KR101152447B1 - Polymers, Radiation Sensitive Compositions for Color Filters, Color Filters and Color Liquid Crystal Display Device or Panel - Google Patents

Abstract

The polymer of the present invention is obtained by reacting an isocyanate having a (meth) acryloyl group with a polymer having a carboxyl group or a carboxylic anhydride group and a hydroxyl group. This polymer provides a radiation sensitive composition for color filters by mixing with a colorant, a polyfunctional monomer and an optical radical generator. This composition provides a color filter having a pixel and a black matrix in which undissolved portions remain during development, scum does not occur at the pattern edge, and defects and undercuts of the pattern edge do not occur even at a low exposure amount.

Polymers, radiation-sensitive compositions, color filters, color liquid crystal display elements or panels

Description

Polymers, Radiation Sensitive Compositions for Color Filters, Color Filters and Color Liquid Crystal Display Device or Panel

The present invention relates to a radiation sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device. In more detail, the radiation sensitive composition used for formation of the coloring layer (pixel and / or black matrix) useful for manufacture of the color filter used for a transmissive or reflective color liquid crystal display device, a color image tube element, etc., this sensitivity The color filter provided with the colored layer formed from the radioactive composition, and the color liquid crystal display element or panel provided with this color filter.

Conventionally, in manufacturing a color filter using a colored radiation-sensitive composition, after applying a colored radiation-sensitive composition on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance, the dried coating film is formed into a desired pattern shape. Method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as "exposure") and developing it (see Japanese Patent Laid-Open No. Hei 2-144502 and Japanese Patent Laid-Open No. Hei 3-53201). This is known.

In recent years, in the technical field of color filters, the movement of shortening the tact time by reducing the exposure amount has become mainstream, but in the conventional colored radiation-sensitive composition, defects or undercuts of pattern edges at the time of development are developed. Is easily generated, it is difficult to obtain a good patterned pixel and black matrix while shortening the tact time.

An object of the present invention is a radiation-sensitive composition for forming a colored layer which exhibits excellent developability, more specifically, undissolved matters remain during development, or scum does not occur at the pattern edge, and defects of the pattern edge are produced even at a low exposure amount. And a radiation-sensitive composition for a novel color filter that provides a pixel and a black matrix that does not cause undercut, a polymer useful as a component of the composition, a color filter formed of the radiation-sensitive composition for color filters, and the color filter. It is providing a liquid crystal display element or a panel.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention firstly,

A copolymer represented by the following formula (1) to a copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) a compound containing at least one hydroxyl group in a molecule, and (a3) another unsaturated compound A polymer obtained by reacting an isocyanate compound (hereinafter referred to as "(A) polymer").

In formula, R <_1> , R <_2> and R <_3> represent a hydrogen atom or group represented by following formula (1a) or 1b independently of each other, provided that R <_1> , R <_2> and R <_3> are not hydrogen atoms at the same time. a, b, c and d are each independently an integer of 0 to 12.

According to the present invention, the above objects and advantages of the present invention are second,

It is achieved by the radiation sensitive composition for color filters containing the said (A) polymer, (B) coloring agent, (C) polyfunctional monomer, and (D) optical radical generator.

As used herein, the term "colored layer" means a layer containing a pixel and / or a black matrix used in a color filter.

According to the present invention, the above objects and advantages of the present invention are third,

It is achieved by the color filter characterized by including the colored layer formed from the radiation sensitive composition for color filters.

According to the present invention, the above objects and advantages of the present invention are fourth,

It is achieved by the color liquid crystal display element or panel provided with the said color filter.

The present invention provides a radiation-sensitive composition for forming a colored layer, which exhibits excellent developability, and more specifically, undissolved matters remain during development or scum does not occur at the pattern edge, and defects and underscores of the pattern edge are obtained even at a low exposure amount. A radiation sensitive composition for a novel color filter providing a pixel and a black matrix which does not generate cuts, a polymer useful as a component of the composition, a color filter formed of a radiation sensitive composition for color filters, and a liquid crystal display comprising the color filter Provide an element or panel.

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

(A) polymer

The polymer (A) in the present invention is composed of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) an unsaturated compound containing at least one hydroxyl group in a molecule, and (a3) another unsaturated compound. It is a polymer obtained by making a copolymer (henceforth "alkali-soluble resin [alpha]") react with the isocyanate compound represented by the said Formula (1) (henceforth "unsaturated isocyanate compound (1)").

In each component which comprises alkali-soluble resin [(alpha)], as (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (henceforth these are collectively called "(a1) unsaturated carboxylic compound"), For example

As a carboxyl group-containing unsaturated monomer, for example

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, 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 monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ester;

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

And the like.

Among these carboxyl group-containing unsaturated monomers, mono succinate (2-acryloyloxyethyl) and mono phthalate (2-acryloyloxyethyl) are trademarks of M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively. It is commercially available.

In alkali-soluble resin [(alpha)], (a1) unsaturated carboxylic acid compound can be used individually or in mixture of 2 or more types.

In alkali-soluble resin [(alpha)], the content rate of the repeating unit derived from (a1) unsaturated carboxylic acid compound becomes like this. Preferably it is 5 to 50 weight%, More preferably, it is 5 to 40 weight%, Especially preferably, it is 5 to 30 wt%. If the content rate of the repeating unit derived from (a1) unsaturated carboxylic acid compound is less than 5 weight%, there exists a tendency for the solubility with respect to the alkaline developing solution of the polymer obtained by reaction with an unsaturated isocyanate compound (1) to fall, while 50 When it exceeds weight%, there exists a possibility that the solubility with respect to the alkaline developing solution of the said polymer may become large too much.

As the at least one hydroxyl group-containing unsaturated compound in the molecule (a2), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;

1,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl acrylate, 3,4-dihydroxybutyl acrylate, 3- [3- (2,3) Acrylic acid hydroxyalkyl esters such as dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl;

Methacrylic acid 1,2-dihydroxyethyl, methacrylic acid 2,3-dihydroxypropyl, methacrylic acid 1,3-dihydroxypropyl, methacrylic acid 3,4-dihydroxybutyl, methacrylic Methacrylic acid hydroxyalkyl esters, such as acid 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl, etc. are mentioned.

