JP2000056118A - Radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new radiation sensitive compsn. for a color filter having good developing ability even in the case of contg. a pigment in high concentration, without generating residual dross or stains on an unexposed portion of a substrate and a light shielding layer, and providing a pixel excellent for adhesion to the substrate and the light shielding layer. SOLUTION: A radiation sensitive compsn. for a color filter has a characteristics contg. (A) a coloring agent, (B) an alkaline soluble resin contg. a copolymer of a monomer, which is selected from a group of di-carbonic acid mono-(2-acryloiloxy ethyl) and di-carbonic acid mono-(2-methacryloiloxy ethyl), and an other copolymerisable monofunctional monomer, (C) a multi functional monomer and (D) a photo polymerization initiator.

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 and the like. The present invention relates to a radiation-sensitive composition for a color filter having excellent developability and the like.

[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. The color filter manufactured in this way, during development,
There is a problem that residues and background stains easily occur on the unexposed part of the substrate or the light-shielding layer, and the degree thereof tends to become significant as the concentration of the pigment contained in the radiation-sensitive composition increases, and therefore, sufficient color It was difficult to achieve the concentration.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive composition for a color filter which exhibits good developability even when a pigment is contained at a high concentration. It is an object of the present invention to provide a novel radiation-sensitive composition for a color filter, which does not generate residue and background stain on the upper and light-shielding layers and provides pixels having excellent adhesion to the substrate and the light-shielding layer.

[0004]

The present invention is selected from the group consisting of (A) a colorant, (B) mono (2-acryloyloxyethyl) dicarboxylate and mono (2-methacryloyloxyethyl) dicarboxylate. An alkali-soluble resin containing a copolymer of a monomer and another copolymerizable monofunctional monomer, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A radiation-sensitive composition for a color filter.

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 color filter to be obtained, and may be an organic colorant or an inorganic colorant. The organic colorant specifically refers to a dye, an organic pigment, a natural pigment, and the like, and the inorganic colorant specifically includes, in addition to the inorganic pigment, an inorganic salt called an extender, 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 colorant having high heat resistance, particularly a colorant having high heat decomposition resistance is preferable, and is usually And an organic colorant, particularly preferably an organic pigment. As the organic pigment, for example,
Color Index (CI; The Society of Dyers and
Compounds classified as Pigment in Colorists Inc.), specifically those having the following color index (CI) numbers.

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 and 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 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, Pigment Black 7. These organic pigments can be used alone or in combination of two or more.

Further, specific examples of the inorganic colorant include:
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, dark blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. These inorganic colorants can be used alone or in combination of two or more.

In the present invention, each of the colorants can be used after modifying its particle surface with a polymer, if desired. As a polymer that modifies the colorant surface,
Examples thereof 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. Such dispersants include, for example, cationic, anionic, nonionic, amphoteric, silicone,
A surfactant such as a fluorine-based surfactant can be used. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol such as polyethylene glycol dilaurate and polyethylene glycol distearate Diesters; sorbitan fatty acid esters;
In addition to fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethylene imines, etc.
KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products Co., Ltd.), Megafac (Dainippon Ink and Chemicals, Inc.)
), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, and Surflon (all manufactured by Asahi Glass Co., Ltd.). These surfactants can be used alone or in combination of two or more. The amount of the surfactant used is usually 50 parts by weight based on 100 parts by weight of the coloring agent.
It is not more than 0 parts by weight, preferably 0 to 30 parts by weight.

[0012] (B) an alkali-soluble resin in the alkali-soluble resin present invention, at least one single selected from the group of dicarboxylic acid mono (2-acryloyloxyethyl) and dicarboxylic acid mono (2-methacryloyloxyethyl) Copolymer (hereinafter, this monomer is referred to as “monofunctional monomer (b1)”) and another copolymerizable monofunctional monomer (hereinafter, referred to as “copolymer (b1)”). B
1) ". ). As the dicarboxylic acid in the monofunctional monomer (b1), for example,
Aliphatic dicarboxylic acids having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid and the like Alicyclic dicarboxylic acids having 7 to 24, preferably 8 to 14 carbon atoms; aromatic dicarboxylic acids having 8 to 24, preferably 8 to 14 carbon atoms such as phthalic acid, isophthalic acid, and terephthalic acid; Can be mentioned. Among these dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 8 carbon atoms are preferable, and succinic acid is particularly preferable. In the present invention, the monofunctional monomers (b1) can be used alone or in combination of two or more.

