KR20090040232A - Radiation-sensitive composition, color filter, and liquid crystal display device for forming colored layer - Google Patents

Abstract

The radiation sensitive composition for forming a colored layer of the present invention is a dispersant in which at least one of (A) a pigment, (B) an acid value and an amine value is greater than zero, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E A photopolymerization initiator and (F) a polymer having a content of a repeating unit having an oxetanyl group is 70% by mass or more.

Accordingly, the radiation-sensitive composition for forming a colored layer of the present invention can form a pixel and a black matrix excellent in resistance to a wide range of solvents and excellent in adhesion to a substrate even at a post-baking temperature of less than 200 ° C. .

Description

Radiation-sensitive composition, color filter and liquid crystal display element for colored layer formation {RADIATION-SENSITIVE COMPOSITION FOR FORMING COLORED LAYER, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display device, and more particularly, the formation of a colored layer useful for a color filter used in a transmissive or reflective color liquid crystal display device, a color image tube device, or the like. It relates to a color filter comprising a radiation-sensitive composition used for, a colored layer formed by using the radiation-sensitive composition, and a color liquid crystal display device comprising the color filter.

A method of forming a color filter using a radiation-sensitive composition for forming a colored layer, wherein a coating film of the radiation-sensitive composition for forming a pigment dispersion-type colored layer is formed on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance. And irradiating radiation through a photomask having a predetermined pattern (hereinafter referred to as "exposure"), developing and dissolving the unexposed portion, and then post-baking to obtain pixels of each color (for example, The following Patent Document 1 and Patent Document 2) are known.

Here, in the post-baking process, a thermosetting treatment of about 30 minutes is generally performed at a temperature of 200 ° C to 250 ° C. In view of the reduction in manufacturing cost and substrates having a limit in heat resistance, such as plastic substrates, the lowering and shortening of the post-baking process have been considered. The development of the radiation sensitive composition for colored layer formation which has the above is highly desired.

On the other hand, with the high color purity of a color liquid crystal display device, there exists a tendency for the density | concentration of the pigment contained in the radiation sensitive composition for colored layer formation to become increasingly high. However, when the density | concentration of the pigment contained in the radiation sensitive composition for colored layer formation becomes high, the problem that resistance to the various solvents of the pattern formed and adhesiveness with a board | substrate fall. In order to solve such a problem, following patent document 3 is proposed to contain the binder polymer which copolymerized the monomer which has an oxetane skeleton in the photosensitive composition for colored layer formation. However, it was not applicable to lowering or shortening the above-described baking process.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Application Laid-Open No. 3-53201

[Patent Document 3] Japanese Unexamined Patent Publication No. 2002-296778

The present invention has been made on the basis of the above circumstances, and the problem is to provide a pixel and a black matrix excellent in resistance to a wide range of solvents and excellent in adhesion to a substrate even at a post-baking temperature of less than 200 ° C. It is providing the radiation sensitive composition for novel colored layer formation which can be provided. An object of this invention is also to provide the color filter formed using such a radiation sensitive composition for colored layer formation, and the liquid crystal display element provided with the said color filter.

MEANS TO SOLVE THE PROBLEM The present inventors included the dispersing agent which has a specific property, and the polymer containing the predetermined amount or more in the photosensitive composition for colored layer formation, and the repeating unit which has a specific frame | skeleton, and is also suitable for a wide range of solvents even at the post-baking temperature below 200 degreeC. It was found that a pixel and a black matrix can be formed that are excellent in resistance and excellent in adhesion to the substrate.

That is, the present invention is, firstly, a dispersing agent in which at least one of (A) pigment, (B) acid value and amine value is greater than zero, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photopolymerization initiator, And (F) It provides the radiation sensitive composition for colored layer formation containing the polymer whose content of the repeating unit which has an oxetanyl group is 70 mass% or more.

Secondly, the present invention provides a color filter formed using the radiation-sensitive composition for forming a colored layer.

A third object of the present invention is to provide a liquid crystal display device comprising the color filter.

According to the radiation sensitive composition for forming a colored layer of the present invention, a pixel and a black matrix excellent in resistance to a wide range of solvents and excellent in adhesion to a substrate can be formed even at a post-baking temperature of less than 200 ° C.

Therefore, the radiation sensitive composition for colored layer formation of this invention is very useful for manufacture of various color filters and liquid crystal display panels, including the color filter for color liquid crystal display panels in the electronic industry.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Radiation-sensitive composition for colored layer formation

The "coloring layer" in the radiation sensitive composition for forming a colored layer of the present invention (hereinafter also referred to simply as "radiation sensitive composition") means a layer containing a pixel and / or a black matrix used in a color filter. do.

Hereinafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

(A) Pigment

The (A) pigment in the present invention is not particularly limited and may be either an organic pigment or an inorganic pigment. Among these, organic pigments are particularly preferred because color filters require high purity and high permeability color development and heat resistance.

Examples of the organic pigments include compounds classified as pigments in the color index (C.I .; issued by The Society of Dyers and Colourists). Specifically, the following color index (C.I.) numbers are given.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment yellow 211;

C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 68, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment orange 74;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment red 272;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 58;

C.I. Pigment Brown 23, C.I. Pigment brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

These organic pigments can be used individually or in mixture of 2 or more types.

Among these organic pigments, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. At least one selected from the group of pigment violet 23 is preferred.

In the present invention, the organic pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof.

Moreover, as an inorganic pigment, for example, titanium oxide, barium sulfate, calcium carbonate, zincation, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III), cadmium red, ultramarine blue, blue blue, chromium oxide green, cobalt) Green, invar, titanium black, synthetic iron black, carbon black and the like.

These inorganic pigments can be used individually or in mixture of 2 or more types.

Moreover, in this invention, you may use together 1 or more types of dyes and natural dyes with the said pigment as needed.

In the present invention, the pigment may be used by modifying its particle surface with a polymer, if necessary. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, the polymer for disperse | distributing various pigments, or oligomer etc. are mentioned, for example.

-(B) dispersant-

The dispersing agent (B) in the present invention is a dispersing agent (hereinafter also referred to as "specific dispersing agent") in which at least one of the acid value and the amine value is more than zero. By selecting such a dispersing agent, the crosslinked structure formed by (F) component mentioned later in a post-baking process becomes stronger, and the pattern excellent in solvent resistance and adhesiveness with a board | substrate can be obtained.

The dispersant is not particularly limited as long as at least one of the acid value and the amine value exceeds 0, but a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, a modified polyurethane, a polyester, an alkyl ammonium salt or a phosphate ester salt of a polymer copolymer, a cationic comb graft polymer, etc. may be mentioned. The cationic comb graft polymer herein refers to a polymer having a structure in which two or more branch polymers are graft-bonded to one molecule of a stem polymer having a plurality of basic groups (cationic functional groups). For example, the stem polymer moiety is a polyethyleneimine or branch polymer The polymer comprised from the ring-opening polymer which is addition (epsilon) -caprolactone is mentioned. Of these dispersants, modified acrylic copolymers, acrylic copolymers, and cationic comb graft polymers are preferred.

In this invention, a dispersing agent can be used individually or in mixture of 2 or more types.

The acid value (mgKOH / g) of the dispersant is preferably 5 to 100, more preferably 10 to 50, particularly preferably 20 to 50, and the amine value (mgKOH / g) is preferably 1 to 100, further Preferably it is 10-70, Especially preferably, it is 20-70. By selecting such a dispersing agent, the pattern which is excellent in solvent resistance and adhesiveness with a board | substrate can be obtained, and also the radiation sensitive composition which is excellent also in storage stability and hardly generate | occur | produces a residue and ground contamination can be obtained. The amine number here refers to the mg number of KOH corresponding to the amount of HCl required to neutralize 1 g of the dispersant solids. In addition, an acid value shows the mg number of KOH which is required to neutralize 1 g of dispersant solid content.

