KR20070079007A - Radiation sensitive composition, color filter and liquid crystal display device - Google Patents

Abstract

(A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl An optical radical comprising an oxime such as] -ethane-1-one oxime-O-acetate and at least one component selected from the group consisting of a biimidazole compound, a benzophenone compound, a thioxanthone compound and a ketocoumarin compound A radiation sensitive composition containing a generator and used for forming a colored layer. The composition provides pixels and black matrices in which no defects and undercuts of the pattern ends are generated under low exposure and harsh developing conditions, and no undissolved matter remains or scum does not occur at the pattern ends during development.

Description

Radiation-sensitive composition, color filter and liquid crystal display device {RADIOSENSITIVE COMPOSITIONS, COLOR FILTERS AND LIQUID CRYSTAL DISPLAY DEVICES}

[Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Document 2] Japanese Unexamined Patent Publication No. 3-53201

TECHNICAL FIELD This invention relates to a radiation sensitive composition, a color filter, and a liquid crystal display element. More specifically, the radiation sensitive composition used for formation of the colored layer useful for the color filter used for a transmissive or reflective color liquid crystal display device, a color image tube element, etc., the color filter which has the colored layer formed from this radiation sensitive composition, And a liquid crystal display device having the 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. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as "exposure") and developing it is known (see Japanese Patent Laid-Open No. Hei 2-144502 and Japanese Patent Laid-Open No. Hei 3-53201). have.

In recent years, in the field of color filter technology, the movement of shortening the tact time by reducing the exposure amount or increasing the substrate conveyance speed in the developing step has become the mainstream. However, since the development conditions become severe due to a decrease in the exposure dose or an increase in the substrate conveyance speed, in the conventional colored radiation-sensitive composition, defects and undercuts of the pattern ends are likely to occur at the time of development, and a good pattern is shortened while the tact time is shortened. It was difficult to obtain shaped pixels and black matrices.

The object of the present invention is firstly, a radiation sensitive composition exhibiting excellent developability, more specifically, no defects and undercuts at the end of the pattern do not occur even under low exposure amounts and harsh development conditions, and furthermore, SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive composition that provides a pixel and a black matrix that remain or do not generate scum at the end of the pattern.

Another object of the present invention is to provide a color filter having a colored layer formed of the radiation-sensitive composition of the present invention.

Another object of the present invention is to provide a liquid crystal display device having the color filter of the present invention.

Still 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 are, firstly,

(A) a colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) at least one component selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2); And an optical radical generator comprising at least one component selected from the group consisting of a biimidazole compound, a benzophenone compound, a thioxanthone compound and a ketocoumarin compound, and is used for forming a colored layer. It is achieved by a radiation sensitive composition.

In formula (1) and formula (2), each R ¹ independently of each other represents a straight chain, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ² independently represents a hydrogen atom, a straight chain having 1 to 12 carbon atoms, Represents a branched or cyclic alkyl group or a phenyl group, each R ³ independently of one another represents a hydrogen atom or a straight, branched or cyclic alkyl group of 1 to 12 carbon atoms, and each R ⁴ , each R ⁵ and each R ⁶ is independent of each other; To a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, provided that the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each of 1 to 6 carbon atoms. It may be substituted with a substituent selected from the group of a linear, branched or cyclic alkoxyl group, a phenyl group and a halogen atom, the phenyl group of R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, carbon number 1 to 6 looms It may be substituted with a substituent selected from the group of chain, branched or cyclic alkoxyl groups, phenyl groups and halogen atoms.

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 second,

It is achieved by a color filter having a colored layer formed of the radiation sensitive composition of the present invention.

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

It is achieved by the liquid crystal display element provided with the color filter of this invention.

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

Radiation-sensitive composition

-(A) colorant-

The colorant in the present invention is not particularly limited in color tone, is appropriately selected depending on the use of the color filter obtained, and may be any of pigments, dyes or natural dyes.

Since the color filter requires high color development and heat resistance, as the colorant in the present invention, a colorant having high color resistance and high heat resistance, particularly a colorant having high thermal decomposition resistance, is preferably used, and pigments are usually used, particularly preferably organic. Pigments, carbon blacks are used.

As the organic pigment, for example, a compound which is classified as Pigment in the color index (CI; issued by The Society of Dyers and Colourists), and specifically, the following color index (CI) number is given. I can hear that.

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.

