble resin Polymerization weight ratio = 15/15/70, Mw = 28,000) 60 parts by weight, (C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 1-hydroxy as a photoradical generator A liquid composition of a radiation-sensitive composition was prepared by mixing 32 parts by weight of cyclohexylphenyl ketone and 1,000 parts by weight of ethyl 3-ethoxypropionate as a solvent. This liquid composition is referred to as composition (r1). [Preparation of Pixel Array] A red pixel array was prepared in the same manner as in Example 1, except that the composition (r1) was used instead of the composition (R1). [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that undissolved substances remained on the substrate. Also,
The residual film ratio of the pixel array was as low as 75%. Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed.

Comparative Example 2 [Preparation of Liquid Composition] (A) 90 parts by weight of CI Pigment Red 177 as a coloring agent, and (B) methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer) as an alkali-soluble resin Polymerization weight ratio = 15/15/70, Mw = 28,000) 60 parts by weight, (C) 60 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-methyl as a photoradical generator 30 parts by weight of -1- (4′-methylthiophenyl) -2-morpholinopropan-1-one and 1,000 parts by weight of ethyl 3-ethoxypropionate as a solvent are mixed to form a liquid of the radiation-sensitive composition. A composition was prepared. This liquid composition was treated as composition (r2)
And [Preparation of Pixel Array] A red pixel array was prepared in the same manner as in Example 1, except that the composition (r2) was used instead of the composition (R1). [Evaluation] Observation of the obtained pixel array with an optical microscope revealed that the pixel pattern was chipped. Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed.

[0053]

The radiation-sensitive composition for a color filter of the present invention comprises a photo-radical generator containing a specific compound having high sensitivity to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray as an essential component. By using, the curing reaction is sufficiently achieved by exposure to a small amount of energy, so that undissolved matter does not remain on the substrate during development and scum does not occur on the edge of the pixel pattern, and undercut A color filter having a good pixel pattern without a defect can be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 4M118 G02F 1/1335 505 G02F 1/1335 505 G03F 7/004 505 G03F 7 / 004 505 7/031 7/031 H01L 27/14 H01L 27/14 DF term (reference) 2H025 AA04 AB13 AC01 AD01 BC14 BC42 BC51 CA01 CA20 CA27 CA28 CB13 CB14 CB43 CB52 CC11 FA03 FA17 FA29 2H048 BA45 BA47 BA48 BB42 BB14 BB14 BB46 2H091 FA02Y FB12 FC10 GA01 GA16 LA12 LA15 LA30 4J002 AA011 BG011 BG041 BG051 BH011 BH021 EE038 EH077 EL098 EN098 EU118 EU208 EV308 FD096 FD147 FD158 GP00 4J038 EA01 FA 221 FA 221 FA 221 FA 221 FA PA17 PB09 4M118 AA10 AB01 GC08 GC17

Claims (2)

[Claims] 1. A colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a compound represented by the following formula (1):
A radiation-sensitive composition for a color filter, comprising a photo-radical generator containing a compound represented by the following formula and a compound represented by the following formula (2) as essential components: Embedded image [In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. [Chemical formula 2] [In the formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ independently represent an alkyl group having 1 to 6 carbon atoms. ] 2. A color filter comprising a pixel formed from the radiation-sensitive composition for a color filter according to claim 1.