Among these (a2) at least one hydroxyl group-containing unsaturated compound, 2-hydroxyethyl (meth) acrylate, 1,2-dihydroxyethyl acrylate, acrylic acid 2,3 from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds -Dihydroxypropyl, methacrylic acid 1,2-dihydroxyethyl, methacrylic acid 2,3-dihydroxypropyl and the like are preferable.

In alkali-soluble resin [(alpha)], the unsaturated compound containing 1 or more hydroxyl group in a molecule | numerator (a2) can be used individually or in mixture of 2 or more types.

In alkali-soluble resin [(alpha)], the content rate of the repeating unit derived from the unsaturated compound containing one or more hydroxyl groups in (a2) molecule becomes like this. Preferably it is 1-50 weight%, More preferably, it is 3-40 weight%, Especially preferably, it is 5-30 weight%. (a2) When the content rate of the repeating unit derived from a hydroxyl-containing unsaturated compound is less than 1 weight%, the introduction rate of an unsaturated isocyanate compound (1) to a polymer will fall and a sensitivity will fall, and exceeding 50 weight% There exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound (1) to fall.

In addition, as another unsaturated compound (a3), for example,

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;

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, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-meth Methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, Unsaturated carboxyl, such as methoxy propylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and 2-hydroxy-3- phenoxypropyl (meth) acrylate Acid esters:

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;

Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide;

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;

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

Among these (a3) other unsaturated compounds, styrene, methyl (meth) acrylate, n-propyl (meth) acrylate and i-propyl (meth) from the viewpoint of the copolymerization reactivity and the solubility in the aqueous alkali solution of the obtained (A) polymer. ) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide and the like are preferable.

In alkali-soluble resin [(alpha)], (a3) another unsaturated compound can be used individually or in mixture of 2 or more types.

In alkali-soluble resin [(alpha)], (a3) The content rate of the repeating unit derived from another unsaturated compound becomes like this. Preferably it is 10 to 70 weight%, More preferably, it is 20 to 50 weight%, Especially preferably, it is 30 to 50 weight %to be. (a3) When the content rate of the repeating unit derived from another unsaturated compound is less than 10 weight%, there exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound (1) to fall, while exceeding 70 weight% The solubility of the polymer in alkaline developing solution tends to be lowered.

Alkali-soluble resin [(alpha)] can be manufactured, for example by polymerizing (a1) unsaturated carboxylic acid compound, (a2) hydroxyl-containing unsaturated compound, and (a3) other unsaturated compound in presence of a radical polymerization initiator in a suitable solvent. have.

As a solvent used for the said superposition | polymerization, for example,

Alcohols such as methanol, ethanol, n-propanol and i-propanol;

Ethers such as tetrahydrofuran and dioxane;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate;

Ethylene glycol monoalkyl ether propionate, such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, and ethylene glycol mono-n-butyl ether propionate Nate;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methylethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether;

Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methylethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate:

Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, and propylene glycol mono-n-butyl ether propionate Nate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, 2-methoxy ethylpropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy N-propyl propionic acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionic acid, 2-n-propoxypropionic acid n-butyl, 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, 3 N-butyl ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, 3-n-propoxyprop N-propyl on-acid, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-n-part Alkyl alkoxypropionates such as n-butyl oxypropionate;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, 4-methoxybutyl acetate, 3-acetic acid 3- Methoxybutyl, 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-butoxybutyl acetate, methyl lactate, ethyl lactate, lactic acid n-propyl, n-butyl lactate, 2-hydroxy-2-methylpropionic acid Methyl, 2-hydroxy-2-methylpropionate, 3-hydroxypropionate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid n-propyl, 3-hydroxypropionic acid n-butyl, 2-hydroxy- 3-Methyl butyrate, methyl methoxyacetate, methoxyacetic acid, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, ethoxyacetic acid methyl, ethoxyacetic acid, ethoxyacetic acid n-propyl, ethoxy N-butyl acetate , n-propoxy acetate, n-propoxy acetate, n-propoxy acetate n-propyl, n-propoxy acetate n-butyl, n-butoxy acetate, n-butoxy acetate, n-part Other esters such as oxyacetic acid n-propyl, n-butoxyacetic acid n-butyl

And the like.

Among these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate ester and the like are preferable.

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

Moreover, it does not specifically limit as said radical polymerization initiator, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2, 2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2- Azo compounds such as methyl propionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate and 1,1-bis (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like.

In addition, when using a peroxide as a radical polymerization initiator, it can also be used together with a reducing agent to make it a redox type initiator.

These radical polymerization initiators can be used individually or in mixture of 2 or more types.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin [α] in the present invention is preferably 3,000 to 300,000. , More preferably, it is 5,000-100,000.

In addition, polystyrene conversion number average molecular weight (henceforth "Mn") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin [(alpha) in this invention becomes like this. Preferably it is 3,000 To 60,000, more preferably 5,000 to 25,000.

If Mw is less than 3,000, alkali developability, residual film ratio, etc. of the resulting film may be reduced, or pattern shape, heat resistance, and the like may be impaired, whereas if it exceeds 300,000, resolution may be reduced or pattern shape may be damaged. have.

(A) polymer in this invention is obtained by making unsaturated isocyanate compound (1) react with alkali-soluble resin [(alpha)].

The alkali-soluble resin [(alpha)] obtained in this way can also be used for manufacture of (A) polymer as it is, and can also be used for manufacture of (A) polymer after isolate | separating from a solution once.

An unsaturated isocyanate compound (1) is a compound represented by following formula (1).

<Formula 1>

In formula, R <_1> , R <_2> and R <_3> represent a hydrogen atom or group represented by following formula (1a) or 1b independently of each other, provided that R <_1> , R <_2> and R <_3> are not hydrogen atoms at the same time. a, b, c and d are each independently an integer of 0 to 12.

<Formula 1a>

<Formula 1b>

As the unsaturated isocyanate compound (1), for example, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 1,1- (bisacryloyloxyethyl) ethyl isocyanate, 1,1- (bisacryloyl Acryl isocyanates such as oxypropyl) ethyl isocyanate;

Meta, such as 1,1- (bismethacryloyloxymethyl) ethyl isocyanate, 1,1- (bismethacryloyloxyethyl) ethyl isocyanate, 1,1- (bismethacryloyloxypropyl) ethyl isocyanate Krill Isocyanate

.

