KR20070098609A - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Abstract

A radiation sensitive composition for forming a color layer, a color filter having the color layer formed from the composition, and a color liquid crystal display device containing the color filter are provided to improve sensitivity, solvent resistance and the adhesion to a substrate and to form a pattern shape with a small amount of exposure light. A radiation sensitive composition comprises a colorant; an alkali-soluble resin; a multifunctional monomer; and a photopolymerization initiator, wherein the alkali-soluble resin comprises a copolymer of (b1) at least one selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride and an unsaturated phenol compound, (b2) an N-substituted maleimide, (b3) an unsaturated compound having a tetrahydrofuran structure and (b43) other unsaturated compound except (b1), (b2) and (b3).

Description

Radiation Sensitive Composition For Forming A Colored Layer, Color Filter and Color Liquid Crystal Display Device}

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

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

[Patent Document 3] Japanese Unexamined Patent Publication No. 8-259876

The present invention relates to a radiation sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device. In more detail, the radiation-sensitive composition used for formation of the colored layer useful for the color filter used for a transmissive or reflective color liquid crystal display device, a color image tube element, etc., and the color filter which has the colored layer formed from the said radiation-sensitive composition And a color liquid crystal display device comprising 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 irradiation with radiation (hereinafter referred to as "exposure") and developing is known (Japanese Patent Laid-Open No. Hei 2-144502 and Japanese Patent Laid-Open No. Hei 3-53201). Reference).

In recent years, in the field of color filter technology, it is mainstream to reduce the exposure time and shorten the tact time. However, in the conventional colored radiation-sensitive composition, when the exposure amount decreases, the residual film ratio decreases after development, or a defect or undercut occurs in the pattern. In addition, since peeling from a board | substrate of a pattern becomes easy to produce, etc., it was difficult to obtain the pixel and black matrix of a favorable pattern shape, shortening a tact time. In addition, even when the exposure amount is lowered to the pixel and the black matrix, the colored layer is required to be excellent in solvent resistance, adhesion to the substrate, and the like, but the conventional colored radiation-sensitive composition was not necessarily satisfactory in these respects.

It is an object of the present invention to provide a novel colored layer-forming radiation-sensitive material which provides a pixel and a black matrix which are highly sensitive and excellent in pattern shape and residual film ratio even at a low exposure amount, and also excellent in solvent resistance to various solvents, adhesion to a substrate, and the like. It is to provide a composition.

Another object of the present invention is to provide a color filter having a colored layer formed from the radiation-sensitive composition and a liquid crystal display device having the same.

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, radiation-sensitive for forming a colored layer containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator. (B) the alkali-soluble resin is (b1) at least one member selected from the group of unsaturated carboxylic acids, unsaturated carboxylic anhydrides and unsaturated phenol compounds, (b2) N-substituted maleimide, (b3) Achieved by a radiation-sensitive composition for forming a colored layer, comprising a copolymer of an unsaturated compound having a tetrahydrofuran skeleton and (b4) an unsaturated compound different from the above (b1), (b2) and (b3). do.

In the present invention, the colored layer means "pixel and / or black matrix".

According to the present invention, the above objects and advantages of the present invention are secondly achieved by a color filter having a colored layer formed from the radiation sensitive composition for forming a colored layer.

According to the present invention, the above objects and advantages of the present invention are thirdly achieved by a color liquid crystal display device comprising the color filter.

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

Colored layer  Forming Radiation  Composition

-(A) colorant-

The coloring agent in this invention is not specifically limited in color tone, It is suitably selected according to the use of the color filter obtained, and can be any of a pigment, dye, or a natural pigment.

Since the color filter requires high color development and heat resistance, the colorant in the present invention is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance. Preferably, organic pigments or inorganic pigments are used, particularly preferably organic pigments, carbon black.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), specifically, The same color index (CI) number is attached | subjected.

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 used, for example, by refining by sulfuric acid recrystallization, solvent washing, or a combination thereof.

In addition, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III)), 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 thereof. Moreover, an organic pigment and an inorganic pigment can 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 desired. 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. are mentioned, for example.

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

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

As said surfactant, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyesters; Tertiary amine modified polyurethanes; In addition to polyethyleneimine and the like, KP (produced by Shin-Etsu Chemical Co., Ltd.), polyflow (produced by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and Mega Pack (die) Nippon ink Kagaku Kogyo Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), BYK, Disperbyk (above, Big Chemi Japan Co., Ltd., Sol Spas (Geneca Co., Ltd.), etc. are mentioned.

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.

In this invention, a radiation sensitive resin composition can be manufactured by a suitable method. In the case of using a pigment as a colorant, the pigment is mixed and dispersed in the solvent in the presence of a dispersant, for example, using a bead mill, a roll mill, or the like, to obtain a pigment dispersion, which is to be described later. It is preferable to manufacture by adding and mixing a component and (D) component with other solvent and the other additive mentioned later as needed.

The amount of the dispersant used in preparing the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, particularly preferably 10 based on 100 parts by weight of the pigment. To 50 parts by weight. When the usage-amount of a dispersing agent exceeds 100 weight part, there exists a possibility that developability etc. may be impaired.

Moreover, as a solvent used when manufacturing a pigment dispersion liquid, the same thing as the solvent illustrated about the liquid composition of the radiation sensitive resin composition mentioned later is mentioned, for example.

The amount of the solvent used when preparing the pigment dispersion is preferably 200 to 1,000 parts by weight, more preferably 300 to 800 parts by weight based on 100 parts by weight of the pigment.