Such dispersants are commercially available, for example

Disperbyk-142 (non-volatile component = 60%, amine value = 43, acid value = 46),

Dispervic-145 (non-volatile component = 100%, amine value = 71, acid value = 76),

Dispervic-161 (non-volatile component = 30%, amine value = 11),

Dispervic -170 (non-volatile component = 30%, acid value = 11),

Dispervic-182 (non-volatile component = 43%, amine number = 13),

Dispervic-2000 (non-volatile component = 40%, amine number = 4),

Dispervic-2001 (non-volatile component = 46%, amine value = 29, acid value = 19),

Dispervic-2020 (non-volatile component = 70%, amine value = 38, acid value = 35),

Dispervic-2150 (non-volatile component = 52%, amine number = 57),

Dispervic -9076 (non-volatile component = 96%, amine value = 44, acid value = 38) [above, manufactured by Big Chemical Co., Ltd.],

Ajisper PB-711 (non-volatile component = 40%, amine number = 45),

Azisper PB-821 (non-volatile component = 100%, amine value = 9, acid value = 13),

Azisper PB-822 (non-volatile component = 100%, amine value = 13, acid value = 16) [above, manufactured by Ajinomoto Fine Techno Co., Ltd.],

Solsperse 24000 (non-volatile component = 100%, amine value = 42, acid value = 25),

Solsperth 32000 (non-volatile component = 100%, amine value = 31, acid value = 15),

Solsper's 32500 (non-volatile component = 40%, amine value = 12, acid value = 7),

Solsperth 32550 (non-volatile component = 50%, amine value = 15, acid value = 7),

Solsper's 32600 (non-volatile component = 40%, amine value = 12, acid value = 6),

Solsper's 35100 (non-volatile component = 40%, amine value = 14, acid value = 6),

Solsperth 35200 (non-volatile component = 40%, amine value = 14, acid value = 6),

Solsper's 37500 (non-volatile component = 40%, amine value = 11, acid value = 5) (above, Lubrizol Co., Ltd. product) etc. are mentioned.

In this invention, another dispersing agent can be used together with a specific dispersing agent.

As said other dispersing agent, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol difatty acid esters such as polyethylene glycol dilaurate, polyethylene glycol distearate; Sorbitan fatty acid esters; And fatty acid-modified polyesters.

These other dispersing agents can be used individually or in mixture of 2 or more types.

The content ratio (solid content conversion) of the other dispersant is preferably 0 to 75% by mass, more preferably 0 to the total mass of the specific dispersant and the other dispersant from the viewpoint of ensuring a good balance between developability and storage stability. To 50 mass%.

Content (solid content conversion) of the specific dispersing agent in this invention is 1-50 mass parts with respect to 100 mass parts of (A) pigments from a viewpoint of the storage stability of a radiation sensitive composition, and the prevention of residue generation on a board | substrate, More preferably, it is 3-30 mass parts.

-(C) alkali-soluble resin-

As (C) alkali-soluble resin in this invention, it acts as a binder with respect to (A) pigment, and when producing a color filter, it is soluble with respect to the developing solution used by the developing process, especially preferably alkaline developing solution. It will not be specifically limited if it has. As such alkali-soluble resin, alkali-soluble resin which has a carboxyl group is preferable, Especially ethylenically unsaturated monomer which has 1 or more carboxyl group (henceforth "carboxyl group-containing unsaturated monomer"), and other ethylenically unsaturated monomer copolymerizable with this Preferred is a copolymer (hereinafter referred to as "copolymerizable unsaturated monomer") (hereinafter referred to as "carboxyl group-containing copolymer").

As a carboxyl group-containing unsaturated monomer, for example

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, 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, mesaconic acid or anhydrides thereof;

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] of bivalent or more polyvalent carboxylic acids, such as succinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] Esters;

Mono (meth) acrylates of the polymer which has a carboxyl group and a hydroxyl group in both terminal, such as (omega) -carboxypolycaprolactone mono (meth) acrylate,

Etc. can be mentioned.

A carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

In the present invention, as the carboxyl group-containing unsaturated monomer, (meth) acrylic acid, monosuccinic acid [2- (meth) acryloyloxyethyl],? -Carboxypolycaprolactone mono (meth) acrylate, and the like are preferable, and in particular ( Meth) acrylic acid is preferred.

Moreover, the following are illustrated as a copolymerizable unsaturated monomer, for example.

N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3 -Maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (acridy N-substituted maleimides such as nil) maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, aromatic vinyl compounds such as m-vinylbenzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol ( Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropyl Lenglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- Unsaturated carboxes such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and ethylene oxide modified (meth) acrylate of paracumylphenol Acid ester;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylic Unsaturated carboxylic acid aminoalkyl esters such as acrylate and 3-dimethylaminopropyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl (meth) acrylamide;

Carboxylic acid vinyl 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;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Macromonomers which have a mono (meth) acryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

In the present invention, the copolymerizable unsaturated monomer is preferably an N-substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, and the like. N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate And ethylene oxide modified (meth) acrylates of paracumylphenol, polystyrene macromonomers, polymethylmethacrylate macromonomers, and the like.

As a specific example of a carboxyl group-containing copolymer, the following are mentioned, for example.

(Meth) acrylic acid / methyl (meth) acrylate copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate copolymers,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) 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 / polymethylmethacrylate macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-m-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-p-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / p-hydroxy-α-methylstyrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer,

Ethylene oxide modified (meth) acrylate copolymers of (meth) acrylic acid / N-phenylmaleimide / styrene / paracumylphenol,

(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / N-p-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer,

 (Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / mono succinate [2- (meth) acryloyloxyethyl] / N-p-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / mono succinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,

(Meth) acrylic acid / mono succinate [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-m-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-p-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-p-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer.

 The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. When this copolymerization ratio is less than 5 mass%, there exists a tendency for the solubility with respect to the alkaline developing solution of the radiation sensitive composition obtained to fall. On the other hand, when it exceeds 50 mass%, there exists a tendency for the solubility to alkaline developing solution to become excessive, and when developing with alkaline developing solution, the fall of the colored layer from the board | substrate and the film roughness of the colored layer surface become easy to be brought about.

The weight average molecular weight (hereinafter referred to as "Mw") of the alkali-soluble resin in the present invention is usually 3,000 to 300,000, preferably 5,000 to 100,000.

In addition, the number average molecular weight (henceforth "Mn") of alkali-soluble resin in this invention is 3,000-60,000 normally, Preferably it is 5,000-25,000.

In this specification, the weight average molecular weight (Mw) means Mw of polystyrene conversion measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran), and the number average molecular weight (Mn) is GPC (elution solvent: tetra). Hydrofuran) to Mn in terms of polystyrene.

In this invention, the radiation sensitive composition excellent in developability is obtained by using alkali-soluble resin which has such specific Mw and Mn. As a result, not only the pixels and the black matrix having sharp pattern ends can be formed, but also residues, ground contamination, film residues, etc. on the substrate and the light shielding layer of the unexposed portion during development are less likely to occur.

Moreover, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin in this invention becomes like this. Preferably it is 1-5, More preferably, it is 1-4.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

Content (solid content conversion) of alkali-soluble resin in this invention is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. When content of alkali-soluble resin is less than 10 mass parts, alkali developability may fall, for example, or a ground contamination and a film residue may generate | occur | produce on the board | substrate or the light shielding layer of an unexposed part. On the other hand, when it exceeds 1,000 mass parts, since a coloring agent density | concentration falls relatively, there exists a possibility that it may become difficult to achieve the target color density as a thin film.

(D) polyfunctional monomer

The polyfunctional monomer in the present invention includes a monomer having two or more polymerizable unsaturated bonds.

As a polyfunctional monomer, for example

Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;

Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and these dicarboxylic acid modified substances;

Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spiran resin;

Di (meth) acrylates of both terminal hydroxylated polymers such as poly-1,3-butadiene of both terminal hydroxyls, polyisoprene of both terminal hydroxyls, and polycaprolactone of both terminal hydroxyls; And

Tris [2- (meth) acryloyloxyethyl] phosphate

Etc. can be mentioned.

Among these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances are preferable. Specifically, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, a compound represented by the following formula (1), a compound represented by the following formula (2), and the like are preferable. Do.

