JP5316596B2 - Radiation sensitive composition for color filter, color filter, and color liquid crystal display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel radiation-sensitive composition for a color filter, which is free of undissolved substances remained or a scum on a pattern edge during development, and gives a pixel and a black matrix without chipping in a pattern edge or undercut even when the luminous energy of exposure is low. <P>SOLUTION: A radiation-sensitive composition for a color filter comprises: (A) a polymer, which is obtained by allowing a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, (a2) an unsaturated compound having at least one hydroxyl group in one molecule and (a3) another unsaturated compound to react with a specified isocyanate compound and which has a structure expressed by formula (2); (B) a colorant; (C) a polyfunctional monomer; and (D) a photo-radical generator. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display panel. More specifically, the present invention relates to a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. RADIATION-SENSITIVE COMPOSITION USED FOR FORMATION OF COLORED LAYER (PIXEL AND / OR BLACK MATRIX) MANUFACTURING, COLOR FILTER HAVING COLORED LAYER FORMED FROM THE RADIATION-SENSITIVE COMPOSITION, AND COLOR WITH THE COLOR FILTER The present invention relates to a liquid crystal display panel.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing.
In recent years, in the technical field of color filters, the trend to shorten the tact time by lowering the exposure amount has become the mainstream. However, with conventional colored radiation-sensitive compositions, pattern edges are missing or underworked during development. Since cuts are likely to occur, it has been difficult to obtain pixels and black matrices having good pattern shapes while shortening the tact time.

JP-A-2-144502 JP-A-3-53201

  The problem of the present invention is that the radiation-sensitive composition for forming a colored layer exhibiting excellent developability, more specifically, no undissolved material remains during development or scum is generated at the pattern edge, A novel radiation sensitive composition for a color filter that gives a pixel and a black matrix that do not cause chipping or undercut of a pattern edge even at a low exposure, a polymer useful as a component of the composition, and a radiation sensitive composition for a color filter Another object of the present invention is to provide a color filter formed from a conductive composition and a liquid crystal display device comprising the color filter.

The present invention, first,
Copolymerization of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) unsaturated compound containing one or more hydroxyl groups in one molecule, and (a3) other unsaturated compound A polymer obtained by reacting the compound with at least one isocyanate compound selected from the following compound group (1) and having a structure represented by the following formula (2), or (a1) an unsaturated carboxylic acid And / or unsaturated carboxylic acid anhydrides, (a2) unsaturated compounds containing one or more hydroxyl groups in one molecule, and (a3) other unsaturated compounds including N-phenylmaleimide or N-cyclohexylmaleimide A polymer obtained by reacting at least one isocyanate compound selected from the following compound group (1) with the copolymer (hereinafter referred to as “(A) polymer”),
(B) a colorant,
It is achieved by a radiation sensitive composition for a color filter, which comprises (C) a polyfunctional monomer and (D) a photo radical generator.

[Compound Group (1)]
1,1- (bisacryloyloxymethyl) ethyl isocyanate, 1,1- (bisacryloyloxyethyl) ethyl isocyanate, 1,1- (bisacryloyloxypropyl) ethyl isocyanate, 1,1- (bismethacryloyloxymethyl) ethyl Isocyanates, 1,1- (bismethacryloyloxyethyl) ethyl isocyanate and 1,1- (bismethacryloyloxypropyl) ethyl isocyanate

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

The present invention secondly,
It is achieved by a color filter comprising a colored layer formed from the radiation sensitive composition for a color filter.

  The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

Third, the present invention
This is achieved by a color liquid crystal display panel comprising the color filter.

The radiation-sensitive composition for forming a colored layer of the present invention uses an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain, so that even when the pigment is contained at a high concentration, the unexposed area during development is No undissolved material remains on the substrate and the light-shielding layer, and no scum is generated at the edges of the pixel pattern and black matrix pattern. In addition, even with low exposure, good pixels with no pattern edges missing and undercut Patterns and black matrix patterns can be formed.
Furthermore, the pixels and black matrix formed using the radiation-sensitive composition for forming a colored layer of the present invention have high surface smoothness and excellent adhesion to the substrate.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display panels in the electronic industry.