In the production of the pigment dispersion, when producing using a bead mill, a pigment mixture containing a pigment, a solvent, and a dispersant is preferably used, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm. It can carry out by mixing and dispersing, cooling with cooling water or the like.

In this case, the filling rate of the beads is preferably 50 to 80% of the mill capacity, and the injection amount of the pigment mixed liquid is preferably about 20 to 50% of the mill capacity. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

In addition, when manufacturing using a roll mill, it can carry out by processing, for example, cooling a pigment mixture liquid with cooling water etc., using three roll mills, two roll mills, etc., for example.

In this case, it is preferable that a roll space | interval is 10 micrometers or less, and a shear force becomes like this. Preferably it is about 10 ⁸ dyn / sec. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

-(B) alkali-soluble resin-

The alkali-soluble resin in the present invention is selected from the group consisting of (b1) unsaturated carboxylic acids, unsaturated carboxylic anhydrides and unsaturated phenol compounds (hereinafter, collectively referred to as "unsaturated compounds (b1)"). Or more, (b2) unsaturated compounds having an N-substituted maleimide, (b3) tetrahydrofuran skeleton (hereinafter referred to as " unsaturated compound (b3) ") and (b4) unsaturated compounds other than the above (hereinafter, " Copolymers of unsaturated compounds (b4) "(hereinafter referred to as" copolymers (BI) "). Copolymer (BI) is a component which has solubility with respect to the alkaline developing solution used at the developing process process at the time of forming a colored layer, acting as a binder with respect to (A) coloring agent.

In the unsaturated compound (b1), examples of the unsaturated carboxylic acid and unsaturated carboxylic anhydride include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

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

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate.

Among these unsaturated carboxylic acids and unsaturated carboxylic anhydrides, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively represented by light ester HOA-MS and light ester HOA-MPE ( It is marketed under the trade name of Kyoeisha Chemical Co., Ltd.).

Moreover, as said unsaturated phenol compound, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, 2-methyl-4- vinyl phenol, 3-methyl-4- vinyl phenol, o-isopropenyl phenol, for example unsaturated phenols such as m-isopropenylphenol and p-isopropenylphenol;

2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1- Unsaturated naphthol, such as naphthol, etc. are mentioned.

In this invention, as an unsaturated compound (b1), (meth) acrylic acid, p-vinylphenol, etc. are preferable, and (meth) acrylic acid is especially preferable.

As the N-substituted maleimide, for example, N-methyl maleimide, N-ethyl maleimide, Nn-propyl maleimide, Ni-propyl maleimide, Nn-butyl maleimide, Nt-butyl maleimide, Nn -Hexyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-1- naphthyl maleimide, etc. are mentioned.

In the present invention, as the N-substituted maleimide, N-cyclohexyl maleimide, N-phenyl maleimide and the like are preferable, and N-phenyl maleimide is particularly preferable.

The said N-substituted maleimide can be used individually or in mixture of 2 or more types.

Moreover, as an unsaturated compound (b3), For example, tetrahydrofuran ester of (meth) acrylic acid, such as tetrahydrofuran-2-yl (meth) acrylate and tetrahydrofuran-3-yl (meth) acrylate;

Tetrahydrofurfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (3-tetrahydrofurfuryloxy) ethyl (meth Tetrahydrofurfuryl group containing ester of (meth) acrylic acid, such as) acrylate;

Phthalic acid [2- (meth) acryloyloxyethyl] (tetrahydrofuran-2-yl), phthalic acid [2- (meth) acryloyloxyethyl] (tetrahydrofuran-3-yl), succinic acid [2- Of divalent carboxylic acids such as (meth) acryloyloxy ethyl] (tetrahydrofuran-2-yl) and succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofuran-3-yl) Meth) acryloyl group containing tetrahydrofuran ester;

(Meth) of divalent carboxylic acids such as phthalic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) and succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) Acryloyl group-containing tetrahydrofurfuryl ester;

Tetrahydro of 2- (meth) acryloyloxypropionic acid, such as 2- (meth) acryloyloxypropionate tetrahydrofuran-2-yl and 2- (meth) acryloyloxypropionic acid tetrahydrofuran-3-yl Furan esters;

2- (meth) acryloyloxypropionic acid tetrahydrofurfuryl, 2- (meth) acryloyloxypropionic acid 3-tetrahydrofurfuryl, 2- (meth) acryloyloxypropionic acid 2- (tetrahydrofurfuryloxy Tetrahydrofurfuryl group-containing esters of 2- (meth) acryloyloxypropionic acid such as) ethyl and 2- (meth) acryloyloxypropionic acid 2- (3-tetrahydrofurfuryloxy) ethyl;

Vinylbenzene derivatives such as (tetrahydrofuran-2-yl) oxy-p-vinylbenzene, tetrahydrofurfuryloxy-p-vinylbenzene and 2- (tetrahydrofurfuryloxy) ethoxy-p-vinylbenzene;

And vinyl ethers such as (tetrahydrofuran-2-yl) vinyl ether, (tetrahydrofurfuryl) vinyl ether, and [2- (tetrahydrofurfuryloxy) ethyl] vinyl ether.

In the present invention, as the unsaturated compound (b3), tetrahydrofurfuryl (meth) acrylate, succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) and the like are preferable.

The said unsaturated compound (b3) can be used individually or in mixture of 2 or more types.