Among them, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the compounds represented by the formulas (1) and (2) are particularly high in the strength of the colored layer and the surface smoothness of the colored layer. It is excellent in that it is difficult to generate background contamination, film residue, etc. on the substrate and the light shielding layer of the unexposed part.

A polyfunctional monomer can be used individually or in mixture of 2 or more types.

In addition, in this invention, a part of polyfunctional monomer can also be replaced by the monofunctional monomer which has one polymerizable unsaturated bond.

As such a monofunctional monomer, For example, the compound similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer which were illustrated in (C) alkali-soluble resin, N- (meth) acryloyl morpholine, N-vinyl-pipi M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item other than a ralidone and N-vinyl- epsilon caprolactam.

These monofunctional monomers can be used individually or in mixture of 2 or more types.

The content rate of a monofunctional monomer is 90 mass% or less normally with respect to the total mass of a polyfunctional monomer and a monofunctional monomer, Preferably it is 50 mass% or less. When the content rate of monofunctional monomer exceeds 90 mass%, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

In this invention, content of a polyfunctional monomer is 5-500 mass parts normally with respect to 100 mass parts (solid content conversion) of (C) alkali-soluble resin, Preferably it is 20-300 mass parts. When the said content is less than 5 mass parts, there exists a tendency for the intensity | strength and surface smoothness of a colored layer to fall. On the other hand, when it exceeds 500 mass parts, alkali developability falls, for example, and it exists in the tendency for background contamination, a film residue, etc. to occur easily on the board | substrate or the light shielding layer of an unexposed part. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

-(E) photoinitiator-

The photopolymerization initiator in the present invention is an activity capable of initiating polymerization of (D) the polyfunctional monomer and the monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like. It is a compound that generates species.

Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, A polynuclear quinone type compound, a xanthone type compound, a diazo type compound, an imide sulfonate type compound, etc. are mentioned.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As a photoinitiator in this invention, 1 or more types chosen from the group of an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound are preferable.

In this invention, the sum total content of a photoinitiator is 0.01-120 mass parts normally with respect to 100 mass parts of (D) polyfunctional monomers, Preferably it is 1-100 mass parts. When content of a photoinitiator is less than 0.01 mass part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement. On the other hand, when it exceeds 120 mass parts, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

As a specific example of an acetophenone type compound among the preferable photoinitiators in this invention, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane- 1-one, 2-benzyl- Acetophenone compounds having a morpholino group such as 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one;

2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1,2 -Octanedione etc. are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-mor Polynophenyl) butan-1-one, 1,2-octanedione, etc. are preferable.

An acetophenone type compound can be used individually or in mixture of 2 or more types.

In this invention, when using an acetophenone type compound as a photoinitiator, the content is 0.01-80 mass parts normally with respect to 100 mass parts of (D) polyfunctional monomers, Preferably it is 1-70 mass parts, More preferably, Preferably from 1 to 60 parts by mass. When content of an acetophenone type compound is less than 0.01 mass part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement. On the other hand, when it exceeds 80 mass parts, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

Moreover, as a specific example of a biimidazole type compound,

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis Bis (halogen substituted phenyl) tetrakis (alkoxy, such as (2-bromophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole) Carbonylphenyl) 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'-tetra Phenyl-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-t And bis (halogen substituted phenyl) tetraphenylbiimidazoles such as ribomophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

Among these biimidazole compounds, 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 and the like are preferred, in particular 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl -1,2'-biimidazole is preferred.

These biimidazole-based compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved products and precipitates, and have high sensitivity, and sufficiently proceed the curing reaction by exposure of a small amount of energy. Curing reaction does not occur. For this reason, the coating film after exposure is clearly divided into the insoluble hardened part with respect to a developing solution, and the unhardened part which has high solubility with respect to a developing solution. Thereby, the high-precision color filter by which the colored layer pattern without undercut is arrange | positioned according to a predetermined arrangement can be formed.

A biimidazole type compound can be used individually or in mixture of 2 or more types.

In this invention, when using a biimidazole type compound as a photoinitiator, the content is 0.01-40 mass parts normally with respect to 100 mass parts of (D) polyfunctional monomers, Preferably it is 1-30 mass parts, More Preferably it is 1-20 mass parts. When content of a biimidazole type compound is less than 0.01 mass part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement. On the other hand, when it exceeds 40 mass parts, there exists a tendency which becomes easy to cause the fall of the colored layer formed at the time of image development, and the film | membrane of the colored layer surface. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

In this invention, when using a biimidazole type compound as a photoinitiator, using the hydrogen donor mentioned later together is preferable at the point which improves a sensitivity further.

The "hydrogen donor" as used here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure.

As a hydrogen donor in this invention, a mercaptan type compound, an amine compound, etc. which are defined below are preferable.

A mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus and having one or more, preferably one to three, more preferably one to two mercapto groups directly bonded to the mother nucleus (hereinafter, "Mercaptan-based hydrogen donor").

The amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, "Amine-based hydrogen donor").

These hydrogen donors may also have a mercapto group and an amino group at the same time.

The hydrogen donor will be described in more detail below.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, or may have both a benzene ring and a heterocycle. When it has 2 or more of these rings, a condensed ring can also be formed.

In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups may be substituted with alkyl, aralkyl or aryl groups as long as one or more free mercapto groups remain. As long as at least one free mercapto group remains, it may have a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms in the form of disulfide.

The mercaptan-based hydrogen donor may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a position other than the mercapto group.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thia Diazole, 2-mercapto-2,5-dimethylaminopyridine, and the like.

Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine-based hydrogen donor may have one or more benzene rings or heterocycles, or may have both a benzene ring and a heterocycle. When it has 2 or more of these rings, a condensed ring can also be formed.

In the amine-based hydrogen donor, at least one amino group may be substituted with an alkyl group or a substituted alkyl group, and at a position other than the amino group, a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, nitrile group or the like. It may be substituted by.

Specific examples of such amine-based hydrogen donors include amino-substituted benzophenones such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, and 4-dimethylaminopropiope. And non-ethyl, 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.

Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzo is particularly preferred. Phenones are preferred.

The amine hydrogen donor also has a function as a sensitizer even in the case of photopolymerization initiators other than the biimidazole compound.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. Particularly, the use of a combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors is preferable in that the formed colored layer is hardly eliminated from the substrate during development, and the colored layer strength and sensitivity are also high.

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4 '-Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino ) Benzophenone, etc. are mentioned. Especially, a more preferable combination is 2-mercapto benzothiazole / 4,4'-bis (diethylamino) benzophenone and 2-mercapto benzoxazole / 4,4'-bis (diethylamino) benzophenone And a particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

The mass ratio of the mercaptan-based hydrogen donor to the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3. .

In this invention, when using a hydrogen donor together with a biimidazole compound, content of a hydrogen donor becomes like this. Preferably it is 0.01-40 mass parts, More preferably 1-30, with respect to 100 mass parts of (D) polyfunctional monomers. It is mass parts, Especially preferably, it is 1-20 mass parts. When content of a hydrogen donor is less than 0.01 mass part, there exists a tendency for the improvement effect of a sensitivity to fall. On the other hand, when it exceeds 40 mass parts, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

Moreover, an amine hydrogen donor can function as a sensitizer when it uses together with photoinitiators other than biimidazole compounds, such as an acetophenone type compound. When using an amine hydrogen donor as a sensitizer, the content is 300 mass parts or less normally, Preferably it is 200 mass parts or less, More preferably, 100 mass parts with respect to 100 mass parts of photoinitiators other than a biimidazole compound. It is as follows. In addition, when such content is too small, since sufficient effect will become difficult to be acquired, it is preferable to make a minimum of content into 2 mass parts, More preferably, 5 mass parts.

In addition, specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 , 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine , 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl)- Triazine type compounds which have halomethyl groups, such as 4, 6-bis (trichloromethyl) -s-triazine, are mentioned.

Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.

The triazine type compound can be used individually or in mixture of 2 or more types.