Hereinafter, the present invention will be described in detail.
(A) Polymer The (A) polymer in the present invention comprises (a1) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) one or more hydroxyl-containing unsaturated compounds, and (a3) other A copolymer with an unsaturated compound (hereinafter referred to as “alkali-soluble resin [α]”) and an isocyanate compound represented by the following formula (1) (hereinafter referred to as “unsaturated isocyanate compound (1)”). ).
Among the components constituting the alkali-soluble resin [α], (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter these are collectively referred to as “(a1) unsaturated carboxylic acid compound”. ), For example,
Examples of carboxyl group-containing unsaturated monomers include:
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 the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.

Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
In the alkali-soluble resin [α], the (a1) unsaturated carboxylic acid compound can be used alone or in admixture of two or more.
In the alkali-soluble resin [α], the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30%. % By weight. In this case, when the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is less than 5% by weight, the solubility of the polymer obtained by the reaction with the unsaturated isocyanate compound (1) in the alkaline developer On the other hand, if it exceeds 50% by weight, the solubility of the polymer in an alkaline developer may become too high.

Examples of the (a2) one or more hydroxyl-containing unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate 1,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl acrylate, acrylic Hydroxyalkyl esters of acrylic acid such as 3,4-dihydroxybutyl acid, 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl acrylate;
1,2-dihydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, 1,3-dihydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 3- [3- (2,3-dihydroxypropoxy methacrylate) ) -2-hydroxypropoxy] methacrylic acid hydroxyalkyl esters such as 2-hydroxypropyl.
Among these (a2) one or more hydroxyl group-containing unsaturated compounds, 2-hydroxyethyl (meth) acrylate, 1,2-dihydroxyethyl acrylate, from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds, Preference is given to 2,3-dihydroxypropyl acrylate, 1,2-dihydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate and the like.

In the alkali-soluble resin [α], (a2) one or more hydroxyl-containing unsaturated compounds can be used alone or in admixture of two or more.
In the alkali-soluble resin [α], (a2) the content of repeating units derived from one or more hydroxyl-containing unsaturated compounds is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, and particularly preferably 5 to 30% by weight. In this case, when the content of the repeating unit derived from the hydroxyl group-containing unsaturated compound (a2) is less than 1% by weight, the introduction rate of the unsaturated isocyanate compound (1) into the polymer tends to decrease and the sensitivity tends to decrease. On the other hand, if it exceeds 50% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (1) tends to decrease.

Moreover, as (a3) other unsaturated compounds, for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, 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-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, Soboruniru (meth) acrylate, dicyclopentadienyl (meth) acrylate, unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, 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, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

Among these (a3) other unsaturated compounds, styrene, methyl (meth) acrylate, and n-propyl (meth) acrylate are obtained from the viewpoint of copolymerization reactivity and solubility of the obtained (A) polymer in an aqueous alkali solution. I-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide and the like are preferable.
In the alkali-soluble resin [α], (a3) other unsaturated compounds can be used alone or in admixture of two or more.
In the alkali-soluble resin [α], the content of the repeating unit derived from (a3) another unsaturated compound is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, particularly preferably 30 to 50% by weight. %. In this case, when the content of the repeating unit derived from (a3) another unsaturated compound is less than 10% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (1) tends to decrease. On the other hand, if it exceeds 70% by weight, the solubility of the polymer in an alkaline developer tends to decrease.