[0013] The other copolymerizable monofunctional monomer means a monomer having one copolymerizable polymerizable unsaturated bond, monofunctional monomer (b1) and It is not limited as long as the copolymer (B1) can be copolymerized and the obtained copolymer (B1) is alkali-soluble. In particular, a monofunctional compound having one or more carboxyl groups other than the monofunctional monomer (b1) Monomer (hereinafter, referred to as “monofunctional monomer (b2)”) and a copolymerizable monofunctional monomer other than the above (hereinafter, simply referred to as “other monofunctional monomer”) Is preferred.) Examples of the monofunctional monomer (b2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid,
Unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid or anhydrides thereof; trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof, and ω-carboxypolycaprolactone Monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like can be mentioned. These monofunctional monomers (b2) can be used alone or in combination of two or more.

Other monofunctional monomers include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, indene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Aromatic vinyl compounds such as benzyl 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, sec- butyl acrylate, s
ec-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, methoxy triacrylate Ethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Unsaturated carboxylic esters such as acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 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 Unsaturated carboxylic acid aminoalkyl esters such as acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate;
Unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl Unsaturated ethers such as glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α
Unsaturated amides such as -chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; 1,3-butadiene Conjugated dienes such as styrene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain, such as butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These other monofunctional monomers can be used alone or in combination of two or more.

As the copolymer (B1), in particular, a monofunctional monomer (b1) and acrylic acid and / or methacrylic acid as essential components, and in some cases ω-carboxypolycaprolactone monoacrylate and / or −
Monofunctional monomer (b2) containing carboxypolycaprolactone monomethacrylate, styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate ,
A copolymer with at least one selected from the group consisting of glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as “alkali-soluble resin (I)”). preferable.

Specific examples of the alkali-soluble resin (I) include (meth) acrylic acid / monofunctional monomer (b1) / styrene copolymer, and (meth) acrylic acid / monofunctional monomer (b1). ) / Methyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer Form (b1) / benzyl (meth)
Acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / glycerol mono (meth) A) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / polystyrene macromonomer Polymer or (meth) acrylic acid / monofunctional monomer (b
1) / a terpolymer composed of a polymethyl methacrylate macromonomer copolymer (hereinafter, referred to as “alkali-soluble resin (Ia)”);

(Meth) acrylic acid / monofunctional monomer (b)
1) / styrene / methyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / Monofunctional monomer (b1)
/ Styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate copolymer, (meth)
Acrylic acid / monofunctional monomer (b1) / styrene / glycerol mono (meth) acrylate copolymer, (meth)
Acrylic acid / monofunctional monomer (b1) / styrene / N-
Phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / poly Methyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth)
Acrylic acid / monofunctional monomer (b1) / methyl (meth)
Acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω- Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / Glycerol mono (meta)
Acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / Methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / Monofunctional monomer (b1) / 2
-Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (B1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b
1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenyl Maleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer ( b1) / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / monofunctional monomer (b)
1) / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-
Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / Glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth)
Acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / polymethyl Methacrylate macromonomer copolymer, (meth) acrylic acid / ω-
Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / Glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth)
Acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / polymethyl Methacrylate macromonomer copolymer, (meth) acrylic acid / ω-
Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / ω-
Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (B1) / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1)
/ Polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / N-phenyl A maleimide / polystyrene macromonomer copolymer, or a quaternary copolymer (meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer (hereinafter, referred to as Alkali-soluble resin (Ib) "
That. );