In the present invention, in the case of using a triazine-based compound as the photopolymerization initiator, the content thereof is preferably 0.01 to 40 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the (D) polyfunctional monomer, Especially preferably, it is 1-20 mass parts. When content of a triazine type compound is less than 0.01 mass part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement. On the other hand, when it exceeds 40 mass parts, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

As the O-acyl oxime compound, for example, 1,2-octanedione, 1- [4- (phenylthiophenyl]-, 2- (O-benzoyloxime); 1- [9-ethyl-6 -Benzoyl-9H-carbazol-3-yl] -nonane-1,2-nonan-2-oxime-O-benzoate; 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -Nonane-1,2-nonane-2-oxime-O-acetate; 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -pentane-1,2-pentane-2-oxime- O-acetate; 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octan-1-one oxime-O-acetate; 1- [9-ethyl-6- (2-methylbenzoyl ) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate; 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9H-carbazole-3 -Yl] -ethane-1-one oxime-O-benzoate; 1- [9-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O -Benzoate; ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9 -Ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl ] -9H-carbazol-3-yl]-, 1- (O-acetyloxime), etc. are mentioned.

Among these O-acyl oxime compounds, especially 1,2-octanedione, 1- [4- (phenylthiophenyl]-, 2- (O-benzoyloxime); ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1-(O-acetyloxime); ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2 -Dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like are preferable.

O-acyl oxime type compounds can be used individually or in mixture of 2 or more types.

In the present invention, in the case of using an O-acyl oxime compound as the photopolymerization initiator, the content thereof is preferably 0.01 to 60 parts by mass, more preferably 1 to 1 to 100 parts by mass of the (D) polyfunctional monomer. 50 parts by mass, particularly preferably 1 to 40 parts by mass. When content of an O-acyl oxime type compound is less than 0.01 mass part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement. On the other hand, when it exceeds 60 mass parts, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

As a xanthone type compound, For example, Xanthone; Thioxanthones, such as thioxanthone, 2, 4- diethyl thioxanthone, and 2-chloro thioxanthone, are mentioned.

In this invention, when using a xanthone type compound as a photoinitiator, its content becomes like this. Preferably it is 0.01-50 mass parts, More preferably, 1-40 mass parts with respect to 100 mass parts of (D) polyfunctional monomers. Especially preferably, it is 1-30 mass parts. When content of a xanthone type compound is less than 0.01 mass part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement. On the other hand, when it exceeds 50 mass parts, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development. In addition, when using together a polyfunctional monomer and a monofunctional monomer, the mass of a monofunctional monomer is contained in the mass of a polyfunctional monomer.

-Polymer whose content of the repeating unit which has (F) oxetanyl group is 70 mass% or more-

The polymer (hereinafter, also referred to as "polymer (F)") having a content of a repeating unit having a (F) oxetanyl group in the present invention (hereinafter, also referred to as "polymer (F)") is a specific dispersant and (C) alkali-soluble in a post-baking step. It is a component which can bridge | crosslink resin. In addition, by heating, the polymer (F) alone can be polymerized to form a crosslinked structure.

In view of obtaining a colored layer having excellent solvent resistance and adhesion even at a low post-baking temperature, the polymer (F) preferably has a content of a repeating unit having an oxetanyl group of 90% by mass or more, particularly 95% by mass or more. desirable. Content of the repeating unit which has an oxetanyl group means here the value based on the total mass of all the repeating units which comprise a polymer (F),

As a monomer which provides the repeating unit which has an oxetanyl group, if it is an unsaturated compound which has an oxetanyl group, it will not specifically limit, For example, the following are illustrated.

3-[(meth) acryloyloxymethyl] oxetane, 3- [2- (meth) acryloyloxyethyl] oxetane, 2-[(meth) acryloyloxymethyl] oxetane, 2- [ (Meth) acryloyloxyalkyloxetanes, such as 2- (meth) acryloyloxyethyl] oxetane;

3-[(meth) acryloyloxymethyl] -2-methyloxetane, 3-[(meth) acryloyloxymethyl] -3-methyloxetane, 3-[(meth) acryloyloxymethyl] 2-ethyloxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 3- [ 2- (meth) acryloyloxyethyl] -3-methyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 3- [2- (meth) acryloyl Oxyethyl] -3-ethyloxetane, 2-[(meth) acryloyloxymethyl] -2-methyloxetane, 2-[(meth) acryloyloxymethyl] -3-methyloxetane, 2- [(Meth) acryloyloxymethyl] -4-methyloxetane, 2-[(meth) acryloyloxymethyl] -2-ethyloxetane, 2-[(meth) acryloyloxymethyl]- 3-ethyloxetane, 2-[(meth) acryloyloxymethyl] -4-ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 2- [2 -(Meth) acryloyloxyethyl -3-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -4-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 2 [(Meth) acryloyloxy such as [2- (meth) acryloyloxyethyl] -3-ethyl oxetane and 2- [2- (meth) acryloyloxyethyl] -4-ethyl oxetane Alkyl] alkyloxetane;

3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) acryloyloxymethyl] -2-pentafluoroethyloxetane, 3-[(meth) Acryloyloxymethyl] -2-phenyloxetane, 3-[(meth) acryloyloxymethyl] -2,2-difluorooxetane, 3-[(meth) acryloyloxymethyl] -2 , 2,4-trifluorooxetane, 3-[(meth) acryloyloxymethyl] -2,2,4,4-tetrafluorooxetane, 3- [2- (meth) acryloyloxy Ethyl] -2-trifluoromethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyl oxetane, 3- [2- (meth) acryloyloxyethyl] 2-phenyloxetane, 3- [2- (meth) acryloyloxyethyl] -2,2-difluorooxetane, 3- [2- (meth) acryloyloxyethyl] -2,2 , 4-trifluorooxetane, 3- [2- (meth) acryloyloxyethyl] -2,2,4,4-tetrafluorooxetane, 2-[(meth) acryloyloxymethyl] 2-trifluoro Methyl oxetane, 2-[(meth) acryloyloxymethyl] -3-trifluoromethyl oxetane, 2-[(meth) acryloyloxymethyl] -4-trifluoromethyl oxetane, 2- [(Meth) acryloyloxymethyl] -2-pentafluoroethyl oxetane, 2- [(meth) acryloyloxymethyl] -3-pentafluoroethyl oxetane, 2- [(meth) acrylo Iloxymethyl] -4-pentafluoroethyl oxetane,

2-[(meth) acryloyloxymethyl] -2,3-difluorooxetane, 2-[(meth) acryloyloxymethyl] -2,4-difluorooxetane, 2-[( (Meth) acryloyloxymethyl] -3,3-difluorooxetane, 2-[(meth) acryloyloxymethyl] -3,4-difluorooxetane, 2-[(meth) acrylo Iloxymethyl] -4,4-difluorooxetane, 2-[(meth) acryloyloxymethyl] -3,3,4-trifluorooxetane, 2-[(meth) acryloyloxy Methyl] -3,4,4-trifluorooxetane, 2-[(meth) acryloyloxymethyl] -3,3,4,4-tetrafluorooxetane, 2- [2- (meth) Acryloyloxyethyl] -2-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-trifluoromethyloxetane, 2- [2- (meth) acrylo Iloxyethyl] -4-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyl oxetane, 2- [2- (meth) acryloyloxy Ethyl] -3-penta Fluoroethyl oxetane, 2- [2- (meth) acryloyloxyethyl] -4-pentafluoroethyl oxetane, 2- [2- (meth) acryloyloxyethyl] -2,3-di Fluorooxetane, 2- [2- (meth) acryloyloxyethyl] -2,4-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,3-di Fluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,4-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -4,4-di Fluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,3,4-trifluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,4 [(Meth) acryloyloxyalkyl] fluorine such as, 4-trifluorooxetane and 2- [2- (meth) acryloyloxyethyl] -3,3,4,4-tetrafluorooxetane Rooxetane;

2-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] -3-phenyloxetane, 2-[(meth) acryloyloxymethyl] 4-phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-phenyloxetane, 2 (Meth) acrylic acid esters such as [(meth) acryloyloxyalkyl] phenyl oxetane such as [2- (meth) acryloyloxyethyl] -4-phenyloxetane;

4- [3- (3-ethyloxetan-3-ylmethoxy) propoxy] styrene, 4- [4- (3-ethyloxetan-3-ylmethoxy) butyloxy] styrene, 4- [5- ( 3-ethyloxetane-3-ylmethoxy) pentyloxy] styrene, 4- [6- (3-ethyloxetane-3-ylmethoxy) hexyloxy] styrene, 4- [7- (3-ethyloxetane Aromatic vinyls such as -3-ylmethoxy) heptyloxy] styrene.