In addition, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zincation, lead sulfate, yellow lead, zinc sulfur, iron group (red iron (III) oxide), cadmium, ultramarine blue, blue blue, chromium oxide, Cobalt rust, umber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

In the present invention, the organic pigment and the inorganic pigment may be used alone or in combination of two or more. For example, an organic pigment and an inorganic pigment can also be used 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 may be used by modifying the particle surface thereof with a polymer if necessary. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., the polymer for various pigment dispersions, or oligomer, etc. which are mentioned are mentioned.

In addition, in the present invention, the colorant may be used together with a dispersant if necessary.

As said dispersing agent, surfactant, such as a cationic type, an anionic type, a nonionic type, amphoteric, a silicone type, and a 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 alkylphenyl 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 polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and MegaPack (Dainitbon) Ink Kagaku Kogyo Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), Disperbyk (Bikkemi Japan Co., Ltd.) (Manufactured by < RTI ID = 0.0 >), < / RTI >

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

The amount of the surfactant to be 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.

-(B) alkali-soluble resin-

The alkali-soluble resin in the present invention is not particularly limited as long as the alkali-soluble resin has solubility in a developer, particularly preferably an alkali developer, used in its development treatment step when producing a color filter while acting as a binder for the (A) colorant. Do not. Of these, alkali-soluble resins having a carboxyl group are preferred, and in particular, ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "carboxyl group-containing unsaturated monomers") and other copolymerizable ethylenically unsaturated monomers (hereinafter, "copolymerizable" Preferred is a copolymer with " unsaturated monomer ") (hereinafter referred to as " carboxyl group-containing copolymer ").

As a carboxyl group-containing unsaturated monomer, for example

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid,

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid,

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof,

Mono [(meth) acryloyloxyalkyl] of divalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester,

The mono (meth) acrylate etc. of the polymer which has a carboxyl group and a hydroxyl group in both terminal, such as (omega)-carboxy polycaprolactone mono (meth) acrylate, are mentioned.

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

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

As the copolymerizable unsaturated monomer, 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,

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

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) arcrelate , sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylic Latex, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclo Hexyl (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, Toxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth Unsaturated carboxylic esters such as acrylate,

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, vinylidene cyanide,

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

Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate,

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether,

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

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

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

As the carboxyl group-containing copolymer in the present invention, (b1) (meth) acrylic acid is an essential component, and optionally succinic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono ( A carboxyl group-containing unsaturated monomer component which further contains 1 or more types of compounds chosen from the group of a meth) acrylate, (b2) Styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth ) At least one copolymerizable unsaturated monomer selected from the group consisting of acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer The copolymer of (hereinafter referred to as "carboxyl group-containing copolymer (B1)") is preferable.

As a specific example of a carboxyl group-containing copolymer (B1),

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

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

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

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

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

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

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

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydride Oxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

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

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

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

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

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

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

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

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

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

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

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

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

(Meth) acrylic acid / omega-carboxypolycaprolactone mono (meth) acrylate / styrene / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, etc. are mentioned.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the copolymerization ratio is less than 5% by weight, the solubility in the alkali developer of the obtained radiation-sensitive composition tends to be lowered, while if it exceeds 50% by weight, the solubility in the alkaline developer is excessive, and when developing with an alkaline developer. There exists a tendency for a colored layer to fall out from a board | substrate, or to become easy to cause the film | membrane unevenness of the colored layer surface.

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 in the present invention is preferably 3,000 to 300,000, more preferably Is 5,000 to 100,000.

In addition, the polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is preferably 3,000 to 60,000, and more. Preferably 5,000 to 25,000.

In the present invention, by using an alkali-soluble resin having such specific Mw and Mn, a radiation-sensitive composition excellent in developability is obtained, whereby a pixel and a black matrix having sharp pattern ends can be formed, and at the same time Residues, background contamination, film residues, etc., on the substrate and the light shielding layer of the unexposed portion become less likely to occur.

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

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

The usage-amount of alkali-soluble resin in this invention becomes like this. Preferably it is 10-1,000 weight part, More preferably, it is 20-500 weight part with respect to 100 weight part of (A) coloring agents. If the amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may be lowered, or background contamination or film residue may occur on the substrate or the light shielding layer of the unexposed part. Since the colorant concentration decreases relatively, there is a possibility that it is difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-

Multifunctional monomers in the present invention include monomers having two or more polymerizable unsaturated bonds in a molecule.