(Meth) acrylic acid / monofunctional monomer (b)
1) / styrene / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene /
Methyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, ) Acrylic acid / ω-carboxypolycaprolactone mono (meth)
Acrylate / monofunctional monomer (b1) / styrene / methyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / glycerol mono ( (Meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / N
-Phenylmaleimide copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / styrene / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2- Hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1)
/ Styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b
1) / Styrene / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate /
N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional Monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b
1) / styrene / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / benzyl (Meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional Water-soluble monomer (b1) / styrene / benzyl (meth) acrylate /
N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer Body (b1) / styrene / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth)
Acrylate / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / glycerol mono ( (Meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (B1) / styrene / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / polymethyl methacrylate macromonomer Polymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / ω- Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer Monomer (b1) / styrene / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / polymethyl methacrylate macromonomer Polymer, (meth) acrylic acid / monofunctional monomer (b1) / s Len / N- phenylmaleimide /
Glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene /
N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b
1) / styrene / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / Benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, Meta)
Acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / monofunctional monomer (b)
1) / Methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth)
Acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl ( (Meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional Monomer (b1) / methyl (meth) acrylate /
Benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) Acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1)
/ Methyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) Acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer Unified, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b
1) / methyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid /
ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide copolymer, (meth)
Acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono ( (Meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / Glycerol mono (meth) acrylate / N
-Phenylmaleimide copolymer, (meth) acrylic acid /
Monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b
1) / methyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) /
2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer; ) Acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer Body (b1)
/ 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) /
2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1)
/ 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate /
Monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / monofunctional monomer (b
1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) A) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macro Monomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / Ω-carboxypolycaprolactone mono (meth) acrylate / Functional monomers (b1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid /
ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (Meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional Water-soluble monomer (b1) / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / monofunctional monomer (b)
1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) Acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer Polymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / Monofunctional monomer (b1) / benzyl (meth) acrylate / Eniru (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1 ) / Benzyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate /
Phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω
-Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) ) Acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate /
Monofunctional monomer (b1) / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / Benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / monofunctional monomer (b)
1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) /
Benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth)
Acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth)
Acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer Body (b1) / phenyl (meth) acrylate / N-
Phenylmaleimide copolymer, (meth) acrylic acid / ω
-Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Monofunctional monomer (b1) / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate /
Glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1)
/ Glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate /
Monofunctional monomer (b1) / N-phenylmaleimide / polystyrene macromonomer copolymer or (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / N A pentapolymer comprising a phenylmaleimide / polymethylmethacrylate macromonomer copolymer (hereinafter referred to as “alkali-soluble resin (Ic)”);

(Meth) acrylic acid / monofunctional monomer (b)
1) / Styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2- Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth)
Acrylic acid / monofunctional monomer (b1) / styrene / 2-
Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate /
Benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (Meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional Monomer (b1)
/ Styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) Acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / monofunctional monomer (b
1) / Styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate /
Glycerol mono (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / polymethyl methacrylate macromonomer Copolymer, (meth) acrylic acid / monofunctional monomer (b1) / styrene /
Phenyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate / polystyrene macromonomer copolymer or (meth) acrylic acid / monofunctional monomer (B1) / styrene / phenyl (meth) acrylate /
A hex copolymer (hereinafter, referred to as “alkali-soluble resin (Id)”) composed of a glycerol mono (meth) acrylate / polymethyl methacrylate macromonomer copolymer may be used.