Moreover, as for carbon number of the alkyl part in said "(meth) acryloyloxyalkyl" and "alkyloxetane", 1-4 are preferable.

Of the unsaturated compounds having these oxetanyl groups, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) Acryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] oxetane, 2-[(meth) acryloyloxymethyl] -4-trifluoromethyloxetane and the like are preferable, and 3- (methacryloyloxymethyl) oxetane and 3- (methacryloyloxymethyl) are particularly preferred. 3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacrylo From the point that the developing margin of the radiation sensitive composition from which oxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. are obtained is wide, and the chemical-resistance of the colored layer obtained is improved. desirable.

In addition, in this invention, as an unsaturated compound which has an oxetanyl group, besides the above, for example,

(3-oxetanylmethoxy) -p-vinylbenzene, [2- (3-oxetanyl) ethoxy] -p-vinylbenzene, (2-oxetanylmethoxy) -p-vinylbenzene, [2- (Oxetanylalkyl) ethers of vinylphenol such as (2-oxetanyl) ethoxy] -p-vinylbenzene;

(3-oxetanylmethyl) vinyl ether, [2- (3-oxetanyl) ethyl] vinyl ether, (2-oxetanylmethyl) vinyl ether, [2- (2-oxetanyl) ethyl] vinyl (Oxetanylalkyl) vinyl ethers such as ether

Etc. can also be used.

In a polymer (F), the unsaturated compound which has an oxetanyl group can be used individually or in mixture of 2 or more types.

In the polymer (F), the other unsaturated compound copolymerizable with this can be copolymerized with the unsaturated compound which has an oxetanyl group.

As another unsaturated compound, N-substituted maleimide, unsaturated carboxylic acid ester, unsaturated carboxylic acid aminoalkyl ester, and unsaturated carboxylic acid glycidyl ester which were mentioned as a copolymerizable unsaturated monomer in (C) alkali-soluble resin , Vinyl cyanide compounds, unsaturated amides, carboxylic acid vinyl esters, unsaturated ethers, aliphatic conjugated dienes, macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain,

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether Can be mentioned.

Mw of the polymer (F) in this invention becomes like this. Preferably it is 2,000-50,000, Especially preferably, it is 2,000-30,000.

Moreover, ratio (Mw / Mn) of Mw and Mn of the polymer (F) in this invention becomes like this. Preferably it is 1.0-2.5, Especially preferably, it is 1.0-2.0.

In this invention, by using the polymer (F) which has such specific Mw and / or Mw / Mn, the solvent resistance of the radiation sensitive composition obtained and adhesiveness with a board | substrate can be improved more.

The polymer (F) in the present invention is, for example, an unsaturated compound having an oxetanyl group in 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-) in a suitable solvent. Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanopropionic acid), 4,4'-azo Bis (4-cyanobutyl acid), 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanoethylbenzoic acid), 4,4'-azobis ( It can manufacture by polymerizing in presence of radical polymerization initiators, such as 4-cyanoethyl cyclohexanecarboxylic acid).

In addition, in the meaning which controls Mw / Mn in the said range, as a polymer (F) in this invention, the unsaturated compound which has an oxetanyl group in presence of the said radical polymerization initiator and the polyhydric thiol compound which acts as a chain transfer agent is mentioned. Preference is given to those prepared by radical polymerization in a suitable solvent. Here, in this specification, a polyvalent thiol compound means the compound which has two or more thiol groups in 1 molecule, For example, trimethylol propane tris (3-mercapto propionate) and pentaerythritol tetrakis (3- mercapto Propionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4- Bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione etc. are mentioned.

The use amount of the polyvalent thiol compound at the time of synthesize | combining a polymer (F) by superposition | polymerization is 0.5-20 mass parts normally with respect to 100 mass parts of unsaturated compounds which have an oxetanyl group, Preferably it is 1-10 mass parts. The usage-amount of a radical polymerization initiator is 0.1-50 mass parts normally with respect to 100 mass parts of said unsaturated compounds, Preferably it is 0.1-20 mass parts.

Moreover, polymerization temperature is 0-150 degreeC normally, Preferably it is 50-120 degreeC. The polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

In this invention, when synthesize | combining a polymer (F) by superposition | polymerization, chain transfer agents other than a polyvalent thiol compound, for example, t-dodecyl mercaptan, 2, 4- diphenyl-4- methyl-1- pentene, etc. 1 or more types of can also be used together in the quantity of 90 mass% or less normally, Preferably it is 60 mass% or less with respect to the total mass of a chain transfer agent.

Content of the polymer (F) in this invention is 1-400 mass parts normally with respect to 100 mass parts (solid content conversion) of (C) alkali-soluble resin, Preferably it is 3-200 mass parts, Especially preferably, 5 To 100 parts by mass. It exists in the tendency for a desired effect to become difficult to be acquired that the said content is less than 1 mass part. Moreover, when it exceeds 400 mass parts, there exists a tendency for the developability to disappear remarkably.

-additive-

The radiation sensitive composition of this invention may contain various additives as needed.

As an additive, an organic acid or an organic amino compound (however, the said hydrogen donor is excluded), a hardening | curing agent, a hardening adjuvant, etc. are mentioned, for example.

An organic acid and an organic amino compound are components which show the effect which further improves the solubility to the alkali developing solution of a radiation sensitive composition, and suppresses the remainder of the undissolved matter after image development.

As an organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has 1 or more carboxyl group in a molecule is preferable.

As aliphatic carboxylic acid, for example

Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasilic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;

Tricarboxylic acids, such as tricarvalic acid, aconitic acid, and camphoronic acid

Etc. can be mentioned.

Moreover, as a phenyl group containing carboxylic acid, the compound which the carboxyl group couple | bonded with the phenyl group directly, the carboxylic acid which the carboxyl group couple | bonded with the phenyl group through a carbon chain, etc. are mentioned, for example.

As a phenyl group containing carboxylic acid, for example

Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and cinnamildenmalonic acid;

Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid;

Phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamylidene acetic acid, kumaric acid, umbelic acid

Etc. can be mentioned.

Among these organic acids, aliphatic dicarboxylic acids are preferable as the aliphatic carboxylic acid from the viewpoint of alkali solubility, solubility in a solvent to be described later, prevention of background contamination on the substrate or the light shielding layer of the unexposed portion, and film residue. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable. Moreover, as a phenyl group containing carboxylic acid, aromatic dicarboxylic acids are preferable and phthalic acid is especially preferable.

An organic acid can be used individually or in mixture of 2 or more types.

Content of an organic acid is 15 mass% or less normally with respect to the whole solid content of a radiation sensitive composition, Preferably it is 10 mass% or less. When content of an organic acid exceeds 15 mass%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

As the organic amino compound, an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule is preferable.

As an aliphatic amine, the following are illustrated, for example.

n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethyl Mono (cyclo) alkylamines such as cyclohexylamine, 3-ethylcyclohexylamine and 4-ethylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- di (cyclo) alkylamines such as sec-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri -i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclo Tri (cyclo) alkylamines such as hexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino Mono (cyclo) alkanolamines such as -1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di ( Di (cyclo) alkanolamines such as 4-cyclohexanol) amine;

Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 Tri (cyclo) alkanolamines such as -cyclohexanol) amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2- Cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3- Amino (cyclo) alkanediols such as propanediol and 2-diethylamino-1,3-propanediol;

1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylamino Amino group-containing cycloalkanethanols such as cyclohexanemethanol and 4-diethylaminocyclohexanemethanol;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 Aminocarboxylic acids such as aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Moreover, as a phenyl group containing amine, the compound which the amino group couple | bonded with the phenyl group directly, the compound which the amino group couple | bonded with the phenyl group through the carbon chain, etc. are mentioned, for example.