Among these unsaturated isocyanate compounds (1), 1,1- (bisacryloyloxymethyl) ethyl isocyanate and 1,1- (bismethacryloyloxymethyl) ethyl from the viewpoint of reactivity with alkali-soluble resin [α]. Isocyanate etc. are preferable.

As a commercial item of the said 1, 1- (bisacryloyl oxymethyl) ethyl isocyanate, Kalenzu BEI (made by Showa Denko Co., Ltd.) is mentioned by brand name.

In reaction of alkali-soluble resin [(alpha)] and unsaturated isocyanate compound (1), unsaturated isocyanate compound (1) can be used individually or in mixture of 2 or more types.

In the present invention, the reaction between the alkali-soluble resin [α] and the unsaturated isocyanate compound (1) is, for example, a catalyst such as dilauric di-n-butyltin (IV) or a polymerization inhibitor such as p-methoxyphenol. It can carry out by dripping the unsaturated isocyanate compound (1) to the alkali-soluble resin [(alpha]) solution containing this, stirring at room temperature or under heating.

The amount of the unsaturated isocyanate compound (1) used in the preparation of the polymer (A) is preferably 0.1 to 90% by weight based on the amount of the (a2) hydroxyl group-containing unsaturated compound used when synthesizing the alkali-soluble resin [α]. More preferably 10 to 80% by weight, particularly preferably 25 to 75% by weight. If the amount of the unsaturated isocyanate compound (1) used is less than 0.1% by weight, the effect on improving sensitivity and elastic properties is small, while if it exceeds 90% by weight, the unreacted unsaturated isocyanate compound (1) remains and the polymer solution obtained There exists a tendency for the storage stability of a radiation sensitive resin composition to fall.

The polymer (A) has a carboxyl group and / or a carboxylic anhydride group and a polymerizable unsaturated bond, and not only has suitable solubility in an alkaline developer, but also can be easily cured by heating without using a special curing agent in combination. The radiation sensitive resin composition containing the polymer (A) does not have cosmetic residues at the time of development, scum does not occur at the pattern edge, and defects and undercuts of the pattern edge do not occur even at a low exposure amount. It provides a pixel and a black matrix.

(A) It is preferable that a polymer has a structure represented by following formula (2).

R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The polymer (A) having the structure represented by the above formula (2), when synthesizing the alkali-soluble resin [α], (a3) at least part of the other unsaturated compound, N-phenylmaleimide, N-cyclohexyl maleimide and the like It can be obtained by using.

(B) colorant

The coloring agent in this invention is not specifically limited in color tone, It selects suitably according to the use of the color filter obtained, Any of a pigment, dye, or a natural dye is not concerned.

Since the color filter requires high color development and heat resistance, the colorant of the present invention is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance, and more preferably an organic pigment or an inorganic pigment is used. In particular, organic pigments and carbon blacks are used.

As the organic pigment, for example, a compound which is classified as Pigment by Color Index (CI; issued by The Society of Dyers and Colorists, Inc.), specifically, the following Color Index (CI) number is given. It can be mentioned.

C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, 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 60, C.I. Pigment Yellow 61, C.I. Pigment Yellow 65, C.I. Pigment Yellow 71, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 100, C.I. Pigment Yellow 101, C.I. Pigment Yellow 104, C.I. Pigment Yellow 106, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 116, C.I. Pigment Yellow 117, C.I. Pigment Yellow 119, C.I. Pigment Yellow 120, C.I. Pigment Yellow 126, C.I. Pigment Yellow 127, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 175, C.I. Pigment Yellow 180, C.I. Pigment yellow 185;

C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, 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 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment orange 73;

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 Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 37, C.I. Pigment Red 38, C.I. Pigment Red 40, C.I. Pigment Red 41, C.I. Pigment Red 42, C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 50: 1, C.I. Pigment Red 52: 1, C.I. Pigment Red 53: 1, C.I. Pigment Red 57, C.I. Pigment Red 57: 1, C.I. Pigment Red 57: 2, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 64: 1, C.I. Pigment Red 81: 1, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 90: 1, C.I. Pigment Red 97,

C.I. Pigment Red 101, C.I. Pigment Red 102, C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108, C.I. Pigment Red 112, C.I. Pigment Red 113, C.I. Pigment Red 114, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 151, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 172, C.I. Pigment Red 174, 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 188, C.I. Pigment Red 190, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment red 265;

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 Green 7, C.I. Pigment green 36;

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 refine | purified by the sulfuric acid recrystallization method, the solvent washing method, these combinations, etc., for example.

As the inorganic pigment, for example, titanium oxide, barium sulfate, calcium carbonate, zincation, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III)), cadmium, ultramarine blue, blue blue, chromium oxide, Cobalt rust, Invar, titanium black, synthetic iron black, carbon black, etc. are mentioned.

In the present invention, the organic pigments and inorganic pigments may be used alone or in combination of two or more, and may use an organic pigment and an inorganic pigment together. When forming a pixel, preferably at least one organic pigment is used, and when forming a black matrix, preferably at least two organic pigments and / or carbon black are used.

In the present invention, each of the pigments can be used by modifying the particle surface thereof with a polymer as desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, the polymer for dispersion | distribution of various pigments, or oligomer etc. are mentioned, for example.

In addition, the colorant in the present invention may be used with a dispersant as desired.

As said dispersing agent, surfactant, such as cationic, anionic, nonionic, amphoteric, silicone type, and fluorine type, is mentioned, for example.

As said surfactant, 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 diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyesters; Tertiary amine modified polyurethanes; In addition to polyethyleneimine and the like, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoesha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products, Inc.), and MegaPak (Dain Nippon Ink) Kagaku Kogyo Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Suflon (above, Asahi Glass Co., Ltd.), Disper byk (Big Chemie Japan ( (Manufactured by Co., Ltd.) and Sol Spas (manufactured by Seneca Co., Ltd.).

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

The amount of the surfactant used is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight with respect to 100 parts by weight of the colorant.