Alkali-soluble resin [α] is, for example, (a1) unsaturated carboxylic acid compound, (a2) hydroxyl group-containing unsaturated compound and (a3) other unsaturated compound in the presence of a radical polymerization initiator in a suitable solvent. It can manufacture by polymerizing under.
As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, 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, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;

Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, 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, dipropylene glycol methyl ethyl 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, 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, propylene glycol mono-n-butyl ether propionate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, n-propyl methoxyacetate Pill, n-butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, n-propyl ethoxy acetate, n-butyl ethoxy acetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propoxyacetate n-propyl, n- Other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetate, n-butyloxybutoxyacetate and the like can be mentioned.
Of these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate, and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

In addition, the radical polymerization initiator is not particularly limited. 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-methylpropionate), Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, etc. And organic peroxides such as hydrogen peroxide.
Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

The polystyrene-converted 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 usually 3,000 to 300,000. 000, preferably 5,000 to 100,000.
The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin [α] in the present invention is usually from 3,000 to 3,000. 60,000, preferably 5,000 to 25,000.
In this case, if the Mw is less than 3,000, there is a risk that the alkali developability, the remaining film ratio, etc. of the resulting film may be reduced, and the pattern shape, heat resistance, etc. may be impaired. If it exceeds 1, the resolution may be reduced, or the pattern shape may be impaired.

The (B) alkali-soluble resin in the present invention is obtained by reacting the alkali-soluble resin [α] with the unsaturated isocyanate compound (1).
The alkali-soluble resin [α] thus obtained may be used for the production of the polymer (A) as it is in the polymerization solution, or once separated from the solution and used for the production of the polymer (A). May be.
The unsaturated isocyanate compound (1) is a compound represented by the following formula (1).

(Wherein R ₁ , R ₂ and R ₃ represent a hydrogen atom or a group having a structure represented by the following formula (I) or (II), and R ₁ , R ₂ and R ₃ are simultaneously hydrogen atoms. A, b, c and d are each independently an integer of 0 to 12.)

Examples of the unsaturated isocyanate compound (1) include 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 1,1- (bisacryloyloxyethyl) ethyl isocyanate, and 1,1- (bisacryloyloxypropyl). ) Acrylic derivatives such as ethyl isocyanate;
Methacryl derivatives such as 1,1- (bismethacryloyloxymethyl) ethyl isocyanate, 1,1- (bismethacryloyloxyethyl) ethyl isocyanate, 1,1- (bismethacryloyloxypropyl) ethyl isocyanate;
Can be mentioned.
Of these unsaturated isocyanate compounds (1), 1,1- (bisacryloyloxymethyl) ethyl isocyanate and 1,1- (bismethacryloyloxymethyl) are preferred in terms of reactivity with the alkali-soluble resin [α]. Ethyl isocyanate and the like are preferable.
As a commercial item of the said 1, 1- (bis acryloyl oxymethyl) ethyl isocyanate, Karenz BEI (made by Showa Denko KK) can be mentioned by a brand name.

In the reaction between the alkali-soluble resin [α] and the unsaturated isocyanate compound (1), the unsaturated isocyanate compound (1) can be used alone or in admixture of two or more.
In the present invention, the reaction between the alkali-soluble resin [α] and the unsaturated isocyanate compound (1) is carried out, for example, by a catalyst such as di-n-butyltin (IV) dilaurate or a polymerization inhibitor such as p-methoxyphenol. It can carry out by dripping the unsaturated isocyanate compound (1) to the alkali-soluble resin [α] solution containing, while stirring at room temperature or under heating.
(A) The amount of unsaturated isocyanate compound (1) used in producing the polymer is based on the amount of (a2) hydroxyl group-containing unsaturated compound used when synthesizing the alkali-soluble resin [α]. Preferably it is 0.1 to 90 weight%, More preferably, it is 10 to 80 weight%, Most preferably, it is 25 to 75 weight%. In this case, if the amount of the unsaturated isocyanate compound (1) used is less than 0.1% by weight, the effect of improving the sensitivity and the elastic properties is small, whereas if it exceeds 90% by weight, the unreacted unsaturated isocyanate compound (1) remains, and the storage stability of the resulting polymer solution and radiation-sensitive resin composition tends to decrease.

(A) The polymer has a carboxyl group and / or a carboxylic anhydride group and a polymerizable unsaturated bond, has an appropriate solubility in an alkali developer, and is used in combination with a special curing agent. The radiation-sensitive resin composition containing (B) an alkali-soluble resin may remain undissolved during development or cause scum at the pattern edge. This provides a pixel and a black matrix that do not cause pattern edge chipping and undercut even at low exposure.
(A) It is preferable that the polymer has a structure represented by the following formula (2).