As a phenyl group containing amine, it is, for example

Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and 4-methyl-N, N-dimethylaniline;

Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, and 4-diethylaminobenzyl alcohol;

Aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol

Etc. can be mentioned.

Among these organic amino compounds, mono (cyclo) alkanolamines, amino () as the aliphatic amines from the viewpoints of solubility in a solvent to be described later, prevention of background contamination on the substrate or the light shielding layer of the unexposed portion, and film residues. Cyclo) alkanediols are preferred, in particular 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3 -Propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol etc. are especially preferable.

A curing agent is a component that reacts with a specific dispersant, a carboxyl group-containing copolymer and / or a polymer (F) to insert itself into a crosslinked structure and to improve the degree of curing and solvent resistance.

As such a hardening | curing agent, an epoxy compound, an oxetane compound (except a polymer (F)), polyhydric carboxylic anhydride, etc. are mentioned, for example.

As an epoxy compound, a polyfunctional epoxy compound is preferable. Specific examples thereof include aromatic epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin and novolac epoxy resin; Other epoxy resins such as cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils; In addition to the brominated derivatives of these epoxy resins, epoxides of (co) polymers of butadiene, epoxides of (co) polymers of isoprene, (co) polymers of glycidyl group-containing unsaturated compounds, triglycidyl isocyanurate, and the like can be given. Can be.

Moreover, an epoxy group containing unsaturated compound is also preferable as an epoxy compound. Specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

As an oxetane compound, a polyfunctional oxetane compound is preferable. As the specific example, bis oxetanyl carbonate, bis oxetanyl adipic acid, bis oxetanyl terephthalate, p-xylylene dicarboxylic acid bis oxetanyl, 1, 4- cyclohexane dicarboxylic acid High molecular compounds, such as low molecular weight compounds, such as bisoxetanyl, and the oxetane etherate of a phenol novolak resin, are mentioned.

Moreover, as an oxetane compound, things other than the monomer used for the said polymer (F) can be used.

Specific examples of the polyhydric carboxylic anhydride include aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride. logistics; Aliphatic polyhydric carboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvallylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride logistics; Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polyhydric carboxylic anhydrides such as water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic acid anhydride, and nadic acid anhydride; In addition to ester group-containing carboxylic anhydrides such as ethylene glycol bistrimellitate anhydride and glycerin tristrimellitate anhydride, Adeka Hadner EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.) and Ricaside HH (Shin Nippon Chemical ( Epoxy resin hardening | curing agent etc. which are marketed by brand names, such as the following), MH-700 (made by Shin-Nippon Chemical Co., Ltd.), etc. are mentioned.

These hardeners can be used individually or in mixture of 2 or more types.

Content of a hardening | curing agent is 30 mass% or less normally with respect to the whole solid content of a radiation sensitive composition, Preferably it is 20 mass% or less. When content of a hardening | curing agent exceeds 30 mass%, there exists a tendency for the storage stability of the radiation sensitive composition obtained to fall.

The curing aid is a component that opens the functional group (eg, epoxy group, oxetanyl group) included in the polymer (F) and the curing agent and promotes the curing reaction without being inserted into the crosslinked structure itself.

Examples of such curing aids include thermal acid generators such as sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, and the like. Sulfonium salts, benzothiazonium salts, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds and the like are preferable.

As a specific example of sulfonium salts, the following are illustrated, for example.

4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, Dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexa Alkylsulfonium salts such as fluoroantimonate;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4 -Methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexa Benzylsulfonium salts such as fluoroarsenate and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl 4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5- dibenzylsulfonium salts such as tert-butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzylsulfonium salts, such as an antimonate and o-chlorobenzyl-3- chloro-4- hydroxyphenyl methylsulfonium hexafluoro antimonate.

Specific examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-meth Oxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, etc. Benzyl benzothiazonium salt etc. are mentioned.

Specific examples of the sulfonic acid ester compound include benzointosylate, α-methylolbenzointosylate, α-methylolbenzoin n-octanesulfonate, pyrogalloltris (trifluoromethanesulfonate), and pyrogalloltris ( Nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10- diethoxyanthracene-2-sulfonate, and the like.

Specific examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide, N- (10-campasulfonyloxy) succinimide, N- (10-campasulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide And N-[(5-methyl-5-carboxymethanebicyclo [2.2.1] hepta-2-yl) sulfonyloxy] succinimide and the like.

Specific examples of the diazomethane compound include bis (cyclohexanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] -decane-7-sul Ponyyl) diazomethane etc. are mentioned.

Among them, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimo Nate, Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, N- ( Trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and the like are preferred.

These curing aids can be used individually or in mixture of 2 or more types.

Content of a hardening adjuvant is 15 mass% or less normally with respect to the whole solid content of a radiation sensitive composition, Preferably it is 10 mass% or less. When content of a hardening aid exceeds 15 weight%, the storage stability of the radiation sensitive composition obtained tends to fall, or the formed colored layer tends to fall off from a board | substrate at the time of image development.

In addition, the minimum of content of a hardening | curing agent and a hardening adjuvant is 0.1 mass part normally with respect to the whole solid content of a radiation sensitive composition, Preferably it is 0.5 mass part.

In addition, as an additive other than the above, for example,

Dispersion aids such as blue pigment derivatives such as copper phthalocyanine derivatives and yellow pigment derivatives;

Fillers such as glass and alumina;

Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, and poly (fluoroalkyl acrylates);

Surfactants such as nonionic, cationic and anionic systems;

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-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter;

Antioxidants such as 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;

Aggregation inhibitors such as sodium polyacrylate;

And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenyllazo-4-methoxy-2,4-dimethylvaleronitrile.

-menstruum-

Although the radiation sensitive composition of this invention makes the said (A)-(F) component an essential component, and contains an additive component as needed, it is normally manufactured as a liquid composition by mix | blending a solvent.

The solvent may be appropriately selected and used as long as it disperses or dissolves the components (A) to (F) and the additive components constituting the radiation-sensitive composition and does not react with these components and has a suitable volatility.

As such a solvent, the following are illustrated, for example.

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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;

(Poly) alkylenes 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 Glycol monoalkyl ether acetates;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, I-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate n-butyl, n-butyl butyrate, methyl pyruvate Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, di, etc. Ethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxy propionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n- Butyl, ethyl pyruvate, etc. are preferable.

A solvent can be used individually or in mixture of 2 or more types.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, together with the solvent High boiling point solvents, such as diethyl oxalate, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Although content of a solvent is not specifically limited, From a viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition is 5-50 mass% normally, Preferably it is 10-40. The amount which becomes mass% is preferable.

Color filter

The color filter of this invention is equipped with the colored layer formed using the radiation sensitive composition for colored layer formation of this invention.

Hereinafter, the method of forming the colored layer in the color filter of this invention is demonstrated.

First, a light shielding layer is formed on the surface of a substrate so as to partition a portion for forming a pixel as necessary, and, for example, a liquid composition of a radiation-sensitive composition in which a red pigment is dispersed is applied onto the substrate, Pre-baking is carried out to evaporate the solvent to form a coating film.

Subsequently, after exposing this coating film through a photomask, it develops using alkaline developing solution, and removes and removes the unexposed part of a coating film. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed.

Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the same procedure as described above is carried out to apply, pre-bak, expose, develop, and post-bak each liquid composition to obtain a green pixel. By sequentially forming the array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in this invention, the order which forms the pixel of each color is not limited to the said thing.

In addition, a black matrix can be formed similarly to the case of formation of the said pixel, for example using the liquid composition of the radiation sensitive composition in which black pigment was disperse | distributed.

As a material of the board | substrate used when forming a pixel and / or a black matrix, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

Furthermore, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as necessary.