Moreover, as an unsaturated compound (b4), for example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-methoxy styrene , p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl Aromatic vinyl compounds such as glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol ( Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropyl Lenglycol (meth) acrylate, methoxydipropyleneglycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Unsaturated carboxylic acid esters such as meth) acrylate and glycerol mono (meth) 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 latex and 3-dimethylaminopropyl (meth) acrylate;

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

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

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

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

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

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

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.

The said unsaturated compound (b4) can be used individually or in mixture of 2 or more types.

In the present invention, the copolymer (BI) is one selected from the group consisting of (meth) acrylic acid or a combination with one or more other unsaturated compounds (b1), N-cyclohexylmaleimide, and N-phenylmaleimide. At least one unsaturated group selected from the group consisting of the above N-substituted maleimide (b2), tetrahydrofurfuryl (meth) acrylate, and succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) Compound (b3) and styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate , Copolymers of one or more unsaturated compounds (b4) selected from the group consisting of benzyl (meth) acrylates, glycerol mono (meth) acrylates, polystyrene macromonomers and polymethylmethacrylate macromonomers Is referred to as "copolymer (BII)".

Specific examples of the copolymer (BII) include (meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate copolymer,

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

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

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

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

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

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,

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

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

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

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

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

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

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

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

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

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

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

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / n-butyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / n-butyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

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

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

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

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

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

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macro Monomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (Meth) acrylate macromonomer copolymers,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / Polystyrene macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / Polymethylmethacrylate macromonomer copolymer,

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

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

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

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

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

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate Copolymer,

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

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

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

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

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylic Latex / glycerol mono (meth) acrylate copolymer,

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

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

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylic Latex / glycerol mono (meth) acrylate copolymer, and

The copolymer etc. which substituted tetrahydrofurfuryl (meth) acrylate in these copolymers with succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) are mentioned.

Of the said copolymer (BII), (meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenyl Maleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenylmaleimide / succinic acid [ 2- (meth) acryloyloxyethyl] tetrahydrofurfuryl / styrene / n-butyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenylmaleimide / succinic acid [2- (meth) acryloyl Oxyethyl] tetrahydrofurfuryl / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer and the like are preferable.

In the copolymer (BI), the copolymerization ratio of the unsaturated compound (b1) is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the N-substituted maleimide is preferably It is 1-50 weight%, Especially preferably, it is 5-40 weight%, The copolymerization ratio of an unsaturated compound (b3) becomes like this. Preferably it is 1-70 weight%, Especially preferably, it is 10-40 weight%, An unsaturated compound (b4 The copolymerization ratio of c) is preferably 1 to 80% by weight, particularly preferably 5 to 60% by weight.

In this invention, the radiation sensitive composition excellent in a sensitivity, board | substrate adhesiveness, and solvent resistance can be obtained by making the copolymerization ratio of each unsaturated compound in a copolymer (BI) into the said range.

In this invention, another alkali-soluble resin can also be used together with copolymer (BI).

It does not specifically limit as said other alkali-soluble resin as long as it has solubility with respect to the alkaline developing solution used at the developing process process at the time of forming a colored layer, acting as a binder with respect to (A) coloring agent. For example, alkali-soluble resin which has a carboxyl group is preferable, As the example, 1 or more types chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride illustrated with respect to copolymer (BI), copolymer (BI) And at least one copolymer selected from the group consisting of N-substituted maleimide and unsaturated compound (b4) and the like (copolymer (BII)).

As other preferable alkali-soluble resin, More specifically, (i) 1 or more unsaturated carboxylic acid which has (meth) acrylic acid as an essential component, and (ii) N-cyclohexyl maleimide, N-phenylmaleimide, styrene, methyl (Meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, And at least one copolymer selected from the group consisting of glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer.

In the present invention, the polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is preferable, respectively. Preferably 2,000 to 300,000, more preferably 3,000 to 100,000.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is preferably 3,000, respectively. To 60,000, more preferably 5,000 to 25,000.

In this invention, the radiation sensitive composition excellent in developability by using the copolymer (BI) which has the said specific Mw and Mn, or using the said copolymer (BI) and other alkali-soluble resin which has the said specific Mw and Mn together. Thus, a pixel and a black matrix having sharp patterned ends can be formed, and at the time of development, residues, background contamination, film residues, etc. on the substrate and the light shielding layer of the unexposed portion are less likely to occur.

In addition, the ratio (Mw / Mn) of Mw and Mn of the copolymer (BI) and other alkali-soluble resins is preferably 1 to 5, more preferably 1 to 4, respectively.

In this invention, copolymer (BI) can be used individually or in mixture of 2 or more types, and also the other alkali-soluble resin is the same.

In the present invention, the total amount of the alkali-soluble resin is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. If the total amount of the alkali-soluble resin is less than 10 parts by weight, alkali developability may decrease, for example, there may be a background contamination or a film residue on the substrate or the light shielding layer of the unexposed part, while exceeding 1,000 parts by weight. When the colorant concentration is relatively lowered, it may be difficult to achieve the target color density as a thin film.

In addition, the use ratio of the copolymer (BI) in alkali-soluble resin becomes like this. Preferably it is 10-100 weight%, Especially preferably, it is 20-100 weight%. If the use ratio of the copolymer (BI) is less than 10% by weight, the desired effect of the present invention may be impaired.

-(C) polyfunctional monomer-

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

As a polyfunctional monomer, For example, Di (meth) acrylate of alkylene glycol, such as ethylene glycol and propylene glycol;

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

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

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

Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone, or

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

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols or their dicarboxylic acid modified substances, specifically trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylic The rate, dipentaerythritol hexamethacrylate, the compound represented by the following formula (1), the compound represented by the following formula (2), and the like are preferable.