In the present invention, among the alkali-soluble resins (Ia), alkali-soluble resins (Ib), alkali-soluble resins (Ic) and alkali-soluble resins (Id), their monofunctional monomers (b1) Resins which are mono (2-acryloyloxyethyl) succinate and / or mono (2-methacryloyloxyethyl) succinate are particularly preferred. The copolymerization ratio of the monofunctional monomer (b1) in the copolymer (B1) is usually 5 to 35% by weight, preferably 10 to 25% by weight. In this case, if the copolymerization ratio of the monofunctional monomer (b1) is less than 5% by weight, residues, background stains, etc. may be generated on the unexposed portion of the substrate or the light-shielding layer. If it exceeds, the formed pixels tend to easily fall off the substrate at the time of development with an alkali developing solution. When the copolymer (B1) is a copolymer of the monofunctional monomer (b1), the monofunctional monomer (b2) and another unsaturated monomer, The copolymerization ratio of the compound (b2) is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of the other unsaturated monomer is usually 15 to 90% by weight, preferably Is 35
~ 80% by weight. In this case, the monofunctional monomer (b
When the copolymerization ratio of 2) is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease. Pixels that have fallen off the substrate and the surface of the pixels tend to be rough. The copolymer (B1) containing the monofunctional monomer (b2) at the specific copolymerization ratio together with the monofunctional monomer (b1) is as follows:
It has excellent solubility in an alkali developer, and the radiation-sensitive composition using the copolymer as a binder has very little undissolved material remaining after development with an alkali developer. Residues, background stains, etc. hardly occur on the exposed portion of the substrate or the light-shielding layer, and the pixels obtained from the composition do not dissolve excessively in the alkali developing solution and have excellent adhesion to the substrate. And has no risk of falling off the substrate. The copolymer (B1) can be used alone or in combination of two or more.

In the present invention, another alkali-soluble resin may be used in combination with the copolymer (B1) in some cases. Examples of the other alkali-soluble resin include a resin having an acidic functional group such as a carboxyl group and a phenolic hydroxyl group. As such another alkali-soluble resin, a resin having a carboxyl group is preferable. More preferably, the monofunctional monomer (b2) exemplified for the copolymer (B1) and the other monofunctional monomer are used. With acrylic acid and / or methacrylic acid as essential components,
Optionally a monofunctional monomer (b) containing ω-carboxypolycaprolactone monoacrylate and / or ω-carboxypolycaprolactone monomethacrylate
2) and styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, co-polymerization with at least one selected from the group of polystyrene macromonomer and polymethyl methacrylate macromonomer Combination (hereinafter referred to as “alkali-soluble resin (II)”) is preferred.

Specific examples of the alkali-soluble resin (II) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, and (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 copolymer Copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / Benzyl (meth) acrylate / N- phenylmaleimide copolymer, (meth) acrylic acid / .omega. carboxypolycaprolactone mono (meth) acrylate / styrene / allyl (meth) acrylate /
Examples include N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl methacrylate / glycerol (meth) acrylate / N-phenylmaleimide copolymer. These alkali-soluble resins (II) can be used alone or in combination of two or more. When the other alkali-soluble resin is used, the amount of the resin is usually 50% by weight or less, preferably 30% by weight, based on the total amount of the alkali-soluble resin.
It is as follows. In this case, when the use amount of the other alkali-soluble resin exceeds 50% by weight, residues, background stains, and the like tend to be easily generated on the unexposed portion of the substrate or the light shielding layer.

The alkali-soluble resin in the present invention contains the copolymer (B1) as an essential component, and polystyrene measured by gel permeation chromatography (GPC; elution solvent: tetrahydrofuran) of each component constituting the alkali-soluble resin. The reduced weight average molecular weight (hereinafter, simply referred to as “weight average molecular weight”) is preferably 3,000 to 300,000, particularly preferably 5,
000 to 100,000. By using an alkali-soluble resin having such a specific weight average molecular weight, a radiation-sensitive composition having excellent developability can be obtained, thereby forming a pixel having a sharp pattern edge, During development, residues, background stains, film residues, and the like hardly occur on the unexposed portion of the substrate or the light-shielding layer. The amount of the alkali-soluble resin used in the present invention is usually 10 to 10 parts by weight of the colorant (A).
It is 1000 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 residues, background stains, etc. may be generated on the unexposed portion of the substrate or the light-shielding layer. If it exceeds 1000 parts by weight,
Since the concentration of the colorant relatively decreases, it may be difficult to achieve the desired color density as a thin film.