(Here, R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
When the (A) polymer having the structure represented by the above formula (2) is used to synthesize the alkali-soluble resin [α], (a3) N-phenylmaleimide, N -It can be obtained by using cyclohexylmaleimide or the like.

(B) Colorant The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural colorant.
Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Pigments are used, and organic pigments and carbon black are particularly preferably used.
Examples of the organic pigment include a color index (CI; The Society of Dyers).
and Colorists (published by and Colorists)), specifically, compounds having a color index (CI) number as shown below.

  CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment ...... DOO 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;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73;
CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

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

CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, C.I. Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60;
CI Pigment Green 7, CI Pigment Green 36;
CI Pigment Brown 23, CI Pigment Brown 25;
CI Pigment Black 1, CI Pigment Black 7.
These organic pigments can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

  Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  In the present invention, the organic pigment and the inorganic pigment can be used alone or in admixture of two or more, and the organic pigment and the inorganic pigment can be used in combination. Preferably, one or more organic pigments are used, and two or more organic pigments and / or carbon black are preferably used in forming the black matrix.

  In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in JP-A-8-259876, and various commercially available pigment-dispersing polymers or oligomers.

Moreover, in this invention, a coloring agent can be used with a dispersing agent depending on necessity. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl. Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). Megafuck (Dainippon Ink and Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Dispersbyk (Bicchemy Japan), Solsparse (Seneca Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.

(C) Polyfunctional monomer The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
As the multifunctional 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 the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,

A compound represented by the following formula (3):

Compound represented by the following formula (4)

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that ground stains, film residues and the like are hardly generated on the top.
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 is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed substrate or the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include (B) compounds similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for the alkali-soluble resin, and N- (meth). In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting colored layer may be insufficient.
The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. In this case, if the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to decrease. There is a tendency that soiling, film residue, etc. are likely to occur on the substrate or the light shielding layer.

(D) Photoradical generator The photopolymerization initiator in the present invention is obtained by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray (hereinafter referred to as “exposure”). A compound capable of generating an active species capable of initiating polymerization of a functional monomer and optionally a monofunctional monomer.
Examples of such photopolymerization initiators include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, and triazine compounds. Etc.
In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, acetophenone compounds, biimidazole compounds, triazine compounds and At least one selected from the group of O-acyloxime compounds is preferred.

Examples of the biimidazole compound include:
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole is preferred, especially 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 substances and precipitates, has high sensitivity, sufficiently advances the curing reaction by exposure with a small amount of energy, and has a contrast. It is high and does not cause a curing reaction in the unexposed area. Therefore, the coated film after exposure is clearly divided into a cured part that is insoluble in the developer and an uncured part that has high solubility in the developer. Accordingly, it is possible to form a high-definition pattern array in which pixel patterns and black matrix patterns without undercuts are arranged according to a predetermined arrangement.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as the photoradical generator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As such a hydrogen donor, a mercaptan compound defined below, an amine compound defined below, and the like are preferable.
The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1-3, more preferably 1-2 mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “mercaptan”). It is referred to as “system hydrogen donor”).
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like at a place 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-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In the amine-based hydrogen donor, one or more of the 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 group may be substituted at a position other than the amino group. Alternatively, it may be substituted with an unsubstituted phenoxycarbonyl group, nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples include ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable. In addition, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone can act as a photoradical initiator alone even in the absence of a biimidazole compound. .

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of a preferred combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like are further preferable combinations. Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothia A Lumpur / 4,4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.
Examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl Examples include phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-1-one. Kill.

Examples of the benzophenone compounds include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone.
Examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone, and the like.
Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 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-ethoxy) Tyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, represented by the following formula (5) Compounds,

Compound represented by the following formula (6)

Examples thereof include compounds having a halomethyl group.
Examples of the O-acyloxime compound include compounds represented by the following formulas (7) and (8).

