KR101408422B1 - Radiation sensitive resin composition and color filter - Google Patents

Abstract

The present invention relates to a copolymer of an unsaturated carboxylic acid (anhydride) and at least one unsaturated phenol compound, an allyl group-containing compound, and an unsaturated compound which is different from any of the above-mentioned compounds and has a polystyrene- A radiation-sensitive resin composition containing an alkali-soluble resin, a colorant, a polyfunctional monomer and a photopolymerization initiator having a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a polystyrene reduced number average molecular weight (Mn) of 1.0 to 2.0 do.

INDUSTRIAL APPLICABILITY According to the present invention, a color filter excellent in solvent solubility of a dry coating film, excellent in reliability in electric characteristics typified by voltage holding ratio and the like without causing color unevenness in a coating film after exposure and development, .

Sensitive resin composition, a color filter, a color liquid crystal display

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive resin composition and a color filter,

The present invention relates to a radiation-sensitive resin composition useful for manufacturing a color filter used in a transmission type or reflection type color liquid crystal device, a color image pickup tube device, etc., a production method thereof, a color filter and a color liquid crystal display device.

As a method for forming a color filter using a color sensitive radiation-sensitive resin composition, a coating film of a colored and radiation-sensitive resin composition is formed on a substrate or on a substrate having a light-shielding layer of a desired pattern formed in advance, (Hereinafter referred to as "exposure"), for example, by developing with an alkali developer to dissolve and remove the unexposed portions, and thereafter post-baking using a clean oven or a hot plate, (See Japanese Patent Application Laid-Open No. 2000-329929).

In recent years, since the size of a substrate used for formation of a color filter has become larger, a method of applying a color sensitive radiation-sensitive resin composition is changed from a method using a center drop type spin coater to a method of applying a liquid- Is replaced by a method using a slit nozzle having a smaller diameter. In the latter slit nozzle method, since the diameter of the liquid outlet portion is small (narrow), the colored radiation-sensitive resin composition remains in the periphery of the tip of the nozzle after coating is finished. When this is dried, The quality of the color filter drops significantly on the color filter, so that the jet cleaning is usually carried out to spray the cleaning solvent to the tip of the nozzle before coating. However, the quality deterioration of the color filter due to dry foreign matter is effectively prevented And the yield of the product is decreased. In addition, in the case of the conventional colored and radiation-curable resin composition, color unevenness may occur in the coating film after exposure and development, and in this case, the yield of the product is lowered.

Therefore, in order to cope with such a problem, in recent years, a coloring and radiation-sensitive resin for a color filter which has high cleansing property by a cleaning solvent, that is, high solubility in a cleaning solvent even after drying and does not cause color unevenness in a coating film after exposure and development A composition is required.

In the technical field of color filters in recent years, there is a strong demand for a color liquid crystal display device that does not cause defects such as firing and after-image over a long period of time in relation to display performance. Therefore, The demand for the improvement of the reliability with regard to the electric characteristics becomes increasingly strong. However, it is very difficult to meet the demand for the conventional colored and radiation-curable resin composition.

It is an object of the present invention to provide a color filter which is excellent in solvent re-solubility of a dry coating film and excellent in reliability in terms of electrical characteristics represented by voltage holding ratio without generating color unevenness in a film after exposure and development, Sensitive resin composition and the like which can be used as a radiation-sensitive resin composition.

Another object of the present invention is to provide a method for efficiently and advantageously producing the radiation-sensitive resin composition.

It is still another object of the present invention to provide a color filter manufactured from the radiation sensitive composition.

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

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 achieved by firstly,

(B) a radiation-sensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) (B2) an allyl group-containing compound; (b3) at least one member selected from the group consisting of an aromatic vinyl compound, an indene, an N-substituted maleimide, and a polymer molecular chain (Meth) acryloyl groups at one end, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides and (B2) and at least one other unsaturated compound selected from the group consisting of an aliphatic conjugated diene and a copolymer of at least one unsaturated compound different from the above (b1) and (b2) (Hereinafter simply referred to as "Mn") measured by gel permeation chromatography (GPC) and polystyrene reduced weight average molecular weight (Mw) Sensitive resin composition for a color filter (hereinafter referred to as "radiation-sensitive resin composition (I)") having a weight average molecular weight (Mw / Mn) of 1.0 to 2.0.