When the liquid composition of the radiation-sensitive composition is applied to a substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating or inkjet may be employed. In particular, the spin coating method and the slit die coating method are preferable.

The coating thickness is a film thickness after drying, which is usually 0.1 to 10 mu m, preferably 0.2 to 8.0 mu m, particularly preferably 0.2 to 6.0 mu m.

As the radiation used for forming the colored layer, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The exposure dose of radiation is preferably 10 to 10,000 J / m 2.

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- Aqueous solutions, such as diazabicyclo- [4.3.0] -5-nonene, are preferable.

A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline developing solution. In addition, after alkali development, water washing is normally performed.

As the developing treatment method, a shower developing method, a spray developing method, an immersion developing method, a puddle developing method and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

As a heating temperature in post-baking, although processing temperature of about 200-250 degreeC is employ | adopted conventionally, Preferably, in the radiation sensitive composition for colored layer formation of this invention, the processing temperature of about 150-200 degreeC Even in the present invention, a color filter having sufficient performance can be formed. Moreover, as heating time, although processing time of about 20-40 minutes is employ | adopted conventionally, in the radiation sensitive composition for colored layer formation of this invention, if it is a heating temperature of 200 degreeC or more, about 10 to 20 minutes, If it is heating temperature below 200 degreeC, the color filter which has a sufficient various performance can be formed also in the processing time of about 20 to 30 minutes.

The film thickness of the pixel formed in this way is 0.5-5.0 micrometers normally, Preferably it is 1.5-3.0 micrometers.

The color filter of the present invention thus obtained is very useful, for example, in a transmissive or reflective color liquid crystal display element, a color image tube element, a color sensor, or the like.

Liquid crystal display element

The liquid crystal display element of this invention is equipped with the color filter of this invention.

As one form of the liquid crystal display element of this invention, it is especially excellent by forming a pixel and / or a black matrix on the thin film transistor substrate array as mentioned above using the radiation sensitive composition for colored layer formation of this invention. The color liquid crystal display element which has a characteristic can be manufactured.

<Example>

Hereinafter, an Example is given and this invention is demonstrated further more concretely. However, the present invention is not limited to the following examples. In addition, "part" and "%" are mass references | standards unless there is particular notice below.

Mw and Mn of resin obtained by each following synthesis example were measured by the gel permeation chromatography (GPC) by the following specification.

Equipment: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.

Elution solvent: tetrahydrofuran containing 0.5% phosphoric acid

The dispersing agent, the polyfunctional monomer, the photoinitiator, and the hardening | curing agent used in the present Example are shown below.

Dispersant

b-1: Dispervic-2001 (non-volatile component = 46%, amine value = 29, acid value = 19, manufactured by Big Chemical Co., Ltd.)

b-2: Solsper 24000 (non-volatile component = 100%, amine value = 42, acid value = 25, Lubrizol Co., Ltd. product)

b-3: Dispervic-192 (non-volatile component = 100%, amine value = 0, acid value = 0, manufactured by BYK Corporation)

Polyfunctional monomer

d-1: dipentaerythritol hexaacrylate

Photopolymerization initiator

e-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one

e-2: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)

e-3: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one

e-4: 2,4-diethyl thioxanthone

e-5: 4,4'-bis (diethylamino) benzophenone

Hardener

g-1: Bisphenol A novolak-type epoxy resin (brand name 157S65, Japan Epoxy Resin Co., Ltd. product)

g-2: trimellitic anhydride

g-3: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide

(C) Synthesis of Alkali-Soluble Resin

Synthesis Example 1

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were put into a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid and 20 parts of N-phenylmaleimide, 10 parts of styrene, 55 parts of benzyl methacrylate, and 5 parts of 2,4-diphenyl-4-methyl-1-pentene (Nippon Yushi Co., Ltd. product name: Nofmer MSD) as a molecular weight regulator were added and nitrogen-substituted. . Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is called "alkali-soluble resin (c-1)". Polystyrene conversion weight average molecular weight by gel permeation chromatography measurement of this alkali-soluble resin was 11,000, and Mw / Mn was 2.6.

Synthesis Example 2

3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts of methacrylic acid, 85 parts of benzyl methacrylate, and As a molecular weight modifier, 5 parts of 2,4-diphenyl-4-methyl-1-pentene (the Nippon Yushi Co., Ltd. make brand name: Nova MSD) was thrown in, and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "alkali soluble resin (c-2)". Polystyrene conversion weight average molecular weight by gel permeation chromatography measurement of this alkali-soluble resin was 13,000, and Mw / Mn was 2.8.

Comparative Synthesis Example 1

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetates were added to the flask equipped with a cooling tube and the stirrer, and 15 parts of methacrylic acid, 70 parts of benzyl methacrylate, and 3 -15 parts of (methacryloyloxymethyl) -3-ethyl oxetane and 5 parts of 2,4-diphenyl-4-methyl-1-pentene (manufactured by Nippon Yushi Co., Ltd.) It injected | thrown-in and replaced with nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is called "alkali-soluble resin (c-3)". Polystyrene conversion weight average molecular weight by gel permeation chromatography measurement of this alkali-soluble resin was 13,000, and Mw / Mn was 2.7.

Synthesis of Polymer (F)

Synthesis Example 3

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 100 parts and 5 parts of 2, 4- diphenyl- 4-methyl- 1-pentene (The Nippon Yushi Co., Ltd. make brand name: Nova MSD) were prepared, and it substituted by nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "polymer (f-1)". Polystyrene conversion weight average molecular weight by the gel permeation chromatography measurement of this polymer was 12,000, and Mw / Mn was 2.9.

Synthesis Example 4

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 100 parts and 7 parts of pentaerythritol tetrakis (3-mercaptopropionate) (the Sakai Chemical Co., Ltd. make brand name: PEMP) were charged, and nitrogen substitution was carried out as a molecular weight regulator. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "polymer (f-2)". The weight average molecular weight of polystyrene conversion by the gel permeation chromatography measurement of this polymer was 7,000, and Mw / Mn was 1.7.

Synthesis Example 5

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 4,4'-azobis (4-cyano valeric acid) and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3 was added. 100 parts of ethyl oxetane and 5 parts of 2,4-diphenyl-4-methyl-1-pentene (Nipbon Yushi Co., Ltd. product name: Nova MSD) were added and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "polymer (f-3)". Polystyrene conversion weight average molecular weight by the gel permeation chromatography measurement of this polymer was 16,000, and Mw / Mn was 2.8.

Synthesis Example 6

3 parts of 2,2'- azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetates were put into the flask equipped with a cooling tube and the stirrer, and 4- [3- (3-ethyloxetane-3-ylmethoxy ) Propoxy] styrene 100 parts and 5 parts of 2, 4- diphenyl- 4-methyl- 1-pentene (The Nippon Yushi Co., Ltd. make brand name: Nova MSD) were prepared, and it substituted with nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and this resin was maintained for 5 hours to polymerize to obtain a resin solution. This resin is referred to as "polymer (f-4)". Polystyrene conversion weight average molecular weight by gel permeation chromatography measurement of this polymer was 11,000, and Mw / Mn was 2.6.

Synthesis Example 7

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 95 parts, benzyl methacrylate 5 parts, and 7 parts of pentaerythritol tetrakis (3-mercapto propionate) (A Sakai Chemical Co., Ltd. make brand name: PEMP) as a molecular weight modifier were thrown in, and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "polymer (f-5)". The weight average molecular weight of polystyrene conversion by the gel permeation chromatography measurement of this polymer was 7,000, and Mw / Mn was 1.7.

Synthesis Example 8

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 90 parts, 10 parts of benzyl methacrylates, and 7 parts of pentaerythritol tetrakis (3-mercaptopropionate) (the Sakai Chemical Co., Ltd. make brand name: PEMP) as a molecular weight regulator were thrown in, and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is called "polymer (f-6)". The weight average molecular weight of polystyrene conversion by the gel permeation chromatography measurement of this polymer was 7,000, and Mw / Mn was 1.7.