[In the above formulas (7) and (8), R ₁ is a group selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a phenyl group. R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms). And a group selected from an alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). R ₄ is a group selected from hydrogen, an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, and a sulfur-containing heterocyclic group having 4 to 20 carbon atoms. R ₅ is a group selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, and an alkoxyl group having 1 to 12 carbon atoms. n is an integer of 1 to 5, m is an integer of 0 to 5, n + m ≦ 5, and l is an integer of 0 to 6. ]

In formula (8) or (9), examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms of R ₁ and the phenyl group include a methyl group, an ethyl group, an 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- An undecyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned.

Moreover, as a C1-C20 linear, branched or cyclic alkyl group and phenyl group of R ₂ and R ₃ , 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 -A dodecyl group, a cyclopentyl group, a cyclohexyl group etc. can be mentioned.

Substituents for the phenyl group of R ₂ and R ₃ are hydrogen, and linear, branched, and cyclic alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and i-propyl. Group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of the linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group. be able to. Examples of the halogen atom include a fluorine atom and a chlorine atom.
Examples of the alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group) include, for example, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a ter-cycloalkyl group, a terpene skeleton-containing group, and an adamantyl skeleton Group.

As R ₄ , hydrogen, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and a sulfur-containing heterocyclic group having 4 to 20 carbon atoms include, for example, a thiolanyl group and an azepinyl group. , Dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, isoxazolyl group, isoxazolyl group, thiazolyl Group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindolyl group, benzofuranyl group, benzo Thiophenyl group, indoli Nyl, chromenyl, quinolinyl, isoquinolinyl, purinyl, quinazolinyl, cinnolinyl, phthalazinyl, pteridinyl, carbazolyl, acridinyl, phenanthridinyl, thioxanthenyl, phenazinyl, phenothiazinyl, phenoxy Examples include a sathiinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. Of these, a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like are particularly preferable.

As R ₅ , hydrogen, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms includes, 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, cyclopentyl Group, cyclohexyl group and the like.
Examples of the linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy, and n-pentyl. An oxy group etc. can be mentioned.
Of these, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, and an ethoxy group are particularly preferable.
n is preferably 1. m is preferably any one of 0, 1, 2 and particularly preferably 1, and l is preferably either 0, 1, or 2 and particularly preferably 1.

Specific examples of such O-acyloxime compounds include
1- [9-Ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-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-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)
Etc.

The said photoradical generator can be used individually or in mixture of 2 or more types.
The total use amount of the photoradical generator in the present invention is usually 0.01 to 100 parts by weight with respect to the total of 100 parts by weight of the (C) polyfunctional monomer and the monofunctional monomer optionally used. 200 parts by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the total use amount of the photo radical generator is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a pattern array in which pixel patterns or black matrix patterns are arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 200 parts by weight, the formed colored layer tends to fall off from the substrate during development, and background stains, film residue, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer. .
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinking / sensitizer can be used in combination with the photoradical generator as necessary.

-Additives-
The radiation sensitive composition for a color filter of the present invention contains the components (A) to (D) as essential components, but may contain other additives as necessary.
Examples of the additive include an organic acid or an organic amino compound (provided to improve the solubility characteristics of the radiation-sensitive composition in an alkaline developer and to further suppress the remaining undissolved product after development) The hydrogen donor is excluded).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the phenyl group via a carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, prevention of soiling and film residue on the substrate or the light-shielding layer in the unexposed area, and the like. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when the usage-amount of organic acid exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
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-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as ethylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, 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, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine 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 (4-cyclo Di (cyclo) alkanolamines such as hexanol) 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-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as 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-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, 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, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in the solvent described later, prevention of soiling and film residue on the unexposed portion of the substrate or the light shielding layer, and the like. And amino (cyclo) alkanediols are preferred, in particular 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention contains the components (A) to (D) as essential components, and contains the additive components as necessary. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