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, 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, and

Tris [2- (meth) acryloyloxyethyl] phosphate etc. are mentioned.

Of these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tri Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate,

Preferred are compounds represented by the following formula (3), compounds represented by the following formula (4), and the like.

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and further, on the substrate and the light shielding layer of the unexposed part. It is preferable in that it does not generate | occur | produce background contamination, film | membrane residue, etc. well.

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

The amount of the polyfunctional monomer used 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 (B) alkali-soluble resin. If the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to decrease, while if it exceeds 500 parts by weight, for example, alkali developability is lowered, or on the substrate of the unexposed part, Background contamination, film residues, etc. tend to occur on the light shielding layer.

Moreover, in this invention, you may use together the monofunctional monomer which has one polymerizable unsaturated bond with a polyfunctional monomer.

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

These monofunctional monomers can be used individually or in mixture of 2 or more types. The use ratio of the monofunctional monomer is preferably 90% by weight or less, and more preferably 50% by weight or less, based on the total of the polyfunctional monomer and the 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 (B) alkali-soluble resin. If the total amount of use 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 the light shielding layer of the unexposed part is reduced. Background contamination, film residues, etc. tend to occur.

-(D) photo radical generator-

The optical radical generator in the present invention is one or more components selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2) (hereinafter referred to as "photo radical generator (D1)") and And at least one component selected from the group consisting of a biimidazole compound, a benzophenone compound, a thioxanthone compound and a ketocoumarin compound (hereinafter referred to as "photo radical generator (D2)"). Such an optical radical generator is, for example, polymerization of (C) a polyfunctional monomer and a monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet light, far ultraviolet ray, charged particle beam, or X-ray. Generates radicals that can initiate.

In the general formulas (1) and (2), examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R ¹ , R ² and R ³ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-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, n-dodecyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Moreover, as a C1-C6 linear, branched, or cyclic alkyl group of R <^4> , R <^5> and R <^6> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

Linear, branched or cyclic having 1 to 6 carbon atoms in the substituent for each alkyl group of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and the substituent for each phenyl group of R ¹ and R ² As an alkoxyl group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, etc. are mentioned, for example, As a halogen atom, For example, a fluorine atom And a chlorine atom.

In addition, as a C1-C6 linear, branched, or cyclic alkyl group among the substituents for each phenyl group of R <^1> and R <^2> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n- A butyl group, t-butyl group, etc. are mentioned.

One or more of these substituents may be present in each alkyl group and each phenyl group.

In formulas (1) and (2), R ¹ is preferably a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, or a phenyl group, and as R ² , a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. are preferable, and as R <^3> , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i -Propyl group, n-butyl group, etc. are preferable, and as R <^4> , R <^5> and R <^6> , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. are preferable.

As a specific example of the preferable radical photogenerating agent (D1) in this invention, 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-nonan-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, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate and the like.

Among these optical radical generators (D1), in particular, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate Is preferred.

The said photo radical generating agent (D1) can be used individually or in mixture of 2 or more types.

Next, as a biimidazole compound in an optical radical generating agent (D2), the compound etc. which have 1 or more types of main skeleton represented by following formula (5a), (5b) or (5c) are mentioned, for example, biimidazole As a specific example of a compound

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,

2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole , 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-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'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole is preferred.

The non-imidazole compound is excellent in solubility in a solvent and does not generate foreign matters such as undissolved products and precipitates, and also has high sensitivity, while sufficiently advancing the curing reaction by exposure of a small amount of energy, and high contrast. Since no hardening reaction occurs at, the coated film after exposure is clearly divided into a hardened part which is insoluble in the developer and an uncured part having high solubility in the developer, whereby the pixel pattern and the black matrix pattern without undercut are predetermined. It is possible to form a precise pattern array arranged in accordance with the arrangement.

Hydrogen donor

Moreover, in this invention, when using a biimidazole compound, 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 to the radical which generate | occur | produced from the biimidazole type 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 ".

On the other hand, these hydrogen donors may have a mercapto group and an amino group simultaneously.

The hydrogen donor will be described in more detail below.

The mercaptan hydrogen donor may have one or more benzene rings or heterocycles, 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. It may be.

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 group, an aralkyl group or an aryl group, and further, one As long as the above free mercapto group remains, it may have a structural unit bonded via a divalent organic group such as two sulfur atom alkylene groups or a structural unit bonded by two sulfur atoms in the form of disulfide.