(C) polyfunctional monomer

Multifunctional monomers in the present invention include monomers 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 modified dicarboxylic acids thereof;

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 both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone,

Tris [2- (meth) acryloyloxyethyl] phosphate

And the like.

Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylic Latex, dipentaerythritol hexamethacrylate,

Compounds represented by the following formula (3), compounds represented by the following formula (4), and the like are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate are particularly high in the strength of the colored layer, It is excellent in the surface smoothness of a colored layer, and it is preferable at the point that a ground contamination, a film | membrane residue, etc. are hard to generate | occur | produce on the board | substrate and the light shielding layer of an unexposed part.

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

The usage-amount of the polyfunctional monomer in this invention becomes like this. Preferably it is 5-500 weight part, More preferably, it is 20-300 weight part with respect to 100 weight part of (A) polymers. If the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, if the amount is more than 500 parts by weight, for example, alkali developability is lowered, or the substrate or light-shielding of the unexposed part is performed. There is a tendency for background contamination, film residue and the like to easily occur on the layer.

In addition, in this invention, you may use together the polyfunctional monomer and the monofunctional monomer which has one polymerizable unsaturated bond simultaneously.

As said monofunctional monomer, the compound similar to the said carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer which were illustrated about the (A) polymer, for example, N- (meth) acryloyl morpholine, N-vinylpyrroli In addition to the toxin and N-vinyl-epsilon caprolactam, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types. The use ratio of a monofunctional monomer becomes like this. Preferably it is 90 weight% or less, More preferably, it is 50 weight% or less with respect to the sum total of a polyfunctional monomer and a monofunctional monomer. When the use ratio of a monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the polymer (A). If the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, if the total amount exceeds 500 parts by weight, for example, alkali developability is lowered, or the substrate or light shielding layer on the unexposed part is used. There is a tendency for background contamination, film residue and the like to occur easily.

(D) photoinitiator

The photopolymerization initiator in the present invention is used for the above-mentioned (C) polyfunctional monomer and in some cases by irradiation of radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron ray, X-ray and the like (hereinafter referred to as "exposure"). Compounds capable of generating active species capable of initiating the polymerization of monofunctional monomers.

As such a photoinitiator, a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, the (alpha)-diketone compound, a polynuclear quinone compound, a xanthone compound, a phosphine compound, a triazine compound etc. are mentioned, for example. Can be mentioned.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more thereof. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyl oxime compound may be used. At least one selected from the group is preferred.

As said biimidazole compound, it is, for example

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole

And the like.

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 and 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred, in particular 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2'-biimidazole is preferred.

The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved products, precipitates, etc., has high sensitivity, sufficiently advances the curing reaction by exposure of a small amount of energy, and has a high contrast. Since no curing reaction occurs in the unexposed portion, the coating film after exposure is clearly divided into an insoluble hardened portion with respect to the developer and an uncured portion with high solubility with the developer, and thus there is no undercut pixel pattern and black matrix pattern. It is possible to form a precise pattern array arranged in accordance with this predetermined arrangement.

Hydrogen donor

Moreover, in this invention, when using a biimidazole compound as an optical radical generating agent, using the following hydrogen donor together is preferable at the point which can improve 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 compound by exposure.

As such a hydrogen donor, the mercaptan compound defined below, the amine compound defined below, etc. are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one mercapto group directly bonded to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter "mercaptan"). Hydrogen donor ".

In addition, 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 referred to as "amine 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 hydrogen donor may have one or more benzene rings or heterocycles, respectively, and may have both a benzene ring and a heterocycle, and in the case of having two or more of these rings, a condensed ring may or may not be formed.

In addition, when the mercaptan hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group, and one or more As long as the 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 hydrogen donor may be substituted by a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like at a point other than the mercapto group.

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

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

Subsequently, the amine hydrogen donor may have one or more benzene rings or heterocycles, respectively, and may have both a benzene ring and a heterocycle, and in the case of having two or more of these rings, a condensed ring may or may not be formed.

Further, in the amine hydrogen donor, one or more amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like at a position other than the amino group It may be substituted by.

Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropy. Phenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid i-amyl, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, and the like.

Among these amine hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable. This is preferred. In addition, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone can act as an optical radical initiator by itself even when a biimidazole compound does not exist. will be.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. The use of a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors is preferred from the viewpoint that the formed colored layer is unlikely to fall off from the substrate during development, and the strength and sensitivity of the colored layer are also high.

Specific examples of preferred combinations of mercaptan hydrogen donors with amine hydrogen donors 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, and the like, and more preferred combinations include 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone and 2-mercaptobenzooxazole / 4,4'-bis ( Diethylamino) benzophenone, with a particularly preferred combination being 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

The weight ratio of the mercaptan hydrogen donor to the amine hydrogen donor in the combination of the mercaptan hydrogen donor and the amine hydrogen donor is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1: 3.

As said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzoyl benzoate, etc. are mentioned, for example.

As the acetophenone compound, for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2- Morpholino-1-propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.

As said benzophenone compound, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. are mentioned, for example.

As said (alpha)-diketone compound, diacetyl, dibenzoyl, methyl benzoyl formate, etc. are mentioned, for example.

As said polynuclear quinone compound, anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1, 4- naphthoquinone, etc. are mentioned, for example.

As said xanthone compound, xanthone, thioxanthone, 2-chloro thioxanthone, etc. are mentioned, for example.

Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine and 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-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)- And compounds having halomethyl groups, such as 4,6-bis (trichloromethyl) -s-triazine and compounds represented by the following formulas (5) and (6).

Moreover, as said O-acyl oxime compound, the compound etc. which are represented by following formula (7) and the like are mentioned, for example.