Synthesis Example 9

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 80 parts, 20 parts of benzyl methacrylates, and 7 parts of pentaerythritol tetrakis (3-mercaptopropionate) (the Sakai Chemical Co., Ltd. make brand name: PEMP) as a molecular weight regulator were thrown in, and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "polymer (f-7)". The weight average molecular weight of polystyrene conversion by the gel permeation chromatography measurement of this polymer was 7,000, and Mw / Mn was 1.7.

Synthesis Example 10

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 70 parts of benzyl methacrylate and 30 parts of benzyl methacrylate and 7 parts of pentaerythritol tetrakis (3-mercaptopropionate) (the Sakai Chemical Co., Ltd. make brand name: PEMP) were prepared, and it substituted by nitrogen. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is called "polymer (f-8)". The weight average molecular weight of polystyrene conversion by the gel permeation chromatography measurement of this polymer was 7,000, and Mw / Mn was 1.7.

Comparative Synthesis Example 2

Into a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate were added thereto, and 3- (methacryloyloxymethyl) -3-ethyl oxetane was added. 60 parts, 40 parts of benzyl methacrylates, and 7 parts of pentaerythritol tetrakis (3-mercaptopropionate) (the Sakai Chemical Co., Ltd. make brand name: PEMP) as a molecular weight modifier were thrown in, and nitrogen-substituted. Then, the mixture was stirred gently to raise the temperature of the reaction solution to 80 ° C., and maintained at this temperature for 5 hours to polymerize, thereby obtaining a resin solution. This resin is referred to as "polymer (f-9)". The weight average molecular weight of polystyrene conversion by the gel permeation chromatography measurement of this polymer was 7,000, and Mw / Mn was 1.7.

Preparation of Pigment Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 242 / C.I. Pigment Yellow 139 = 45/30/25 (mass ratio) 20 parts of a mixture, (b-1) 5 parts (solid content conversion) as a dispersing agent, 75 parts of propylene glycol monomethyl ether acetate as a solvent are processed by the bead mill, pigment dispersion liquid (R) was prepared.

Preparation Example 2

(A) As a coloring agent, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 parts of a mixture of 150 = 50/50 (mass ratio), 5 parts (in terms of solids) (b-2) as a dispersant, and 75 parts of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to give a pigment dispersion (S ) Was prepared.

Preparation Example 3

(A) As a coloring agent, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 parts of a mixture of 150 = 50/50 (mass ratio), 20 parts (b-3) (solid content conversion) as a dispersant, and 75 parts of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to give a pigment dispersion (T ) Was prepared.

Example 1

100 parts of the pigment dispersion (R), 10 parts of the alkali-soluble resin (c-1) solution (solid content conversion), 3 parts of the polymer (f-1) solution (solid content conversion), (D) as a polyfunctional monomer (d-1) 17 parts, (E) 5 parts of (e-1) as a photoinitiator, (e-4) 3 parts, and propylene glycol monomethyl ether acetate as a solvent were mixed and the liquid composition (R-1) of 25% of solid content concentration was manufactured. It was.

The liquid composition (R-1) was evaluated by forming a pattern according to the following procedure. The evaluation results are shown in Table 3 below.

Formation of patterns

After apply | coating a liquid composition (R-1) on the surface of a glass substrate using a spin coater, it pre-baked at 90 degreeC for 4 minutes, and formed the coating film with a film thickness of 1.3 micrometers. Subsequently, three board | substrates were cooled to room temperature, and it exposed to the coating film on each board | substrate by the exposure amount of 2,000 J / m <2> through the photomask using the high pressure mercury lamp for the coating film on each board | substrate. Subsequently, after showering by discharging a 0.04% potassium hydroxide aqueous solution of 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) to the coating films on the substrates, post-baking was performed at 220 ° C. or 180 ° C. for 30 minutes. To form a 200 x 200 탆 dot pattern.

Solvent resistance evaluation

Three substrates prepared by post-baking at 220 ° C. or 180 ° C. for 30 minutes were each N-methylpyrrolidone (referred to as “NMP” in Tables 3 and 4) at 25 ° C., and an aqueous 18% HCl solution (Table 3 And immersion in 5% aqueous KOH solution (referred to as "KOH" in Tables 3 and 4) for 30 minutes, respectively, and the dot pattern before and after immersion was observed with the scanning electron microscope. And when the pattern is formed satisfactorily and the film thickness ratio (film thickness after immersion x 100 / film thickness before immersion) before and after dipping is 95% or more, the film thickness ratio before and after dipping is less than 95%, or The case where a defect was recognized by one part was evaluated as B and the case where all the patterns peeled from a board | substrate after immersion is C.

Adhesion Evaluation

After apply | coating a liquid composition (R-1) on the surface of a glass substrate using a spin coater, it pre-baked at 90 degreeC for 4 minutes, and formed the coating film with a film thickness of 1.3 micrometers. Subsequently, after cooling this board | substrate at room temperature, it exposed on the coating film by the exposure amount of 2,000 J / m <2> using the high pressure mercury lamp. Subsequently, after showering was performed by discharging an aqueous 0.04% potassium hydroxide solution at 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm), the film was post-baked at 180 ° C. for 30 minutes. Next, in accordance with JIS K5400 standard, the coating film was cross-cut into 100 grid | lattices, and the adhesive test was done. And the case where A peeling does not generate | occur | produce A and the case where 1-10 pieces of a lattice are peeled off were evaluated as B and the case where more than 10 lattice peels.

Examples 2-16

Liquid compositions (R-2) to (R-16) were produced in the same manner as in Example 1, except that the compounding ingredients and the compounding amounts shown in Table 1 were changed.

Next, it evaluated similarly to Example 1 except having used liquid compositions (R-2)-(R-16) instead of liquid composition (R-1), respectively. Table 3 shows the results of the evaluation.

Comparative Examples 1 to 4

Liquid compositions (R-17) to (R-20) were produced in the same manner as in Example 1, except that the compounding ingredients and the compounding amounts shown in Table 1 were changed.

Next, it evaluated similarly to Example 1 except having used liquid compositions (R-17)-(R-20) instead of liquid composition (R-1), respectively. Table 3 shows the results of the evaluation.

Example 17

100 parts of the pigment dispersion (S), 12 parts of the alkali-soluble resin (c-1) solution (solid content conversion), 3 parts of the polymer (f-1) solution (solid content conversion), (D) as a polyfunctional monomer (d-1) 10 parts, (E) 5 parts of (e-3) as a photoinitiator, (e-5) 1 part, and propylene glycol monomethyl ether acetate as a solvent are mixed, and the liquid composition (S-1) of 25% of solid content concentration is manufactured. It was.

Next, except having used liquid composition (S-1) instead of liquid composition (R-1), it carried out similarly to Example 1, and formed the pattern and evaluated. The evaluation results are shown in Table 4 below.

Examples 18-32

Liquid compositions (S-2) to (S-16) were produced like Example 17 except having changed into the compounding component and compounding quantity shown in following Table 2.

Next, it evaluated similarly to Example 1 except having used liquid compositions (S-2)-(S-16) instead of liquid composition (R-1), respectively. The evaluation results are shown in Table 4.

Comparative Examples 5 to 9

Liquid compositions (S-17) to (S-20) and (T-1) were produced in the same manner as in Example 17, except that the compounding ingredients and the compounding amount shown in Table 2 were changed.

Next, it evaluated like Example 1 except having used liquid compositions (S-17)-(S-20) and (T-1) instead of liquid composition (R-1), respectively. The evaluation results are shown in Table 4.

Claims (5)

At least any one of (A) pigment, (B) acid value, and amine value is more than 0, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photoinitiator, and (F) oxetanyl group The radiation sensitive composition for colored layer formation containing the polymer whose content of the repeating unit which has is 70 mass% or more. The radiation sensitive composition for colored layer formation of Claim 1 whose ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) in (F) component is 1.0-2.5. The radiation sensitive composition for colored layer formation of Claim 1 whose (F) component is a polymer obtained by superposing | polymerizing in presence of a polyhydric thiol compound. The color filter formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-3. The liquid crystal display element provided with the color filter of Claim 4.