In addition, 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 portion 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, 2-mercaptobenzoxazole, and the like are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine hydrogen donor may have one or more benzene rings or heterocycles, and may also have both benzene rings and heterocycles, and in the case of having two or more of these rings, may form a condensed ring. You may not.

In addition, the amine hydrogen donor may be substituted with at least one amino group by an alkyl group or a substituted alkyl group, and 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 in a portion other than the amino group. It may be substituted.

Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Ethyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid i-amyl, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, etc. are mentioned.

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

In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof, but the combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors may be performed by using a colored layer formed from a substrate during development. It is preferable at the point which does not fall easily but also the intensity | strength and the sensitivity of a colored layer are high.

Specific examples of preferred combinations of mercaptan hydrogen donors and amine hydrogen donors include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4 '. -Bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) Benzophenone etc. are mentioned, A more preferable combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (di Ethylamino) benzophenone, a particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

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

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

Moreover, as said thioxanthone compound, For example, thioxanthone, 2-chloro thioxanthone, 2, 4- diethyl thioxanthone, 2-methyl thioxanthone, 2-i-propyl thioxanthone, etc. Can be mentioned.

Moreover, as said ketocoumarin compound, 3-ketocoumarin etc. are mentioned, for example.

In the present invention, as the optical radical generator (D2), 2,4-diethyl thioxanthone, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (4- Ethoxycarbonylphenyl) -1,2'-biimidazole, 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzothiazole, etc. are preferable.

The said photo radical generating agent (D2) can be used individually or in mixture of 2 or more types.

The optical radical generator in the present invention may further include components other than the optical radical generator (D1) and the optical radical generator (D2) (hereinafter referred to as "other optical radical generators").

As another optical radical generating agent, other O-acyl oxime compound, a benzoin compound, an acetophenone compound, the (alpha)-diketone compound, a polynuclear quinone compound, a phosphine compound, a triazine compound, etc. are mentioned, for example.

As said other O-acyl oxime compound, the 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyl oxime), 1,2-butanedione-1-, for example [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2 -Octadione-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadione-1- [4- (phenylthio) phenyl] -2- [O- ( 4-methylbenzoyloxime)] etc. are mentioned.

Moreover, 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.

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

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

Moreover, as said phosphine compound, bis (2, 4, 6- trimethyl benzoyl) phenyl phosphine oxide, 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, etc. are mentioned, for example.

As the triazine compound, for example, 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-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxy And compounds having a halomethyl group, such as phenyl) -4,6-bis (trichloromethyl) -s-triazine, a compound represented by the following formula (6), and a compound represented by the following formula (7).

In the present invention, other photoradical generators may be used alone or in combination of two or more thereof.

In the present invention, the total amount of the radical generating agent used is preferably 0.01 to 200 parts by weight, more preferably 1 to 1, based on 100 parts by weight of the total amount of the (C) polyfunctional monomer and the monofunctional monomer used in some cases. 120 parts by weight, particularly preferably 1 to 100 parts by weight. When the total amount of use of the radical radical 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. When it exceeds, the formed colored layer will fall easily from a board | substrate at the time of image development, and a background contamination, a film | membrane residual, etc. will be easy to generate | occur | produce on the board | substrate or the light shielding layer of an unexposed part.

In addition, the use ratio of the photoradical generator (D2) is preferably 10 to 50% by weight, more preferably 10 to 30% by weight, based on the total of the photoradical generator (D1) and the photoradical generator (D2). %to be. If the use ratio of the optical radical generating agent (D2) is less than 10% by weight, it may be difficult to obtain a pixel pattern, while if it exceeds 50% by weight, the desired effect of the present invention may be impaired.

In addition, the use ratio of another optical radical generator is preferably 50 weight% or less, and more preferably 30 weight% or less with respect to the total of the optical radical generators. When the use ratio of another photo radical generating agent exceeds 50 weight%, the desired effect of this invention may be impaired.

In the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinker and a sensitizer may be used in combination with the optical radical generator.

-additive-

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

The additive includes an organic acid or an organic amino compound (except for the hydrogen donor), which further improves the solubility of the radiation-sensitive composition in the alkaline developer and further suppresses the residual of the undissolved product after development. Etc. can be mentioned.