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

(Poly) alkylene glycol monoalkyl ether acetates 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, propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 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-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoints of solubility, pigment dispersibility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-acetate -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl Rubin acid and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.
The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition. An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

Color filter The color filter of the present invention comprises a colored layer formed from the radiation-sensitive composition for forming a colored layer of the present invention.
The method for forming the color filter of the present invention will be described below.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
The black matrix can be formed in the same manner as in the pixel formation using the radiation-sensitive composition for forming a colored layer of the present invention.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, 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, gas phase reaction method, vacuum deposition, etc., if desired.
When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred.
Exposure of radiation is preferably 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The color filter of the present invention thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

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

The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components. Specific examples of particularly preferred compositions are as follows. (D)
(A) (B) A radiation-sensitive composition for forming a colored layer containing an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain.
(B) (C) The radiation sensitive material for forming a colored layer according to (a), wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Sex composition.
(C) (D) The photo radical generator is 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-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,
2,2′-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-mercaptobenzoxazole, 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)
(B) The radiation-sensitive composition for forming a colored layer, comprising at least one selected from the group.
(D) (A) The radiation-sensitive composition for forming a colored layer according to (a), (b) or (c), wherein the colorant contains an organic pigment and / or carbon black.

Further, the preferred color filter of the present invention is
(E) A pixel and / or a black matrix formed from the radiation-sensitive composition for forming a colored layer according to (a), (b), (c) or (d).

The preferred color liquid crystal display panel of the present invention is
(F) comprising the color filter of (e),
A more preferred color liquid crystal display panel of the present invention is
(G) A pixel and / or a black matrix formed from the radiation-sensitive composition for forming a colored layer of (A), (B), (C) or (D) above is provided on a thin film transistor substrate array. .

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Here, parts and% are based on weight.
Mw and Mn of the resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (manufactured by Showa Denko KK).
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.
Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 18.8 N-phenylmaleimide. 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-methylstyrene dimer which is a chain transfer agent as a molecular weight control agent After charging 5 parts by weight and substituting with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring and polymerized for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour, whereby a resin solution (solid content concentration = 33.0% by weight) was obtained. The 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 of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name Karenz BEI, manufactured by Showa Denko KK) and 0.1 part of 4-methoxyphenol were added to the alkali-soluble resin (α-1) solution. Then, the mixture was reacted by stirring at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. Progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the alkali-soluble resin (α-1) was confirmed by IR (infrared absorption) spectrum. It was confirmed that the peak near 2270 cm ⁻¹ derived from the isocyanate group of 1,1- (bisacryloyloxymethyl) ethyl isocyanate decreased with the progress of the reaction. A polymer solution having a solid content concentration of 35.0% was obtained. This polymer is referred to as “(A) Polymer-1”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 13 parts by weight of methacrylic acid, 77 parts by weight of benzyl methacrylate, -10 parts of hydroxyethyl methacrylate and 5 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent were charged, and after nitrogen substitution, the reaction solution was heated to 80 ° C while gently stirring, The polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour, whereby a resin solution (solid content concentration = 33.0% by weight) was obtained. The obtained resin was Mw = 17,000 and (Mw / Mn) = 2.5. This resin is referred to as “alkali-soluble resin (α-2)”.
Subsequently, 10 parts of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name Karenz BEI, manufactured by Showa Denko KK) and 0.1 part of 4-methoxyphenol were added to the alkali-soluble resin (α-2) solution. Then, the mixture was reacted by stirring at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. Progress of the reaction between the isocyanate group derived from 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the hydroxyl group of the alkali-soluble resin (α-2) was confirmed by IR (infrared absorption) spectrum. It was confirmed that the peak near 2270 cm ⁻¹ derived from the isocyanate group of 1,1- (bisacryloyloxymethyl) ethyl isocyanate decreased with the progress of the reaction. A polymer solution having a solid content concentration of 35.0% was obtained. This polymer is referred to as “(A) Polymer-2”.