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer and excellent surface smoothness of the colored layer, while on the substrate and light shielding layers of the unexposed part. This is particularly preferable in that it is difficult to generate soil contamination, film residues and the like.

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 is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, if the amount is more than 500 parts by weight, for example, alkali developability is lowered, or the substrate or light-shielding of the unexposed part is performed. Background contamination, film residues, etc., tend to occur on the 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 compound illustrated with respect to unsaturated compound (b1), N-substituted maleimide, and unsaturated compound (b4) in (B) alkali-soluble resin, for example, N- (meth) In addition to acryloyl morpholine, N-vinylpyrrolidone, and N-vinyl- epsilon caprolactam, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

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

The use ratio of the monofunctional monomer is preferably 90% by weight or less, 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 used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, if the total amount exceeds 500 parts by weight, for example, alkali developability is lowered, or the substrate or light shielding layer on the unexposed part is used. There is a tendency for background contamination, film residues, etc. to occur easily.

-(D) photoinitiator-

The photopolymerization initiator in the present invention can initiate polymerization of the above-mentioned (C) polyfunctional monomer and the monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like. Is a compound that generates active species.

As such a photoinitiator, an acetophenone type compound, a biimidazole type compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a diazo type, A compound, an O-acyl oxime type compound, an onium salt type compound, an imide sulfonate type compound, etc. are mentioned. These compounds are components which generate an active radical or active acid by exposure or both an active radical and an active acid.

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

In this invention, the usage-amount of a photoinitiator becomes like this. Preferably it is 0.01-120 weight part, More preferably, it is 1-100 weight part with respect to a total of 100 weight part of (C) polyfunctional monomer or this and monofunctional monomer. When the usage-amount of a photoinitiator is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 120 weight part, the coloring formed There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

As a specific example of an acetophenone type compound among the preferable photoinitiators in this invention, 2-hydroxy-2-methyl-1- phenyl propane- 1-one and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione, etc. are mentioned.

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

The acetophenone compounds may be used alone or in combination of two or more thereof.

In the present invention, the amount of the acetophenone-based compound used as the photopolymerization initiator is preferably 0.01 to 80 parts by weight, more preferably based on 100 parts by weight of the total of the (C) polyfunctional monomer or monofunctional monomer. Is 1 to 60 parts by weight, more preferably 1 to 30 parts by weight. If the amount of the acetophenone-based compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which a colored layer pattern is arranged in accordance with a predetermined arrangement. There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

Moreover, as a specific example of the said biimidazole type 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'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferred, in particular 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole is preferred.

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

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

In the present invention, the amount of use of the biimidazole-based compound as the photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably based on the total of the (C) polyfunctional monomer or monofunctional monomer. 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount of the non-imidazole compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which a colored layer pattern is arranged in accordance with a predetermined arrangement. When it does, it exists in the tendency which comes out of the board | substrate of the formed colored layer, and the film | membrane roughness of the colored layer surface becomes easy.

In this invention, when using a biimidazole type compound as a photoinitiator, it is preferable to use the following hydrogen donor together at the point which can improve a sensitivity further.

As used herein, the term "hydrogen donor" means a compound capable of donating a hydrogen atom to radicals generated from a biimidazole compound by exposure.

As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2 mercapto groups directly bonded to the mother nucleus (hereinafter, , “Mercaptan-based hydrogen donor”).

The amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one amino group, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, "amine" System 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-based hydrogen donor may have one or more benzene rings or heterocycles, and may also have both benzene rings and heterocycles. When it has 2 or more of these rings, a condensed ring can also be formed.

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

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

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

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

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

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

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

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

On the other hand, the amine-based hydrogen donor also has a function as a sensitizer even in the case of radical generators other than the biimidazole-based compound.

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

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'- Bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzo Phenone etc. are mentioned. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, in particular Preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

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

In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total of (C) the polyfunctional monomer or the monofunctional monomer. Preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, when the amount of the hydrogen donor exceeds 40 parts by weight, the formed colored layer tends to fall off the substrate during development.

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

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

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

In the present invention, the amount of the triazine-based compound used as the photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight in total of the (C) polyfunctional monomer or monofunctional monomer. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the triazine-based compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged in accordance with a predetermined arrangement. There exists a tendency for it to fall easily from a board | substrate at this time of image development.

In addition, specific examples of the O-acyl oxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime) and 1- [4- (phenylthio) Phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H -Carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetyloxime ), And the like.

Among these O-acyl oxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime) and the like are preferred.

The O-acyl oxime compounds may be used alone or in combination of two or more thereof.

In the present invention, the amount used when the O-acyl oxime compound is used as the photopolymerization initiator is preferably 0.01 to 40 parts by weight, based on 100 parts by weight of the total of (C) the polyfunctional monomer or the monofunctional monomer. More preferably, it is 1-30 weight part, Especially preferably, it is 1-20 weight part. When the usage-amount of O-acyl oxime type compound is less than 0.01 weight part, hardening by exposure may become inadequate and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 40 weight part, There exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

Moreover, as said onium salt type compound, a diaryl iodonium salt, a triaryl sulfonium salt, a diaryl phosphonium salt, etc. are mentioned, for example.