In formula, R <_1> is a C1-C20 linear or branched alkyl group, a C3-C8 cycloalkyl group, or a phenyl group, R <_2> and R <_3> is a hydrogen atom, a C1-C20 linear or branched alkyl group, respectively. , A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (however, may be substituted with one or more of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, phenyl groups and halogen atoms) or ali having 7 to 20 carbon atoms. Is a cyclic group (excluding the cycloalkyl group), and R ₄ is selected from a hydrogen atom, an oxygen containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur containing heterocyclic group having 4 to 20 carbon atoms R ₅ is hydrogen, an alkyl group of 1 to 12 carbon atoms or an alkoxyl group of 1 to 12 carbon atoms, n is an integer of 1 to 5, m is an integer of 0 to 5, 1 is an integer of 0 to 6 Where n + m ≤ 5 All.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms and cycloalkyl group having 3 to 8 carbon atoms of R ₁ in Formula 7 or 8 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group and n-butyl Group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodec A real group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Moreover, as a C1-C20 linear or branched alkyl group and C3-C8 cycloalkyl group of R <_2> , R <_3> , it is a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl, for example. Group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodec A real group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

The alkyl group having 1 to 6 carbon atoms as a substituent for the phenyl group of R ₂ and R ₃ may be linear, branched or cyclic. Examples of the alkyl group include methyl, ethyl, n-propyl and i-propyl groups. , n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

In addition, alkoxy groups having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy groups. and t-butoxy group. As a halogen atom, a fluorine atom, a chlorine atom, etc. are mentioned, for example.

Examples of the alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group) include a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a tert-cycloalkyl group, a terpene skeleton-containing group, an adamantyl skeleton-containing group, and the like. Can be mentioned.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms for R ₄ , the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms include, for example, a thioranyl group, an azepinyl group and a dihydroazinyl group. , Dioxoranyl group, triazinyl group, oxatinyl group, thiazolyl group, oxadiazinyl group, dioxazinyl group, dihianaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isooxa Zolyl group, thiazolyl group, isothiazolyl group, pyrazolyl group, prazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyridinyl group, pyrrolinyl group, morphonyl group, piperazinyl Group, quinucridinyl group, indolyl group, isoindolyl group, benzoprayl group, benzothiophenyl group, indridinyl group, chromenyl group, quinolinyl group, isoquinolinyl group, prinyl group, quinazolinyl group, cinnaolinyl group , Phthaladinyl group, pterridinyl group, carbazoryl group, acridi And a phenyl group, a phenanthridinyl group, a thioxanthenyl group, a phenadidinyl group, a phenothiadinyl group, a phenoxatinyyl group, a phenoxadinyl group, a thianthrenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. Among these, tetrahydrofuranyl group, tetrahydropyranyl group, etc. are especially preferable.

The alkyl group having 1 to 12 carbon atoms of R ₅ may be linear, branched or cyclic, and as such alkyl group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec- Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclophene Tyl group, cyclohexyl group, etc. are mentioned.

In addition, the alkoxy group having 1 to 12 carbon atoms may be linear, branched or cyclic. Examples of such alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group and t- Butoxy group, n-pentyloxy group, etc. are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, methoxy group and ethoxy group are preferable.

It is preferable that n is 1. It is preferable that m is any one of 0, 1, 2, It is especially preferable that it is 1, It is preferable that l is any one of 0, 1, 2, It is especially preferable that it is 1.

As a specific example of such an O-acyl oxime compound,

1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonan-2-oxime-O-benzoate,

1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate,

1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate,

1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -octane-1-one oxime-O-acetate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetateethanone,

1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime) ethanone,

1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime) ethanone,

1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime) ethanone,

1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime)

And the like.

The said photoradical generator can be used individually or in mixture of 2 or more types.

The total amount of the photoradical generator used in the present invention is preferably 0.01 to 200 parts by weight based on 100 parts by weight of (C) the polyfunctional monomer or 100 parts by weight of the monofunctional monomer used therein. More preferably, it is 1-120 weight part, Especially preferably, it is 1-100 weight part. If the total amount of the photoradical generating agent is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pattern array in which the pixel pattern or the black matrix pattern is arranged in accordance with a predetermined arrangement, and on the other hand, 200 weight parts. When the portion is exceeded, the formed colored layer easily falls off from the substrate at the time of development, and background contamination, film residue, and the like tend to occur on the substrate or the light shielding layer of the unexposed portion.

Moreover, in this invention, 1 or more types of a sensitizer, a hardening accelerator, or a polymer photocrosslinking-sensitizer can also be used together with the said optical radical generator as needed.

-additive-

Although the radiation sensitive composition for color filters of this invention makes each component of said (A)-(D) an essential component, it may contain another additive as needed.

As said additive, the organic acid or organic amino compound which shows the effect which further improves the dissolution characteristic with respect to the alkaline developing solution of a radiation sensitive composition, and suppresses the remainder of the undissolved matter after image development, except the said hydrogen donor ), And the like.

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

As said 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, pimeric acid, suberic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;

Tricarboxylic acids such as tricarbaric acid, aqua nitric acid and camphoronic acid

And the like.

Moreover, as said 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 via the 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 and terephthalic 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, cinnamiledic acid, cumalic acid, umbelic acid

And the like.

Among these organic acids, aliphatic dicarboxylic acids are preferable as the aliphatic carboxylic acid from the viewpoints of alkali solubility, solubility in a solvent to be described later, prevention of background contamination or film residue on the substrate or the light shielding layer of the unexposed portion, and 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 acid is preferable and phthalic acid is especially preferable.

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

The usage-amount of an organic acid is 15 weight% or less with respect to the whole radiation sensitive composition, Preferably it is 10 weight% or less. When the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Moreover, as said organic amino compound, the aliphatic amine or phenyl group containing amine which has 1 or more amino group in a molecule | numerator is preferable.

As said aliphatic amine, it is, 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-dimethylaminocyclo Amino group-containing cycloalkanethanols such as hexanemethanol 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 And aminocarboxylic acids such as -aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Moreover, as said phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, 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, 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;

And aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamine and amino (cyclo) are used as 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 retention. Alkanediol is preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propane Diol, 4-amino-1,2-butanediol, etc. are preferable. Moreover, as a phenyl group containing amine, aminophenol is preferable and 2-aminophenol, 3-amino phenol, 4-aminophenol etc. are especially preferable.

The said organic amino compound can be used individually or in mixture of 2 or more types.