(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. Alkylene glycol diacrylates or dimethacrylates;
Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and dicarboxylic acids thereof Acid-modified product;
Oligoacrylates or oligomethacrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin; both ends hydroxyhydroxy-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone, etc. Examples include diacrylate or dimethacrylate of terminal hydroxylated polymer, tris (2-acryloyloxyethyl) phosphate, tris (2-methacryloyloxyethyl) phosphate, and the like.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products 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 (1) and the like are preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate have high pixel strength, Excellent pixel surface smoothness and unexposed areas on the substrate or Stain on the light-shielding layer, are unlikely to generate film residue and the like.

[0035]

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The 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 a monofunctional monomer include the monofunctional monomer (b2) exemplified for the copolymer (B1) and the other monofunctional monomers, as well as commercially available products. M-5400, M-56
00 (trade name, manufactured by Toagosei Co., Ltd.) and the like. These monofunctional monomers can be used alone or in combination of two or more. The use ratio of the monofunctional monomer is usually 90% by weight or less, preferably 0 to 0% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer.
50% by weight. In this case, if the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the obtained pixel may be insufficient. The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is,
(B) The amount 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. In this case, if the used amount is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to decrease, while 50
If the amount is more than 0 parts by weight, for example, alkali developability tends to decrease, and background stains, film residue, and the like tend to easily occur on the unexposed portion of the substrate or the light shielding layer.

(D) Photopolymerization initiator The photopolymerization initiator in the present invention includes visible light, ultraviolet light,
Exposure to far ultraviolet rays, electron beams, X-rays or the like causes decomposition or cleavage of bonds to generate active species, such as radicals, cations and anions, which can initiate the polymerization of the polyfunctional monomer (C). Means a compound that Examples of such a photopolymerization initiator include imidazole compounds having at least one main skeleton represented by the following formula (2), formula (3) or formula (4), benzoin compounds, acetophenone compounds, Examples include benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, xanthone-based compounds, and triazine-based compounds.

[0038]

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[0039]

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[0040]

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Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 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-methoxycarbonylphenyl) -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-
(Methoxycarbonylphenyl) -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-methoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4
-Ethoxycarbonylphenyl) -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-methoxycarbonylphenyl)
-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-methoxycarbonylphenyl) -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, 2,2'-
Bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4-methoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-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-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,
2,2′-bis (2-cyanophenyl) -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'-tetra Phenyl-
1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -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-ethylphenyl) -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-phenylphenyl) -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 can be mentioned.

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 not high in the unexposed areas, the exposed coating film clearly shows a cured part insoluble in the developing solution and an uncured part having high solubility in the developing solution. As a result, a high-definition pixel array in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed.

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 and 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, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like. Specific examples of the benzophenone-based compound include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate and the like. Specific examples of the polynuclear quinone-based compound include anthraquinone, 2
-Ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone and the like. Specific examples of the xanthone compound, xanthone,
Thioxanthone, 2-chlorothioxanthone and the like can be mentioned. 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 the like.

These photopolymerization initiators can be used alone or
A mixture of more than one species can be used. The amount of the photopolymerization initiator used in the present invention is usually 0.01 to 200 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer (C) and the optionally used monofunctional monomer. Parts, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which a pixel pattern is arranged according to a predetermined arrangement, On the other hand, when the amount exceeds 200 parts by weight, the formed pixels easily fall off the substrate at the time of development, and the background and the light-shielding layer on the unexposed portion are liable to cause soiling, film residue and the like. 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 photopolymerization initiator, if necessary.

In the present invention, as the photopolymerization initiator,
In particular, it is preferable to use a combination of a biimidazole compound and an acetophenone compound and / or a benzophenone compound in that 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-based compound and another component are used in combination as the photopolymerization initiator, the proportion of the other component used is preferably 80% by weight or less of the entire photopolymerization initiator. Here, when the particularly preferred photopolymerization initiator in the present invention is shown as a combination of its constituent components, the following can be mentioned. 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
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 (2,4-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-dibromophenyl) -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-dibromophenyl) -4,4 ′, 5,5′-
Tetraphenyl-1,2'-biimidazole / 4,4 '
-Bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone.