As a specific example of the said diaryl iodonium salt, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, diphenyl iodonium hexafluoro arsenate, diphenyl iodonium tri Fluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodo Hexafluorophosphonate, 4-methoxyphenylphenyl iodonium Hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium tri Fluoroacetate, 4-methoxyphenylphenyl iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexa Fluoroarsenate, bis (4-tert- Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, etc. Can be mentioned.

Specific examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethanesulfonate , Triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate , 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxy Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, 4-phenylthiophenyldiphenyl hexa Safluoro arsenate, 4-phenylthio phenyl diphenyl trifluoro methanesulfonate, 4-phenylthio phenyl diphenyl trifluoro acetate, 4-phenyl thiophenyl diphenyl- p-toluenesulfonate, etc. are mentioned. have.

As a specific example of the said diaryl phosphonium salt, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron hexafluoro phosphonate etc. are mentioned.

Among these onium salt compounds, diphenyl iodonium hexafluorophosphonate, triphenylsulfonium trifluoromethanesulfonate, and the like are particularly preferable.

The onium salt compounds may be used alone or in combination of two or more thereof.

In the present invention, the amount of use of the onium salt-based compound as the photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably to 100 parts by weight of the total amount of the (C) polyfunctional monomer or monofunctional monomer. 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the onium salt-based compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged in accordance with a predetermined arrangement. There exists a tendency for it to fall easily from a board | substrate at this time of image development.

-additive-

The radiation sensitive composition for coloring layer formation of this invention can contain various additives as needed.

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

The said organic acid and organic amino compound are components which show the effect which further suppresses the remainder of the undissolved matter after image development, further improving the solubility to the alkaline developing solution of a radiation sensitive composition.

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

As said aliphatic carboxylic acid, For example, monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;

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

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

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

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, or

And phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamiledic acid, kumaric acid, and umbelic acid.

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

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

The 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.

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

As said aliphatic amine, it is n-propylamine, i-propylamine, n-butyl amine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-, for example. Heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4- Mono (cyclo) alkylamines such as methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine and 4-ethylcyclohexylamine;

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

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

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

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

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

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

1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclo Amino group-containing cycloalkanethanols such as hexanemethanol and 4-diethylaminocyclohexanemethanol; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 And aminocarboxylic acids such as -aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

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

As 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 Aromatic amines such as 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and 4-methyl-N, N-dimethylaniline;

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

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) s are used as aliphatic amines in view of solubility in a solvent to be described later and prevention of background contamination or film residue on a substrate or a light shielding layer of an unexposed part. 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, aminophenol is preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol etc. are especially preferable.

The said hardening | curing agent is a component which hardens the said (B) alkali-soluble resin by reacting with the carboxyl group and / or tetrahydrofuran ring in (B) alkali-soluble resin.

As such a hardening | curing agent, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

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

Moreover, an epoxy group containing unsaturated compound is also preferable as said epoxy compound, As a specific example, glycidyl (meth) acrylate, 3, 4- epoxy butyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.

Moreover, as said oxetane compound, a polyfunctional oxetane compound is preferable, As a specific example, bisoxetanyl carbonate, bisoxetanyl adipic acid, bisoxetanyl terephthalate, bis p-xylylenedicarboxylic acid bis High molecular compounds such as low molecular compounds such as oxetanyl and 1,4-cyclohexanedicarboxylic acid bisoxetanyl, oxetane ethers of phenol novolak resins, and (co) polymers of oxetane group-containing unsaturated compounds Can be mentioned.

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

The usage-amount of a hardening | curing agent becomes like this. Preferably it is 30 weight% or less with respect to the whole solid content of a radiation sensitive composition, More preferably, it is 20 weight% or less. When the usage-amount of a hardening | curing agent exceeds 30 weight%, there exists a tendency for the storage stability of the radiation sensitive composition obtained to fall.

The said hardening adjuvant is a component which accelerates | stimulates the hardening reaction by the said hardening | curing agent by ring-opening the epoxy group and / or oxetane ring which the said hardening | curing agent has.

As such a hardening adjuvant, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an amino compound, a thermal acid generator, etc. are mentioned, for example.

As a specific example of the said polyhydric carboxylic acid, the thing similar to the compound which has two or more carboxyl groups in the said organic acid is mentioned, As a specific example of the said amino compound, the thing similar to the said organic amino compound is mentioned.

Moreover, as a specific example of the said polyhydric carboxylic anhydride, aromatic polyhydric carboxylic anhydrides, such as a phthalic anhydride, a pyromellitic dianhydride, a trimellitic anhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, are mentioned. ; Aliphatic polyhydric carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvalylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ; Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polyhydric carboxylic acid anhydrides such as water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride and anhydrous acid; In addition to ester group-containing carboxylic anhydrides such as ethylene glycol bistrimellitate anhydride and glycerin tristrimellitate anhydride, Adeka Hardner EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.) and lycaside HH (Shin Nippon Rika Co., Ltd.) Epoxy resin hardening | curing agent etc. which are marketed by brand names, such as (the manufacture) and MH-700 (made by Shin-Nippon Rika Co., Ltd.), are mentioned.

Examples of the thermal acid generator include sulfonium salts (except triarylsulfonium salts exemplified for the photopolymerization initiator (D)), benzothiazonium salts, ammonium salts, and phosphonium salts. have.

Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium Hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4 Alkylsulfonium salts such as acetoxyphenylsulfonium hexafluoroantimonate;

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

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

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzyl sulfonium salts, such as an antimonate and o-chlorobenzyl-3- chloro-4- hydroxyphenyl methyl sulfonium hexafluoro antimonate, etc. are mentioned.