The amount of the organic amino compound to be used is preferably 15% by weight or less, preferably 10% by weight or less based on the whole radiation-sensitive composition. When the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Moreover, as additives other than the said organic acid and organic amino compound, For example, Dispersion adjuvant, such as blue pigment derivatives, such as a copper phthalocyanine derivative, and a yellow pigment derivative;

Fillers such as glass and alumina;

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

Surfactants such as nonionic, cationic and anionic;

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 Adhesion promotion of hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. My;

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 alkoxybenzophenone;

An anti-aggregation agent such as sodium polyacrylate;

Thermal radical generating agents such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile

And the like.

menstruum

The radiation sensitive composition for colored layer formation of this invention makes the said (A)-(D) component an essential component, contains the said additive component as needed, Preferably it mixes a solvent and is manufactured as a liquid composition.

As said solvent, (A)-(D) component and additive component which comprise a radiation sensitive composition are disperse | distributed or melt | dissolved, and it can select suitably and can use, if it does not react with these components and has moderate volatility.

As such a solvent, 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 such as tripropylene glycol monoethyl ether 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 methylethyl ether, diethylene glycol diethyl ether, 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-methylbutane, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate Butyl, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, 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, N-methylpyrrolidone

And the like.

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, from the viewpoint of solubility, pigment dispersibility, coating property, etc. Diethylene glycol methylethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3-methyl-3 Methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, ethyl butyrate i-propyl, n-butyl butyrate, ethyl pyruvate, and the like. desirable.

The said 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 the usage-amount of a solvent is not specifically limited, From the 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 weight% normally, Preferably it is 10-40. The amount which becomes weight% is preferable.

Color filter

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

Below, the method of forming 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, Prebaking is performed to evaporate the solvent and form a coating film. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, post-baking after dissolving the unexposed part of a coating film, and forming the pixel array in which the red pixel pattern was arrange | positioned in the predetermined | prescribed arrangement. .

Thereafter, using the liquid composition of each radiation-sensitive composition in which green or blue pigments are dispersed, coating, preliminary baking, exposure, development and post-baking of each liquid composition are carried out in the same manner as above to obtain a green pixel array and By sequentially forming a blue pixel array on the same substrate, a color filter in which pixel arrays of three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, a black matrix can be formed similarly to the case of said pixel formation using the radiation sensitive composition for colored layer formation of this invention.

As a 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.

Further, 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 desired.

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, a spin coating method and a slit die coating method are preferable.

The coating thickness is a film thickness after drying, preferably 0.1 to 10 µm, more preferably 0.2 to 8.0 µm, particularly preferably 0.2 to 6.0 µm.

As radiation used when forming the pixel and / or black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used. Preference is given to radiation in which the wavelength is in the range of 190 to 450 nm.

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, Aqueous solutions, such as 5-diazabicyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like can also be added to the alkaline developer. After the alkali development, water washing is preferably performed.

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

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

Color liquid crystal display or panel

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

Further, as one embodiment of the color liquid crystal display element or panel of the present invention, using the radiation-sensitive composition for forming a colored layer of the present invention, a pixel and / or a black matrix as described above on a thin film transistor substrate array. By forming the, a color liquid crystal display panel having particularly excellent properties can be manufactured.

The radiation sensitive composition for colored layer formation of this invention contains the said (A)-(D) component as an essential component. Specific examples of particularly preferred compositions are as follows (a) to (d).

(A) The radiation sensitive composition for colored layer formation containing the (A) polymer which has an ethylenically unsaturated double bond in (B) side chain.

(B) For the colored layer formation (a), wherein the polyfunctional monomer (C) comprises at least one member selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Radiation-sensitive composition.

(C) (D) the photo radical generator is 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one;

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone;

2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole;

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate ethanone,

1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime) ethanone,

1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime) ethanone,

1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime) ethanone,

1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime)

The radiation sensitive composition for colored layer formation of said (B) which consists of 1 or more types chosen from the group.

(D) The radiation sensitive composition for forming a colored layer of said (A), (B) or (C) whose (B) colorant contains an organic pigment and / or carbon black.

In addition, the preferred color filter of the present invention,

(E) The pixel and / or black matrix formed from the radiation sensitive composition for colored layer formation of said (a), (b), (c) or (d) are provided.

Moreover, the preferable color liquid crystal display panel of this invention is

(F) The color filter of said (e) is provided.

More preferred color liquid crystal display device of the present invention,

(G) A pixel and / or a black matrix formed of the radiation-sensitive composition for forming the colored layer of (a), (b), (c) or (d) are provided on the thin film transistor substrate array.

As described above, the radiation-sensitive composition for forming a colored layer of the present invention uses a polymer having an ethylenically unsaturated double bond in its side chain, so that even when it contains a pigment at a high concentration, on the substrate and the light shielding layer of the unexposed part at the time of development Undissolved matters remain on the surface, or scum does not occur at the edges of the pixel pattern and the black matrix pattern, and even a low exposure amount can form a good pixel pattern and a black matrix pattern without defects and undercuts of the pattern edge.

Moreover, the pixel and black matrix formed using the radiation sensitive composition for colored layer formation of this invention have high surface smoothness, and are excellent also in adhesiveness with a board | substrate.

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

<Examples>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

Where parts and% are based on weight.

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

Apparatus: 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.

Mobile phase: Tetrahydrofuran comprising 0.5% by weight phosphoric acid.

Synthetic example  One

In a flask equipped with a cooling tube and a stirrer, 3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added, and then 15 parts by weight of methacrylic acid and N-phenylmaleimide 18.8 Parts by weight, 35 parts by weight of benzyl methacrylate, 11.2 parts by weight of styrene, 10 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of ω-carboxy-polycaprolactone monoacrylate and α as a chain transfer agent as a molecular weight control agent. -5 parts by weight of methyl styrene dimer was added, and after nitrogen substitution, the reaction solution was heated to 80 ° C while stirring slowly, and maintained at this temperature to polymerize for 3 hours. Thereafter, the reaction solution was heated to 100 ° C, 0.5 part by weight of 2,2'-azobisisobutyronitrile was added, and the polymerization solution was continued for 1 hour, thereby obtaining a resin solution (solid content concentration = 33.0% by weight). Got it. Obtained resin was Mw = 12,000 and (Mw / Mn) = 1.8. This resin is referred to as "alkali-soluble resin (α-1)".