Additives The radiation-sensitive composition for a color filter of the present invention can contain various additives as necessary. Examples of the additive include an organic acid having an effect of further improving the solubility of the radiation-sensitive composition for a color filter in an alkaline developer 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. 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 Dicarboxylic acids such as acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid; and tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid. Also,
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, and specific examples thereof. As 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;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanic acid, and pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, and 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 have alkali solubility and solubility in a solvent described below. This is preferable from the viewpoint of preventing background contamination and film residue on the unexposed portion of the substrate or light-shielding layer. The organic acids can be used alone or in combination of two or more. The amount of the organic acid to be used is generally 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, based on the whole radiation-sensitive composition. in this case,
If the amount of the organic acid exceeds 10% by weight, the adhesion of the formed pixel to the substrate tends to decrease.

Specific 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 mono- Polymer compounds such as alkyl ethers and poly (fluoroalkyl acrylates); surfactants such as 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-
Adhesion promoters such as chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol);
Antioxidants such as -di-t-butylphenol; 2- (3
-T-butyl-5-methyl-2-hydroxyphenyl)
UV absorbers such as -5-chlorobenzotriazole and alkoxybenzophenones; aggregation preventing agents such as sodium polyacrylate; thermal crosslinking agents such as epoxy compounds, melamine compounds and bisazide compounds.

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. Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 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 ,
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 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. Of these high-boiling solvents, γ-butyrolactone and the like are preferred. The high boiling solvents can be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, but from the viewpoint of the applicability of the obtained radiation-sensitive composition, stability and the like, the total concentration of each component excluding the solvent of the composition is usually A desirable amount is 5 to 50% by weight, preferably 10 to 40% by weight.

Method for Forming a 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 to be formed. On this substrate, for example, a liquid composition of a radiation-sensitive composition in which a red pigment is dispersed After applying the object, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, after this coating film is exposed to radiation 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 to form a red pixel pattern. A pixel array arranged in a predetermined arrangement is formed. 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 By sequentially forming a green pixel array and a blue pixel array on the same substrate,
A color filter in which pixel arrays of three primary colors of red, green and blue are arranged on a substrate is obtained. As a substrate used when forming a color filter, for example, glass,
Silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like can be mentioned. 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 10 μm, preferably 0.2 to 5.0 μm, as a film thickness after drying.
m, 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. . The irradiation energy amount of the radiation is preferably 1 to 1000 mJ / cm ² . Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-
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. 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. The developing condition is preferably 5 to 300 seconds at room temperature.
After the alkali development, the film is usually washed with water. The color filter thus formed is, for example, a transmission type or reflection type color liquid crystal display device, a color image pickup tube element,
Very useful for color sensors and the like.

[0053]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The radiation-sensitive composition for a color filter of the present invention contains the above-mentioned components (A) to (D) as essential components. And (a) to (g) below. (A) (B) The alkali-soluble resin contains the alkali-soluble resin (I), and (D) the photopolymerization initiator is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′- Tetrakis (4-ethoxycarbonylphenyl) -1,2'-
At least one selected from the group consisting of biimidazole and 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole A radiation-sensitive composition for a color filter, comprising the biimidazole compound of formula (I). (B) (B) The alkali-soluble resin contains the alkali-soluble resin (I), and (D) the photopolymerization initiator 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'- A radiation-sensitive composition for a color filter, comprising at least one biimidazole compound selected from the group of tetraphenyl-1,2'-biimidazole. (C) The radiation-sensitive composition for a color filter according to the above (A) or (B), wherein (D) the photopolymerization initiator further contains an acetophenone-based compound and / or a benzophenone-based compound. (D) (B) The alkali-soluble resin (I) is an alkali-soluble resin (Ia), an alkali-soluble resin (Ib), an alkali-soluble resin (Ic) and an alkali-soluble resin (I).
The radiation-sensitive composition for a color filter according to the above (A), (B) or (C), comprising at least one resin selected from the group of d). (E) The monofunctional monomer (b1) in the alkali-soluble resin (I) contains mono (2-acryloyloxyethyl) succinate and / or mono (2-methacryloyloxyethyl) succinate. (A), (B), (C) or (D), the radiation-sensitive composition for a color filter. (F) (C) the polyfunctional monomer comprises at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate ), (D) or (e), a radiation-sensitive composition for a color filter. (G) (A) wherein the colorant contains an organic pigment;
(B) The radiation-sensitive composition for a color filter according to (c), (d), (e) or (f).