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, diethylacetic acid, enanthic acid, caprylic acid,

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

Tricarboxylic acids, such as a tricarvalic acid, aconitic acid, and a camphoric acid, etc. are mentioned.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, carboxylic acid in which the carboxyl group is bonded to a phenyl group via a carbon chain, and the like.

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, and

Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamiledic acid, kumaric acid, umbelic acid and the like.

Among these organic acids, aliphatic dicarboxylic acid is preferable as the aliphatic carboxylic acid from the viewpoint of alkali solubility, solubility in a solvent to be described later, ground contamination on the substrate or light shielding layer of the unexposed part, and prevention of film residue. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable. Moreover, as a phenyl group containing carboxylic acid, aromatic dicarboxylic 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 amount of the organic acid used is preferably 15% by weight or less, and more preferably 10% by weight or less based on the whole radiation-sensitive composition. 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.

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

As 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-ethylcyclohexyl amine, 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, dicyclohexylamine,

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-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, 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 cycloalkanethanol, 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, 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) alkanolamines and amino (cyclo) alkanediols are mentioned as aliphatic amines in view of solubility in a solvent to be described later, background contamination on the substrate or the light shielding layer of the unexposed part, and the like. Preferred are, 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 said organic amino compound can be used individually or in mixture of 2 or more types.

The usage-amount of an organic amino compound becomes like this. Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less with respect to 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, a yellow pigment derivative,

Fillers such as glass and alumina,

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

Surfactants such as nonionic, cationic and anionic systems,

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter,

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

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

Agglomeration inhibitors such as sodium polyacrylate,

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

menstruum

The radiation sensitive composition of the present invention contains the above-mentioned (A) to (D) components as essential components and, if necessary, contains the additive component, but is preferably prepared as a liquid composition by blending a solvent.

The solvent may be appropriately selected and used as long as it does not react with these components while dispersing or dissolving the components (A) to (D) and the additive component constituting the radiation-sensitive composition.

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, tri (Poly) alkylene glycol monoalkyl such as propylene glycol monoethyl ether Termini,

(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, 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-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n -Butyl, i-butyl acetate, 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-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate,

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, in view of solubility, pigment dispersibility, coating property, etc. Diethylene glycol methylethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 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, etc. desirable.

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

In addition, 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 And high boiling point solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

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 a viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition becomes like this. Preferably it is 5-50 weight%, More preferably, It is preferable that the amount is 10 to 40% by weight.

Color filter

The color filter of this invention has the colored layer formed from the radiation sensitive composition of this invention.

Hereinafter, 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 part which forms a pixel as needed, and after apply | coating the liquid composition of the radiation sensitive composition which red pigment disperse | distributed on this board | substrate, for example, Baking is performed to evaporate the solvent to form a coating film.

Subsequently, after exposing this coating film through a photomask, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and then post-bakes, and forms the pixel array in which the red pixel pattern was arrange | positioned in the predetermined array. .

Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, coating, prebaking, exposure, developing and postbaking of each liquid composition are carried out in the same manner as above, and the green pixel array and By sequentially forming blue pixel arrays on the same substrate, a color filter in which pixel arrays of three primary colors of red, green and blue are arranged on a substrate is obtained. 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 case of the pixel formation by using the radiation-sensitive composition of the present invention.

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

If desired, 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.

When apply | coating the liquid composition of a radiation sensitive composition to a board | substrate, the appropriate coating methods, such as the spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet method, are employ | adopted, for example. can do. In particular, the spin coating method and the slit die coating method are preferable.

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

As radiation used when forming the pixel and / or black matrix, for example, visible light, ultraviolet light, deep 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.

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

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. On the other hand, after alkali development, it washes with water preferably.

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

Thus, the color filter of this invention obtained is very useful for a transmissive or semi-reflective color liquid crystal display element, a color image tube element, a color sensor, etc., for example.

Liquid crystal display device

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

Moreover, as one Embodiment of the liquid crystal display element of this invention, using the radiation sensitive composition of this invention, forming a pixel and / or a black matrix on a thin film transistor substrate array as mentioned above is especially excellent characteristic. The liquid crystal display element which has can be manufactured.

Although the radiation sensitive composition of this invention contains the said (A)-(D) component as an essential component, when a particularly preferable composition is concretely illustrated, it is as follows (a)-(c).

(A) The radiation sensitive composition in which (B) alkali-soluble resin contains a carboxyl group-containing copolymer (B1).