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

And the color filter formed by using the radiation-sensitive resin composition (I).

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

And a color liquid crystal display device including the color filter.

Hereinafter, the present invention will be described in detail.

Sensitizing radiation property  Resin composition (I)

- (A) Colorant -

The coloring agent in the radiation-sensitive resin composition (I) is not particularly limited and may be any one of a pigment, a dye and a natural coloring matter. Since color filters are required to have high purity and high light transmittance coloring and heat resistance, pigments are preferable, and organic pigments or carbon black are particularly preferable.

As the organic pigment, for example, a compound classified as a pigment in a color index, specifically, a color index (CI) number given below is given.

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

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

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

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38; C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment Blue 80; C.I. Pigment Green 7, C.I. Pigment Green 36; C.I. Pigment Brown 23, C.I. Pigment Brown 25;

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

Among these organic pigments, C.I. Pigment Yellow 83, C.I. Pigment Yellow 139, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36; C.I. Pigment Violet 23, C.I. Pigment Blue 60 and C.I. Pigment Blue 80 is preferable.

The organic pigments may be used alone or in combination of two or more. Further, an organic pigment and carbon black may be mixed and used.

In the present invention, the radiation-sensitive resin composition (I) can be produced by a suitable method. When a pigment is used as the coloring agent, the pigment is dispersed in a solvent in the presence of a dispersing agent such as a bead mill, (B), the components (C) and (D) described below and, if necessary, additional solvents and other additives to be described later, and mixing them with each other to prepare a pigment dispersion. .

As the dispersing agent used for the preparation of the pigment dispersion, a suitable dispersing agent such as cationic, anionic, nonionic or amphoteric can be used. Among them, a dispersing agent containing a compound having a urethane bond (hereinafter referred to as "urethane-based dispersing agent") is preferable.

The urethane bond is generally represented by the formula R'-NH-COO-R "wherein R 'and R" are, independently of each other, an aliphatic, alicyclic or aromatic monovalent or multivalent organic group, Group is referred to as being bonded to a group having another urethane bond or another group) and may be present in the lipophilic group and / or the hydrophilic group in the urethane-based dispersant and may be present in the main chain and / or side chain of the urethane- Also, one or more of the urethane dispersants may be present. When two or more urethane bonds are present in the urethane-based dispersant, each urethane bond may be the same or different.

Examples of such urethane-based dispersing agents include reaction products of diisocyanate and / or triisocyanate with a polyester having a hydroxyl group at one end and / or a polyester having a hydroxyl group at both ends.

Examples of the diisocyanate include benzene diisocyanate such as benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; Toluene diisocyanate such as toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, and toluene-3,5-diisocyanate; 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3- Aromatic diisocyanates such as xylylene diisocyanate such as isocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2,5-diisocyanate and 1,4- And the like.

Examples of the triisocyanate include benzene triisocyanate such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate and benzene-1,3,5-triisocyanate; Toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, and toluene-2,4,6-triisocyanate; Xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2,4,5-triisocyanate, - 2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4-xylene-2,3,5-triisocyanate, 1,4- And aromatic triisocyanates such as xylene triisocyanate such as 6-triisocyanate.

These diisocyanates and triisocyanates may be used alone or in combination of two or more.

Examples of the polyester having a hydroxyl group at one terminal and the polyester having a hydroxyl group at both terminals include polycaprolactone having a hydroxyl group at one terminal or both terminals, polyvalerolactone having a hydroxyl group at one terminal or both terminals, A polylactone having a hydroxyl group at one end or both ends of a polypropiolactone or the like having a hydroxyl group at one end or both ends; Polyethylene terephthalate having a hydroxyl group at one end or both ends, and polybutylene terephthalate having a hydroxyl group at one end or both terminals, and polycondensed polyester having a hydroxyl group at one or both terminals.

The polyester having a hydroxyl group at one end thereof and the polyester having a hydroxyl group at both terminals may be used alone or in combination of two or more.