Subsequently, 10 parts by weight of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name Karens BEI, manufactured by Showa Denko Co., Ltd.) and 4-methoxyphenol in the alkali-soluble resin (α-1) solution. After adding 0.1 parts by weight, the reaction was stirred at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. The progress of reaction of the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of alkali-soluble resin ((alpha) -1) was confirmed by IR (infrared absorption) spectrum. As the reaction proceeded, it was confirmed that the peak near 2270 cm ⁻¹ derived from the isocyanate group of 1,1- (bisacryloyloxymethyl) ethyl isocyanate is decreasing. The polymer solution of 35.0 weight% of solid content concentration was obtained. This polymer is referred to as "(A) polymer-1".

Synthetic example  2

In a flask equipped with a cooling tube and a stirrer, 3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Then, 13 parts by weight of methacrylic acid and benzyl methacrylate 77 5 parts by weight of α-methylstyrene dimer, which is a chain transfer agent, was added as a part by weight, 10 parts by weight of 2-hydroxyethyl methacrylate, and a molecular weight control agent, and after nitrogen replacement, the reaction solution was heated to 80 ° C while stirring slowly. The polymerization was carried out for 3 hours while maintaining the temperature. Thereafter, the reaction solution was heated to 100 ° C, 0.5 part by weight of 2,2'-azobisisobutyronitrile was added, and the polymerization solution was continued for 1 hour to thereby obtain a resin solution (solid content concentration = 33.0% by weight). Got it. Obtained resin was Mw = 17,000 and (Mw / Mn) = 2.5. This resin is referred to as "alkali-soluble resin (? -2)".

Subsequently, 10 parts by weight of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name Karens BEI, manufactured by Showa Denko Co., Ltd.) and 4-methoxyphenol in the alkali-soluble resin (α-2) solution. After adding 0.1 parts by weight, the reaction was stirred at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. The progress of reaction of the isocyanate group derived from 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the hydroxyl group of alkali-soluble resin (α-2) was confirmed by IR (infrared absorption) spectrum. As the reaction proceeded, it was confirmed that the peak around 2270 cm ⁻¹ derived from the isocyanate group of 1,1- (bisacryloyloxymethyl) ethyl isocyanate is decreasing. The polymer solution of 35.0 weight% of solid content concentration was obtained. This polymer is referred to as "(A) polymer-2".

Example  One

(B) C.I. Pigment Red 254 / C.I. Pigment Red 177 = 80/20 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight (in terms of solids) of Dispervic-2001 as a dispersant, methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate air 6 parts by weight of coalescing (copolymerization weight ratio = 20/30/20/30, Mw = 9,500, Mn = 5,000) and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to prepare a preliminary dispersion (R1). It was.

Next, 100 parts by weight of the preliminary dispersion (R1), 7.5 parts by weight of (A) polymer-1 synthesized in Synthesis Example 1 as the polymer (A), and 7.5 parts by weight of dipentaerythritol hexaacrylate as the (C) polyfunctional monomer. (D) 0.5 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator and 150 parts by weight of ethyl 3-ethoxypropionate as a solvent and propylene glycol mono 25 weight part of methyl ether acetates were mixed, and the radiation sensitive composition for color filters (R1-1) was produced.

<Evaluation>

When the pixel array on the substrate was observed with an optical microscope, no development residue was recognized on the substrate of the unexposed portion, and scum and defects were not recognized at the edge of the pixel pattern.

Moreover, when the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), undercut was not recognized.

Comparative example  One

<Production of Liquid Composition and Formation of Colored Layer>

It carried out similarly to Example 1 except having used alkali-soluble resin ((alpha) -1) instead of the said polymer (A) -1, and manufactured the radiation sensitive composition (r1-1).

Subsequently, it carried out similarly to Example 1 except having used the radiation sensitive composition (r1-1) instead of the radiation sensitive composition (R1-1) for color filters, and the red striped pixel pattern was carried out on the board | substrate. An array of pixel arrays was formed.

(evaluation)

When the pixel array on the substrate was observed with an optical microscope, no development residue was recognized on the substrate of the unexposed portion, but a defect in the edge of the pixel pattern was recognized.

Moreover, when the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), undercut was recognized.

Example  2

<Production of Liquid Composition and Formation of Colored Layer>

(B) C.I. Pigment Green 36 / C.I. Pigment Yellow 138 / C.I. Pigment Yellow 150 = 50/40/10 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of dispervic-2001 (solid equivalent), methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N- as a dispersant 5 parts by weight of phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000), and propylene as a solvent 76 parts by weight of glycol monomethyl ether acetate were treated in the same manner as in Example 1 to prepare a preliminary dispersion (G1).

Next, 100 parts by weight of the preliminary dispersion (G1), 7 parts by weight of (A) polymer-2 synthesized in Synthesis Example 2 as the polymer (A), and 8 parts of dipentaerythritol hexaacrylate as the (C) polyfunctional monomer. (D) 0.5 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as photopolymerization initiator, 0.1 part by weight of malonic acid as an additive, and 3-methine as a solvent 125 parts by weight of oxybutyl acetate and 50 parts by weight of propylene glycol methyl ether acetate were mixed to prepare a radiation sensitive composition for color filters (G1-1).

Subsequently, it carried out similarly to Example 1 except having used the radiation sensitive composition (G1-1) for color filters instead of the radiation sensitive composition (R1-1) for color filters. A pixel array in which pixel patterns are arranged is formed.

Example  3

<Production of Liquid Composition and Formation of Colored Layer>

(B) C.I. Pigment Blue 15: 6 and C.I. 15 parts by weight of a 95/5 (weight ratio) mixture with pigment violet 23, 4 parts by weight of Dispervic-2001 (solid content equivalent) as a dispersant, methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmalee Mid / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymer weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) 5 parts by weight and propylene glycol monomethyl as solvent 76 parts by weight of ether acetate was treated in the same manner as in Example 1 to prepare a preliminary dispersion (B1).

Subsequently, 100 parts by weight of the preliminary dispersion (B1), 6 parts by weight of (A) polymer-1 synthesized in Synthesis Example 1 as the polymer (A), and 9 parts of dipentaerythritol hexaacrylate as the (C) polyfunctional monomer. (D) 0.5 parts by weight of 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propanone 1 as the photopolymerization initiator, and A-60 (trade name, manufactured by KAO Co., Ltd.) as an additive. Nonionic surfactant) 0.5 parts by weight and 150 parts by weight of ethyl 3-ethoxypropionate and 25 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed to prepare a radiation sensitive composition for color filters (B1-1).