(B) The radiation-sensitive properties of (a), wherein the polyfunctional monomer (C) comprises at least one member selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Composition.

(C) The radical radical generator (D1) is 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate The radiation-sensitive composition of the (A) or (B) comprising a.

In addition, the preferred color filter of the present invention

(D) It has a pixel and / or a black matrix formed from the radiation sensitive composition of said (A), (B) or (C).

Moreover, the preferable liquid crystal display element of this invention is

(E) comprising the color filter of (d) above,

More preferred liquid crystal display device of the present invention

(F) The color filter of (d) is provided on the thin film transistor substrate array.

As mentioned above, the radiation sensitive composition of this invention is especially the group which consists of an optical radical generating agent (D1) with high sensitivity to radiation, a biimidazole compound, a benzophenone compound, a thioxanthone compound, and a ketocoumarin compound. By using an optical radical generator comprising at least one selected radical radical generator (D2), a low exposure amount, for example, a set exposure amount of 400 J / m 2, and a severe development condition, for example, a development temperature of 30 ° C. Even when the shower pressure is 110 KPa and the developer flow rate is 1.2 liter / min, there is no defect or undercut of the end of the pattern, and a good pixel pattern and a black matrix pattern in which undissolved matter remains at the time of development or scum does not occur at the end of the pattern are produced. Can be formed.

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

Therefore, the radiation sensitive composition of this invention can be used very favorably for manufacture of various color filters including the color filter for liquid crystal display elements in the electronic industry.

Example

Hereinafter, an Example is given and this invention is demonstrated further more concretely. The present invention is not limited to the following examples.

Where parts and% are based on weight.

<(B) Production of Alkali Soluble Resin>

Synthesis Example  One

In a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were added, followed by 15 parts of methacrylic acid and styrene 15. Part, 25 parts of N-phenylmaleimide, 35 parts of benzyl methacrylate, 10 parts of glycerol monomethacrylate, and 5 parts of α-methylstyrene dimer as a chain transfer agent were added thereto for nitrogen replacement, and then the mixture was gradually stirred to give 80 parts of the reaction solution. It heated up at ° C, maintained this temperature, and superposed | polymerized for 3 hours. Thereafter, the reaction solution was heated to 100 ° C, 0.5 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the resin solution (solid content concentration = 33.0%) was obtained by further polymerizing for 1 hour. .

Obtained resin was Mw = 10,000 and Mn = 5,900. This resin is referred to as "resin (B-1)".

Example  One

<Production of Liquid Composition>

(A) As a coloring agent, C.I. Pigment Blue 15: 6 and C.I. 78 parts 95/5 (weight ratio) mixture with pigment violet 23, (B) 60 parts resin (B-1) as alkali-soluble resin, (C) 90 parts dipentaerythritol hexaacrylate as a polyfunctional monomer, light 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name CGI-) as a radical generator (D1) 242, manufactured by Ciba Specialty Chemicals Co., Ltd., 10 parts, and 2,4-diethyl thioxanthone (trade name KAYACUREDETX-S, manufactured by Nippon Kayaku Co., Ltd.) as a photo radical generator (D2), and 15 parts of solvent As a mixture, 1,000 parts by weight of a 80/20 (weight ratio) mixture of cyclohexanone and propylene glycol monomethyl ether acetate was mixed to prepare a liquid composition (B1) of a radiation sensitive composition.

<Formation of Colored Layer>

The liquid composition (B1) was applied to a soda glass substrate having a SiO ₂ film formed thereon to prevent elution of sodium ions on its surface using a spin coater, and then prebaked for 100 seconds on an 80 ° C hot plate to obtain a film thickness of 2.5 μm. A coating film was formed.

Subsequently, after cooling the substrate to room temperature, ultraviolet rays containing respective wavelengths of 365 nm, 405 nm and 436 nm were exposed to the coating film through a photomask (slit width 90 mu m) using a high pressure mercury lamp. The exposure amount at this time was set to a low value at 400 J / m 2. Then, the board | substrate was shower-developed on the conditions of developing temperature of 30 degreeC, shower pressure of 110 KPa, and developing solution flow volume 1.2 liter / min using 0.04% potassium hydroxide aqueous solution. Subsequently, the substrate was washed with ultrapure water and air dried, followed by postbaking in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which blue striped pixel patterns were arranged on the substrate.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and scum and defects were not seen at the end of the pixel pattern.