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.

EXAMPLES Example 1 (A) CI Pigment Red 177 as a coloring agent
0 parts by weight, (B) methacrylic acid / mono (2-acryloyloxyethyl succinate) / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer (copolymer weight ratio = 15. 0 / 10.0 / 11.2 / 35.0 /
10.0 / 18.8, weight average molecular weight = 20,000)
60 parts by weight, (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2,2′-bis (2,4-dichlorophenyl) -4,4 ′ as a photopolymerization initiator. 5,5'-tetraphenyl-1,
10 weight parts of 2'-biimidazole, 10 weight parts of 4,4'-bis (diethylamino) benzophenone and 50 weight parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, Then, 1000 parts by weight of ethyl 3-ethoxypropionate as a solvent was mixed to prepare a liquid composition (1) of the radiation-sensitive composition. The pigment concentration of the liquid composition (1) is about 43% of the total solids.
% By weight. -Formation of Color Filter- The liquid composition (1) is applied using a spin coater on the surface of a soda glass substrate on which a SiO ₂ film for preventing sodium ions from being eluted is formed, and then is applied at 80 ° C for 10 minutes. Pre-baking was performed for 2 minutes to form a coating film having a thickness of 2.0 μm. Then, after cooling the substrate to room temperature, the coating film is applied to the coating film through a photomask using a high-pressure mercury lamp.
Ultraviolet rays having wavelengths of 65 nm, 405 nm and 436 nm were exposed at an exposure amount of 100 mJ / cm ² . Next, the substrate was immersed in a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 230 ° C. for 30 minutes to form a red striped color filter on the substrate. When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a light projector, no background stain was observed on the unexposed portion of the substrate. . Furthermore, when the unexposed substrate surface of the color filter was rubbed 10 times with Toraysee (trade name, lens cleaner manufactured by Toray Industries Inc.) containing ethanol, the Toraysee was not colored red. Did not. In addition, the adhesion between the pixel of the color filter and the substrate was excellent.

Example 2 (A) CI Pigment Red 177 as a coloring agent
0 parts by weight, (B) as an alkali-soluble resin, methacrylic acid / mono (2-acryloyloxyethyl succinate) / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide copolymer (copolymerization weight ratio = 15.0 / 10.0 / 11.2 / 1
0.0 / 35.0 / 18.8, weight average molecular weight = 25,
000) 60 parts by weight, (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer,
(D) 10 parts by weight of 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole as a photopolymerization initiator and 4,4 ′ −
Bis (diethylamino) benzophenone 10 parts by weight and 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (50 parts by weight) and 1000 parts by weight of ethyl 3-ethoxypropionate as a solvent are mixed to form a liquid of the radiation-sensitive composition. Composition (2) was prepared. The liquid composition (2) had a pigment concentration of about 43% by weight of the total solids. -Formation of Color Filter- A red striped color filter was formed in the same manner as in Example 1 except that the liquid composition (2) was used instead of the liquid composition (1). When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a light projector, no background stain was observed on the unexposed portion of the substrate. . Furthermore, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with Toraysee soaked in ethanol,
Toraysee was not colored red. Moreover,
The adhesion between the pixel of the color filter and the substrate was also excellent.