Subsequently, it carried out similarly to Example 1 except having used the radiation sensitive composition for color filters (B1-1) instead of the radiation sensitive composition for color filters (R1-1), and carried out a blue stripe pattern on the board | substrate. A pixel array in which pixel patterns are arranged is formed.

<Evaluation>

When the pixel array on the substrate was observed under an optical microscope, no development residue was recognized on the substrate of the unexposed portion, and scum and defects were not recognized at the edge of the pixel pattern.

Moreover, when the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), undercut was not recognized.

Example  4

<Production of Liquid Composition and Formation of Colored Layer>

(B) 20 parts by weight of carbon black (manufactured by Mikuni Shikiso Co., Ltd.) as a coloring agent, 2 parts by weight (in terms of solids) of methacrylic acid / ω-carboxypolycaprolactone monoacrylate / as a dispersant 4 parts by weight of N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymer weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) and 3- 74 parts by weight of methoxybutyl acetate was treated in the same manner as in Example 1 to prepare a preliminary dispersion (BK1).

Next, 100 parts by weight of the preliminary dispersion (BK1), 4.5 parts by weight of (A) polymer-2 synthesized in Synthesis Example 2 as the polymer (A), and 5.5 parts of dipentaerythritol hexaacrylate as the (C) polyfunctional monomer. (D) 1-part by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and A-60 (trade name, manufactured by KAO Co., Ltd.) as an additive. Nonionic surfactant) 0.5 part by weight and 125 parts by weight of propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone were mixed to prepare a colored layer-forming composition (BK1-1).

Subsequently, it carried out similarly to Example 1 except having used the radiation sensitive composition for color filters (BK1-1) instead of the radiation sensitive composition for color filters (R1-1), and formed a black stripe shape on the board | substrate. A pixel array in which pixel patterns are arranged is formed.

<Evaluation>

When the pixel array on the substrate was observed with an optical microscope, no development residue was recognized on the substrate of the unexposed portion, and scum and defects were not recognized at the edge of the pixel pattern.

Moreover, when the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), undercut was not recognized.

Example  5

<Production of Liquid Composition and Formation of Colored Layer>

(B) 20 parts by weight of carbon black (manufactured by Mikuni Shikiso Co., Ltd.) as a coloring agent, 2 parts by weight of dispervic-2001 (solid content conversion) as a dispersant, methacrylic acid / ω-carboxypolycaprolactone monoacrylate / 4 parts by weight of N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymer weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) and 3- 74 parts by weight of methoxybutyl acetate was treated in the same manner as in Example 1 to prepare a preliminary dispersion (BK2).

Next, 100 parts by weight of the preliminary dispersion (BK2), 4.5 parts by weight of polymer (A) -2 synthesized in Synthesis Example 2 as the polymer (A), and 5.5 parts by weight of dipentaerythritol hexaacrylate as the (C) polyfunctional monomer. (D) 1 weight of 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate as a photoinitiator Part, 0.5 parts by weight of A-60 (trade name, nonionic surfactant manufactured by KAO Co., Ltd.) as an additive, and 125 parts by weight of propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone as a solvent, to form a colored layer. The composition (BK2-1) was prepared.

Subsequently, it carried out similarly to Example 1 except having used the radiation sensitive composition for color filters (BK2-1) instead of the radiation sensitive composition for color filters (R1-1), and formed black stripe shape on the board | substrate. A pixel array in which pixel patterns are arranged is formed.

<Evaluation>

When the pixel array on the substrate was observed with an optical microscope, no developing residue was recognized on the substrate of the unexposed portion, and scum and defects were not recognized at the edge of the pixel pattern. In addition, it was confirmed that a thinner pixel pattern could be formed as compared with Example 4, and the sensitivity was improved.

Moreover, when the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), undercut was not recognized.

Claims (4)

In a copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) a compound containing at least one hydroxyl group in a molecule, and (a3) another unsaturated compound, 1,1- ( Bisacryloyloxymethyl) ethyl isocyanate, 1,1- (bisacryloyloxyethyl) ethyl isocyanate, 1,1- (bisacryloyloxypropyl) ethyl isocyanate, 1,1- (bismethacryloyl At least one isocyanate compound selected from the group consisting of oxymethyl) ethyl isocyanate, 1,1- (bismethacryloyloxyethyl) ethyl isocyanate and 1,1- (bismethacryloyloxypropyl) ethyl isocyanate Polymer obtained by The radiation sensitive composition for color filters containing (A) the polymer of Claim 1, (B) coloring agent, (C) polyfunctional monomer, and (D) optical radical generating agent (However, in Claim 1 The polymer (A) described as a structure derived from another unsaturated compound (a3) shall not have a structure represented by following General formula (2). <Formula 2>

R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. The compound containing at least one hydroxyl group in the molecule (a2) is at least one compound selected from the group consisting of acrylic acid hydroxyalkyl esters and methacrylic acid hydroxyalkyl esters, (a3) Other unsaturated compounds include aromatic vinyl compounds, indenes, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, vinyl cyanide compounds, unsaturated amides, unsaturated imides, carboxyl A polymer that is at least one compound selected from the group consisting of acid vinyl esters, unsaturated ethers, aliphatic conjugated dienes, and macromonomers having a mono (meth) acryloyl group at the ends of the polymer molecular chain. The compound according to claim 2, wherein the compound containing at least one hydroxyl group in the molecule (a2) is at least one compound selected from the group consisting of acrylic acid hydroxyalkyl esters and methacrylic acid hydroxyalkyl esters, (a3) Other unsaturated compounds include aromatic vinyl compounds, indenes, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, vinyl cyanide compounds, unsaturated amides, unsaturated imides, carboxyl At least one compound selected from the group consisting of acid vinyl esters, unsaturated ethers, aliphatic conjugated dienes, and macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, (C) The radiation-sensitive composition in which the multifunctional monomer is a monomer having two or more polymerizable unsaturated bonds.