In addition, specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p- Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, etc. Benzyl benzothiazonium salt etc. are mentioned.

Among these thermal acid generators, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoro Antimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, and the like. desirable.

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

The usage-amount of a hardening adjuvant becomes like this. Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less with respect to the whole solid of a radiation sensitive composition. When the usage-amount of a hardening aid exceeds 15 weight%, there exists a tendency for the storage stability of the radiation sensitive composition obtained to fall, or the colored layer formed to fall easily from a board | substrate at the time of image development.

Moreover, as an additive of that excepting the above, For example, Dispersion adjuvant, such as blue pigment derivatives, such as a copper phthalocyanine derivative, and a yellow pigment derivative;

Fillers such as glass and alumina;

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

Surfactants, such as nonionic, cationic, and anionic:

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

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

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

Aggregation inhibitors such as sodium polyacrylate;

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

menstruum

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

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) or 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, tri (Poly) alkylenes such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether Recall monoalkyl ether;

(Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates;

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

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

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

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutane, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, n-amyl 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, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

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

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3-methyl-3 Methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, ethyl butyrate i-propyl, n-butyl butyrate, ethyl pyruvate, and the like. desirable.

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

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

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

Although the usage-amount of a solvent is not specifically limited, From 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 for colored layer formation of this invention.

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

First, a light shielding layer is formed on the surface of a substrate so as to partition a 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 through a photomask to this coating film, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and then post-bakes to form the pixel array in which the red pixel pattern was arrange | positioned in the predetermined arrangement.

Thereafter, using the liquid composition of each radiation-sensitive composition in which the green or blue pigment is dispersed, the liquid pixel composition and the blue pixel array and the blue color are applied in the same manner as described above by applying, prebaking, exposing, developing and post-baking the liquid composition. By sequentially forming 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.

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

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

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

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

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

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

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- 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 developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid soaking) developing method, and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

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

Color liquid crystal display element

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

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

Although the radiation sensitive composition for colored layer formation 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)-(d).

(A) The radiation sensitive composition for colored layer formation in which (B) alkali-soluble resin contains a copolymer (BII).

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

(C) The colored layer of (A) or (B) wherein the photopolymerization initiator comprises at least one member selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyl oxime compounds. Radiation-sensitive composition for formation.

(D) The radiation sensitive composition for colored layer formation of said (A), (B) or (C) whose (A) coloring agent contains an organic pigment or carbon black.

Moreover, the preferable color filter of this invention has the pixel and / or black matrix formed from the radiation sensitive composition for colored layer formation of said (a), (b), (c) or (d).

Moreover, the preferable color liquid crystal display element of this invention is equipped with (f) the color filter of said (e), The more preferable color liquid crystal display element of this invention is (g) the color of said (e) on a thin film transistor substrate array. It is equipped with a filter.

<Example>

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

Synthesis of Alkali Soluble Resin

Synthesis Example 1

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid and 15 parts of N-phenylmaleimide. Parts by weight, 30 parts by weight of tetrahydrofurfuryl methacrylate, 10 parts by weight of styrene, 30 parts by weight of n-butyl methacrylate, 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator, and after nitrogen replacement, Stirring was started, the temperature of the reaction solution was raised to 80 ° C., and the solution was maintained by polymerization for 5 hours to obtain a solution of the copolymer (BI). This copolymer (BI) is referred to as "alkali-soluble resin (B-1)".

Synthesis Example 2

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid and 15 parts of N-phenylmaleimide. Parts by weight, succinic acid (2-methacryloyloxyethyl) (tetrahydrofurfuryl) 30 parts by weight, styrene 10 parts by weight, n-butyl methacrylate 30 parts by weight, α-methylstyrene dimer 3 weights as a molecular weight regulator After adding the part and replacing with nitrogen, stirring was started gently, the temperature of the reaction solution was raised to 80 ° C, and the temperature was maintained for 5 hours to obtain a solution of the copolymer (BI). This copolymer (BI) is referred to as "alkali-soluble resin (B-2)".

Comparative Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 3 parts by weight of 2,2'-azobisisobutyronitrile, 200 parts by weight of propylene glycol monomethyl ether acetate, 15 parts by weight of methacrylic acid, 45 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of n-butyl methacrylate, 3 parts by weight of α-methylstyrene dimer as a molecular weight modifier were added thereto, and after nitrogen substitution, gently stirring was started to raise the temperature of the reaction solution to 80 ° C. The solution of the copolymer was obtained by hold | maintaining this temperature for 5 hours and superposing | polymerizing. This copolymer is referred to as "alkali-soluble resin (B-3)".

Preparation of Pigment Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 177 = 80/20 (weight ratio) 20 parts by weight of the mixture, 5 parts by weight of BYK-2001 (in terms of solids) as a dispersant, and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to obtain a pigment dispersion ( R1) was prepared.

Preparation Example 2

A pigment dispersion (R2) was prepared in the same manner as in Production Example 1, except that 5 parts by weight (in terms of solids) of Solpas 24000 was used instead of BYK-2001.

Preparation Example 3

(A) As a coloring agent, C.I. Pigment Green 36 / C.I. Pigment Yellow 150 = 50/50 (weight ratio) 20 parts by weight of the mixture, 5 parts by weight of BYK-2001 as a dispersant (in terms of solids), and 75 parts by weight of propylene glycol monomethyl ether acetate as the solvent were treated with a bead mill to obtain a pigment dispersion ( G1) was prepared.