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

Comparative example  One

<Production of Liquid Composition and Formation of Colored Layer>

As an optical radical generator, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime- which is an optical radical generator (D1) A radiation sensitive composition (b1) was produced in the same manner as in Example 1 except that only 10 parts of O-acetate were used.

Subsequently, except for using the liquid composition (b1) instead of the liquid composition (B1), a pixel array in which blue striped pixel patterns were arranged on a substrate was formed in the same manner as in Example 1.

<Evaluation>

When the pixel array on the board | substrate was observed with the optical microscope, although the image development residue was not seen on the board | substrate of an unexposed part, the defect of the edge part of a pixel pattern and peeling of the pattern itself were seen.

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

Example  2

<Production of Liquid Composition and Formation of Colored Layer>

(A) As a coloring agent, C.I. Pigment Blue 15: 6 and C.I. 80 parts of 95/5 (weight ratio) mixture of pigment violet 23, (B) 60 parts of resin (B-1) as alkali-soluble resin, (C) 90 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer, an optical radical 5 parts of 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate as a generator (D1), 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole as radical generator (D2) 2 parts, 4 parts of 4,4'-bis (diethylamino) benzophenone and 2 parts of 2-mercaptobenzothiazole and 80/20 (weight ratio) mixture of cyclohexanone and propylene glycol monomethyl ether acetate as solvent 1,000 By mixing the parts by weight to prepare a liquid composition (B2) of the radiation sensitive composition.

Subsequently, except for using the liquid composition (B2) instead of the liquid composition (B1), a pixel array in which blue striped pixel patterns were arranged on a substrate was formed in the same manner as in Example 1.

<Evaluation>

When the pixel array on the board | substrate was observed with the optical microscope, the development residue was not seen on the board | substrate of the unexposed part, and scum and defect were not seen at the edge part of a pixel pattern.

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

Comparative example  2

<Production of Liquid Composition and Formation of Colored Layer>

As an optical radical generator, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime- which is an optical radical generator (D1) A radiation sensitive composition (b2) was prepared in the same manner as in Example 2 except that only 5 parts of O-acetate were used.

Subsequently, except for using the liquid composition (b2) instead of the liquid composition (B2), in the same manner as in Example 2, a pixel array in which blue striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

When the pixel array on the board | substrate was observed with the optical microscope, although the image development residue was not seen on the board | substrate of an unexposed part, the defect of the edge part of a pixel pattern and peeling of the pattern itself were seen.

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

According to the present invention, a radiation-sensitive composition exhibiting excellent developability, more specifically, no defects and undercuts at the end of the pattern do not occur even under low exposure amount and harsh developing conditions, and undissolved matters remain during development It is possible to provide a radiation-sensitive composition that provides a pixel and a black matrix in which scum does not occur at an end portion.

In addition, according to the present invention, it is possible to provide a color filter having a colored layer formed of the radiation-sensitive composition of the present invention and a liquid crystal display device having the same.

Claims (4)

At least one component selected from the group consisting of (A) a colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) a compound represented by the following general formula (1) and a compound represented by the following general formula (2), An optical radical generator comprising at least one component selected from the group consisting of a biimidazole compound, a benzophenone compound, a thioxanthone compound, and a ketocoumarin compound, and is used for forming a colored layer. Radiation-sensitive composition. <Formula 1>

<Formula 2>

In formula (1) and formula (2), each R ¹ independently of each other represents a straight chain, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ² independently represents a hydrogen atom, a straight chain having 1 to 12 carbon atoms, Represents a branched or cyclic alkyl group or a phenyl group, each R ³ independently of one another represents a hydrogen atom or a straight, branched or cyclic alkyl group of 1 to 12 carbon atoms, and each R ⁴ , each R ⁵ and each R ⁶ is independent of each other; To a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, provided that the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each of 1 to 6 carbon atoms. Or a substituent selected from the group of a linear, branched or cyclic alkoxyl group, a phenyl group and a halogen atom, wherein the phenyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, Of 1 to 6 carbon atoms With a substituent selected from linear, branched, or an alkoxy group, a phenyl group and a group of the halogen atom of the cyclic it may be substituted. The color filter which has a colored layer formed from the radiation sensitive composition of Claim 1. The liquid crystal display element which comprises the color filter of Claim 2. Use of the radiation sensitive composition of Claim 1 as formation of the colored layer of a color filter.