Example 1
(B) CI Pigment Red 254 / CI Pigment Red 177 = 80/20 (weight ratio) mixture 15 parts by weight as a colorant, Disperbyk-2001 4 parts by weight (in terms of solid content) as a dispersant, methacrylic acid / N-phenyl 6 parts by weight of maleimide / styrene / benzyl methacrylate copolymer (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 The pre-dispersion liquid (R1) was prepared by processing with a bead mill.
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 a polymer (A), and (C) difunctional as a polyfunctional monomer. 7.5 parts by weight of pentaerythritol hexaacrylate, (D) 0.5 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator and 3- 150 parts by weight of ethyl ethoxypropionate and 25 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a radiation sensitive resin composition (R1-1) for color filters.

Comparative Example 1
<Preparation of liquid composition and formation of colored layer>
Except having used alkali-soluble resin ((alpha) -1) instead of the said (A) polymer-1, it implemented similarly to Example 1 and prepared the radiation sensitive composition (r1-1).
Subsequently, it implemented similarly to Example 1 except having replaced with the radiation sensitive composition composition (R1-1) for color filters, and having used red sensitive composition (r1-1) on a board | substrate. A pixel array in which the stripe pixel patterns were arranged was formed.
<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, but chipping of the edge of the pixel pattern was observed.
Moreover, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed.

Example 2
<Preparation of liquid composition and formation of colored layer>
(B) CI Pigment Green 36 / CI Pigment Yellow 138 / CI Pigment Yellow 150 = 50/40/10 (weight ratio) 15 parts by weight of the mixture as a colorant, and 4 parts by weight of Disperbyk-2001 as a dispersant (in terms of solid content) , Methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6 000, Mn = 3,000) and 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent 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 (A) polymer, (C) dipentaerythritol as polyfunctional monomer 8 parts by weight of hexaacrylate, (D) 0.5 part by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and 0.1% of malonic acid as an additive The radiation sensitive composition for color filters (G1-1) was prepared by mixing 125 parts by weight of 3-methoxybutyl acetate and 50 parts by weight of propylene glycol methyl ether acetate as a solvent.
Subsequently, it implemented similarly to Example 1 except having used the radiation sensitive composition for color filters (G1-1) instead of the radiation sensitive composition for color filters (R1-1), and on a board | substrate. A pixel array in which green stripe pixel patterns were arranged was formed.
<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

Example 3
<Preparation of liquid composition and formation of colored layer>
(B) 15 parts by weight of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, 4 parts by weight (in terms of solid content) of Disperbyk-2001 as a dispersant, methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) and 5 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated in the same manner as in Example 1 to prepare a preliminary dispersion (B1).
Next, 100 parts by weight of the preliminary dispersion (B1), 6 parts by weight of (A) polymer-1 synthesized in Synthesis Example 1 as a polymer (A), and (C) dipenta as a polyfunctional monomer 9 parts by weight of erythritol hexaacrylate, (D) 0.5 parts by weight of 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propanone-1 as a photopolymerization initiator, and A-60 (commercial product) Name, Kao Co., Ltd. Nonionic Surfactant) 0.5 part and 150 parts by weight of ethyl 3-ethoxypropionate and 25 parts by weight of propylene glycol methyl ether acetate as a solvent are mixed to produce a radiation sensitive composition for color filters. A product (B1-1) was prepared.
Subsequently, it implemented similarly to Example 1 except having replaced with the radiation sensitive composition for color filters (R1-1), and having used the radiation sensitive composition for color filters (B1-1), on a board | substrate. A pixel array in which blue stripe pixel patterns were arranged was formed.
<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