Preparation Example 4

A pigment dispersion (G2) was prepared in the same manner as in Production Example 3, except that 5 parts by weight (in terms of solids) of Solpas 24000 was used instead of BYK-2001.

Preparation Example 5

(A) As a coloring agent, C.I. Pigment Blue 15: 6 / C.I. Pigment Violet 23 = 90/10 (weight ratio) 20 parts by weight of the mixture, 5 parts by weight of BYK-2001 (in terms of solids) as a dispersant, and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to obtain a pigment dispersion ( B1) was prepared.

Preparation Example 6

A pigment dispersion (B2) was prepared in the same manner as in Production Example 5, except that 5 parts by weight (in terms of solids) of Solpas 24000 was used instead of BYK-2001.

Example 1

100 weight part of pigment dispersion (R1), 15 weight part (solid content conversion) of alkali-soluble resin (B-1), (C) 20 weight part of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) as a photoinitiator 5 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and propylene glycol monomethyl ether acetate as a solvent were mixed to form a liquid composition having a solid content concentration of 25% by weight ( R1-1) was prepared.

The liquid composition (R1-1) was evaluated by forming a pattern according to the following procedure. The evaluation results are shown in Table 1.

Formation of patterns

After apply | coating liquid composition (R1-1) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 4 minutes, and formed the coating film with a film thickness of 1.3 micrometers. Thereafter, six of these substrates were cooled to room temperature, and 300 J / m 2, 400 J / m 2, 500 J / m 2, 750 J / m 2, 1,000 J through a photomask using a high pressure mercury lamp for the coating film on each substrate. It exposed at each exposure amount of / m <2> or 2,000 J / m <2>. Then, shower development was performed by discharging a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C. at a developing pressure of 1 kgf / cm 2 (nozzle diameter 1 mm) to the coating films on each substrate, followed by post-baking at 220 ° C. for 30 minutes. A dot pattern of 200 × 200 μm was formed.

Evaluation of sensitivity

The dot pattern on each board | substrate was observed with the scanning electron microscope, and the case where a pattern is formed satisfactorily and the residual film ratio (film thickness after development x 100 / film thickness before development) computed as the film thickness ratio before and behind image development is 90% or more. (Triangle | delta) and the case where a pattern is not formed were evaluated as (x) for the case where a pattern is formed favorable but the residual film ratio before and behind image development is less than 90%, or a defect is seen in a part of pattern.

Solvent-resistant  evaluation

Each substrate was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and the dot pattern before and after immersion was observed with a scanning electron microscope, and there was no change in the pattern, and the film thickness ratio before and after immersion (film thickness after immersion x 100 ?, The case where the film thickness ratio before and after immersion was less than 95%, or a defect was seen in a part of the pattern before and after immersion, and the case where all the patterns were peeled off from the substrate after immersion were evaluated as ×. . On the other hand, when the dot pattern could not be formed due to lack of sensitivity, no evaluation was made (indicated by "-" in Table 1).

Evaluation of adhesion

After apply | coating liquid composition (R1-1) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 4 minutes, and formed the coating film with a film thickness of 1.3 micrometers. Then, after cooling this board | substrate to room temperature, it exposed to the coating film by the exposure amount of 2,000 J / m <2> using the high pressure mercury lamp. Then, shower development was performed by discharging a 0.04 weight% potassium hydroxide aqueous solution of 23 degreeC to the coating film at the developing pressure (1 mm of nozzle diameter) of 1 kgf / cm <2>, and post-baking was performed at 220 degreeC for 30 minutes. Thereafter, the coating film was cross-cut into 100 checkerboard grid shapes in accordance with JIS K5400 standard to evaluate the adhesion, and ○, the case where 1 to 10 of the checkerboard scales were peeled off △, the checkerboard scale The case where peeling more than these 10 pieces was evaluated as x.

Example 2

In Example 1, (D) the photoinitiator is 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime) 5 Except having changed to the weight part, it carried out similarly to Example 1, and manufactured the liquid composition (R1-2).

Next, it evaluated like Example 1 except having used liquid composition (R1-2) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 3

100 parts by weight of the pigment dispersion (R1), 12 parts by weight (in terms of solid content) of the alkali-soluble resin (B-1), (C) 20 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, and (D) a photopolymerization initiator. Bisphenol A novolak-type epoxy resin (brand name 157S65, Japan epoxy resin Co., Ltd.) as 5 weight part of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane-1-one, and a hardening | curing agent Manufacture) 3 weight part and propylene glycol monomethyl ether acetate were mixed as a solvent, and the liquid composition (R1-3) of 25 weight% of solid content concentration was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R1-3) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 4

100 weight part of pigment dispersion (R1), 15 weight part (solid content conversion) of alkali-soluble resin (B-1), (C) 20 weight part of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) as a photoinitiator 5 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 1 part by weight of trimellitic anhydride as a curing agent, and propylene glycol monomethyl ether acetate as a solvent To prepare a liquid composition (R1-4) having a solid concentration of 25% by weight.

Next, it evaluated like Example 1 except having used liquid composition (R1-4) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 5

In Example 1, except having changed the alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-2), it carried out similarly to Example 1, and a liquid composition (R1-5) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R1-5) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 6

In Example 1, the liquid composition (R2-1) was produced like Example 1 except having changed the pigment dispersion (R1) into 100 weight part of pigment dispersions (R2).