Example 3 (A) CI Pigment Green 36 as a colorant
0 parts by weight, (B) methacrylic acid / mono (2-acryloyloxyethyl succinate) / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymer weight ratio = 15.0 / 10.0 / 6) as alkali-soluble resin
0.0 / 15.0, weight average molecular weight = 30,000) 6
0 parts by weight, (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2,2'-bis (2,4-dichlorophenyl) -4,4 ', as a photopolymerization initiator. 5,5'-tetraphenyl-1,2 '
-10 parts by weight of biimidazole, 10 parts by weight of 4,4'-bis (diethylamino) benzophenone and 2-benzyl-
50 parts by weight of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and propylene glycol monomethyl ether acetate 10 as a solvent
The liquid composition (3) of the radiation-sensitive composition was prepared by mixing 00 parts by weight. The pigment concentration of the liquid composition (3) was about 41% by weight of the total solids. -Formation of Color Filter- A green striped color filter was formed in the same manner as in Example 1 except that the liquid composition (3) was used instead of the liquid composition (1). When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a light projector, no background stain was observed on the unexposed portion of the substrate. . Furthermore, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with Toraysee soaked in ethanol,
Toraysee was not colored red. Moreover,
The adhesion between the pixel of the color filter and the substrate was also excellent.

Example 4 (A) CI Pigment Blue 15 as a coloring agent in 100 parts
Parts by weight, (B) methacrylic acid / mono (2-acryloyloxyethyl succinate) / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide copolymer (copolymer weight ratio = 15) as alkali-soluble resin 0.0 / 10.0 / 11.2 / 10.0
/35.0/18.8, weight average molecular weight = 35,000
0) 60 parts by weight, (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D)
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl- as a photopolymerization initiator
10 parts by weight of 1,2′-biimidazole, 10 parts by weight of 4,4′-bis (diethylamino) benzophenone and 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one And 1000 parts by weight of ethyl 3-ethoxypropionate as a solvent to prepare a liquid composition (4) of a radiation-sensitive composition. The pigment concentration of the liquid composition (4) is about 3% of the total solids.
It was 8% by weight. -Formation of Color Filter- A blue striped color filter was formed in the same manner as in Example 1 except that the liquid composition (4) was used instead of the liquid composition (1). When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a light projector, no background stain was observed on the unexposed portion of the substrate. . Furthermore, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with Toraysee soaked in ethanol,
Toraysee was not colored red. Moreover,
The adhesion between the pixel of the color filter and the substrate was also excellent.

Comparative Example 1 Instead of 60 parts by weight of the alkali-soluble resin (B) of Example 1, a copolymer of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate (copolymerization weight ratio = 15/15) was used as the alkali-soluble resin. / 70, weight average molecular weight = 28,000) Except for using 60 parts by weight, a liquid composition of the radiation-sensitive composition was prepared in the same manner as in Example 1, and a red striped color was formed on the substrate. A filter was formed. When the obtained color filter was observed with an optical microscope, a residue was found on the unexposed portion of the substrate, and when observed using a light projector, background stain was also found on the unexposed portion of the substrate. Further, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with a tracey containing ethanol, the tracey was colored red.

[0059]

The radiation-sensitive composition for a color filter of the present invention exhibits excellent developability even when a pigment is contained at a high concentration, and causes residue and background stain on the unexposed portion of the substrate and the light-shielding layer during development. And a pixel having excellent adhesion to the substrate and the light-shielding layer can be provided. Therefore, the radiation-sensitive composition for a color filter of the present invention can be very suitably used for production of various color filters including a color filter for a color liquid crystal display device in the field of electronics.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA04 AA14 AB13 AC01 AC03 AD01 BC33 BC34 BC35 BC37 BC43 BC49 BC50 CA01 CA02 CA03 CA04 CA09 CA11 CA28 CB43 CB55 CC11 DA31 EA04 FA03 FA16 FA29 2H048 BA45 BB02 BB12 BB42 BB46

Claims (1)

[Claims] 1. A copolymer of a monomer selected from the group consisting of (A) a colorant, (B) mono (2-acryloyloxyethyl) dicarboxylate and mono (2-methacryloyloxyethyl) dicarboxylate. Radiation-sensitive radiation for a color filter, comprising an alkali-soluble resin containing a copolymer with a possible monofunctional monomer, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. Composition.