Example 4
<Preparation of liquid composition and formation of colored layer>
(B) 20 parts by weight of carbon black (manufactured by Mikuni Dye Co., Ltd.) as a colorant, 2 parts by weight of Disperbyk-2001 (in terms of solid content) as a dispersant, methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenyl 4 parts by weight of maleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000), and 3- A preliminary dispersion (BK1) was prepared by treating 74 parts by weight of methoxybutyl acetate in the same manner as in Example 1.
Next, 100 parts by weight of the preliminary dispersion (BK1), (A) as a polymer, 4.5 parts by weight of (A) polymer-2 synthesized in Synthesis Example 2 above, and (C) as a polyfunctional monomer 5.5 parts by weight of dipentaerythritol hexaacrylate, (D) 1 part by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and A- 60 parts (trade name, nonionic surfactant manufactured by Kao Corporation) and 125 parts by weight of propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone as a solvent were mixed to form a colored layer forming composition (BK1- 1) was prepared.
Subsequently, it implemented like Example 1 except having replaced with the radiation sensitive composition for color filters (R1-1), and having used the radiation sensitive composition for color filters (BK1-1), on a board | substrate. A pixel array in which black stripe pixel patterns were arranged was formed.
<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

Example 5
<Preparation of liquid composition and formation of colored layer>
(B) 20 parts by weight of carbon black (manufactured by Mikuni Dye Co., Ltd.) as a colorant, 2 parts by weight of Disperbyk-2001 (in terms of solid content) as a dispersant, methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenyl 4 parts by weight of maleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000), and 3- A preliminary dispersion (BK2) was prepared by treating 74 parts by weight of methoxybutyl acetate in the same manner as in Example 1.
Next, 100 parts by weight of the preliminary dispersion (BK2), (A) as a polymer, 4.5 parts by weight of (A) polymer-2 synthesized in Synthesis Example 2 above, and (C) as a polyfunctional monomer 5.5 parts by weight of dipentaerythritol hexaacrylate, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate 1 part by weight, 0.5 parts A-60 (trade name, nonionic surfactant manufactured by Kao Corporation) as an additive and as a solvent A colored layer forming composition (BK2-1) was prepared by mixing 125 parts by weight of propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone.
Subsequently, it implemented like Example 1 except having replaced with the radiation sensitive composition for color filters (R1-1), and having used the radiation sensitive composition for color filters (BK2-1), and on a board | substrate. A pixel array in which black stripe pixel patterns were arranged was formed.
<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, it was confirmed that a thinner pixel pattern can be formed as compared with Example 4 and the sensitivity is improved.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

Claims (4)

(A) (a1) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) an unsaturated compound containing one or more hydroxyl groups in one molecule, and (a3) another unsaturated compound A polymer obtained by reacting at least one isocyanate compound selected from the following compound group (1) with a copolymer having a structure represented by the following formula (2):
(B) a colorant,
A radiation-sensitive composition for a color filter, comprising (C) a polyfunctional monomer, and (D) a photoradical generator.
[Compound Group (1)]
1,1- (bisacryloyloxymethyl) ethyl isocyanate, 1,1- (bisacryloyloxyethyl) ethyl isocyanate, 1,1- (bisacryloyloxypropyl) ethyl isocyanate, 1,1- (bismethacryloyloxymethyl) ethyl Isocyanates, 1,1- (bismethacryloyloxyethyl) ethyl isocyanate and 1,1- (bismethacryloyloxypropyl) ethyl isocyanate

(Here, R ³ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.) (A) (a1) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) an unsaturated compound containing one or more hydroxyl groups in one molecule, and (a3) N-phenylmaleimide or N -A polymer obtained by reacting at least one isocyanate compound selected from the following compound group (1) with a copolymer with another unsaturated compound containing cyclohexylmaleimide,
(B) a colorant,
A radiation-sensitive composition for a color filter, comprising (C) a polyfunctional monomer, and (D) a photoradical generator.
[Compound Group (1)]
1,1- (bisacryloyloxymethyl) ethyl isocyanate, 1,1- (bisacryloyloxyethyl) ethyl isocyanate, 1,1- (bisacryloyloxypropyl) ethyl isocyanate, 1,1- (bismethacryloyloxymethyl) ethyl Isocyanates, 1,1- (bismethacryloyloxyethyl) ethyl isocyanate and 1,1- (bismethacryloyloxypropyl) ethyl isocyanate   A color filter comprising a colored layer formed from the radiation-sensitive composition for a color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 3.