Next, it evaluated like Example 1 except having used liquid composition (R2-1) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 7

In Example 1, the pigment dispersion (R1) was changed to 100 parts by weight of the pigment dispersion (R2), and the alkali-soluble resin (B-1) was changed to 15 parts by weight (solid content conversion) of the alkali-soluble resin (B-2). A liquid composition (R2-2) was prepared in the same manner as in Example 1 except for the above.

Next, it evaluated like Example 1 except having used liquid composition (R2-2) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 8

100 weight part of pigment dispersion (G1), 20 weight part (solid content conversion) of alkali-soluble resin (B-1), (C) 10 weight part of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) as a photoinitiator 10 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and propylene glycol monomethyl ether acetate as a solvent were mixed to obtain a liquid composition having a solid content of 25% by weight (G1). -1) was prepared.

Next, it evaluated like Example 1 except having used liquid composition (G1-1) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 9

In Example 8, the liquid composition (G2-1) was produced like Example 8 except having changed the pigment dispersion (G1) into 100 weight part of pigment dispersion (G2).

Next, it evaluated like Example 1 except having used liquid composition (G2-1) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 10

In Example 8, except having changed the alkali-soluble resin (B-1) into 20 weight part (solid content conversion) of alkali-soluble resin (B-2), it carried out similarly to Example 8, and liquid composition (G1-2) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (G1-2) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 11

In Example 8, the pigment dispersion (G1) was changed to 100 parts by weight of the pigment dispersion (G2), and the alkali-soluble resin (B-1) was changed to 20 parts by weight (solid content conversion) of the alkali-soluble resin (B-2). A liquid composition (G2-2) was prepared in the same manner as in Example 8 except for the above.

Next, it evaluated like Example 1 except having used liquid composition (G2-2) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 12

100 parts by weight of the pigment dispersion (B1), 15 parts by weight of the alkali-soluble resin (B-1) (solid content conversion), (C) 15 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, and (D) as the photopolymerization initiator. 4 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 1 part by weight of 2,4-diethylthioxanthone, propylene glycol monomethyl ether as a solvent Acetate was mixed to prepare a liquid composition (B1-1) having a solid concentration of 25% by weight.

Next, it evaluated like Example 1 except having used liquid composition (B1-1) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 13

In Example 12, the liquid composition (B2-1) was produced like Example 12 except having changed the pigment dispersion (B1) into 100 weight part of pigment dispersions (B2).

Next, it evaluated like Example 1 except having used liquid composition (B2-1) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 14

Example 12 WHEREIN: Except having changed alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-2), it carried out similarly to Example 12, and liquid composition (B1-2) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (B1-2) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Example 15

In Example 12, the pigment dispersion (B1) was changed to 100 parts by weight of the pigment dispersion (B2), and the alkali-soluble resin (B-1) was changed to 15 parts by weight (solid content conversion) of the alkali-soluble resin (B-2). A liquid composition (B2-2) was prepared in the same manner as in Example 12 except for the above.

Next, it evaluated like Example 1 except having used liquid composition (B2-2) instead of liquid composition (R1-1). The evaluation results are shown in Table 1.

Comparative Example 1

Example 1 WHEREIN: Except having changed alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 1, and liquid composition (R1-6) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R1-6) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 2

Example 2 WHEREIN: Except having changed alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 2, and liquid composition (R1-7) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R1-7) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 3

Example 3 WHEREIN: Except having changed alkali-soluble resin (B-1) into 12 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 3, and liquid composition (R1-8) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R1-8) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 4

Example 4 WHEREIN: Except having changed alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 4, and liquid composition (R1-9) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R1-9) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 5

Example 6 WHEREIN: Except having changed the alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 6, and the liquid composition (R2-3) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (R2-3) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 6

In Example 8, it carried out similarly to Example 8 except having changed alkali-soluble resin (B-1) into 20 weight part (solid content conversion) of alkali-soluble resin (B-3), and liquid composition (G1-3) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (G1-3) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 7

Example 9 WHEREIN: Except having changed alkali-soluble resin (B-1) into 20 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 9, and liquid composition (G2-3) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (G2-3) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 8

In Example 12, it carried out similarly to Example 12 except having changed alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-3), and liquid composition (B1-3) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (B1-3) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

Comparative Example 9

Example 13 WHEREIN: Except having changed alkali-soluble resin (B-1) into 15 weight part (solid content conversion) of alkali-soluble resin (B-3), it carried out similarly to Example 13, and liquid composition (B2-3) Was prepared.

Next, it evaluated like Example 1 except having used liquid composition (B2-3) instead of liquid composition (R1-1). The evaluation results are shown in Table 2.

As described above, the radiation-sensitive composition for forming a colored layer of the present invention has a high sensitivity, a pixel and a black matrix having excellent pattern shape and residual film ratio even at a low exposure amount, and excellent solvent resistance to various solvents, adhesion to a substrate, and the like. Can be formed.

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

Claims (3)

It is a radiation sensitive composition for colored layer formation containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (B) alkali-soluble resin is (b1) unsaturated carbon At least one selected from the group consisting of an acid, an unsaturated carboxylic anhydride and an unsaturated phenol compound, (b2) an N-substituted maleimide, (b3) an unsaturated compound having a tetrahydrofuran skeleton and (b4) the above (b1) A radiation sensitive composition for forming a colored layer, comprising a copolymer of an unsaturated compound different from), (b2) and (b3). The color filter which has a colored layer formed from the radiation sensitive composition for colored layer formation of Claim 1. The color liquid crystal display element provided with the color filter of Claim 2.