The urethane-based dispersant in the present invention is preferably a reaction product of an aromatic diisocyanate and a polylactone having a hydroxyl group at one end and / or a polylactone having hydroxyl groups at both ends, and more preferably a reaction product of a toluene diisocyanate and a poly The reaction products of caprolactone and / or polycaprolactone having hydroxyl groups at both terminals are preferred.

Specific examples of such a urethane-based dispersing agent include trade names such as Disperbyk 161, Disperbyk 170 (manufactured by BYK), EFKA (manufactured by EFKA), Diparron 170 Manufactured by Sumitomo Kasei Co., Ltd.) and the like.

The Mw of the urethane-based dispersant in the present invention is preferably 5,000 to 50,000, more preferably 7,000 to 20,000.

These urethane dispersants may be used alone or in combination of two or more.

It is also preferable as a (meth) acrylic dispersion system dispersant containing a (co) polymer of a (meth) acrylic monomer.

Specific examples of such a (meth) acrylic dispersant include Disperbyk 2000, Disperbyk 2001 (manufactured by BYK), and the like.

The (meth) acrylic dispersant may be used alone or as a mixture of two or more thereof.

The amount of the dispersant to be used in the preparation of 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, 10 to 50 parts by weight. If the amount of the dispersing agent used is more than 100 parts by weight, developability and the like may be deteriorated.

Examples of the solvent to be used in the preparation of the pigment dispersion include the same solvents as those exemplified for the liquid composition of the radiation-sensitive resin composition described later.

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

In the production of the pigment dispersion, when a bead mill is used, a pigment mixture, a pigment, a solvent and a dispersing agent are preferably mixed with glass beads or titania beads having a diameter of about 0.5 to 10 mm, Can be carried out by mixing and dispersing while cooling with 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 mixture is preferably about 20 to 50% of the mill capacity. The treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

In addition, when the roll mill is produced, for example, a three-roll mill or a two-roll mill may be used and the pigment mixture may be cooled, preferably with cooling water or the like.

In this case, the roll interval is preferably 10 m or less, and the shearing force is preferably about 10 ⁸ dyn / sec. 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 radiation-sensitive resin composition (I) is at least one compound (b1) selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an unsaturated phenol compound (hereinafter referred to as "unsaturated compound (b1) (B2) an allyl group-containing compound (hereinafter referred to as "unsaturated compound (b2)"), (b3) an unsaturated compound different from (b1) ) (Hereinafter also referred to as "polymerizable unsaturated compound" in combination of components (b1) to (b3)), a copolymer having a ratio Mw / Mn of Mw / Mn of 1.0 to 2.0 (Hereinafter referred to as "copolymer (B1)").

Examples of the unsaturated carboxylic acid or its acid anhydride in the unsaturated compound (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof; Mono [(meth) acryloyloxyalkyl] monovalent monocarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and phthalic acid mono [2- (meth) acryloyloxyethyl] ester; (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate and the like.

Among these unsaturated carboxylic acids or acid anhydrides thereof, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively referred to as light ester HOA-MS and light ester HOA- (Manufactured by Kyoeisha Chemical Co., Ltd.).

Examples of the unsaturated phenol compound include o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3- unsaturated phenols such as m-isopropenyl phenol and p-isopropenyl phenol; 2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl- And unsaturated naphthol such as naphthol.

In the present invention, examples of the unsaturated compound (b1) include (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono (meth) acrylate, p- (Meth) acrylic acid is particularly preferable.

As the unsaturated compound (b2), a compound having an allyl group and another polymerizable unsaturated bond as a polymerizable unsaturated bond (hereinafter referred to as an "unsaturated compound (b2-1)"), a compound having only an allyl group as a polymerizable unsaturated bond And the like. Of these, the unsaturated compound (b2-1) is preferred.

Examples of the unsaturated compound (b2-1) include allyl (meth) acrylate, allyl crotonate, allyl alpha -chloroacrylate, allyl cinnamate, monoallyl maleate, monoallyl fumarate and the like. Among these, allyl (meth) acrylate is particularly preferable.

Examples of the unsaturated compound (b2) other than the unsaturated compound (b2-1) include allyl acetate, allyl propionate, allyl butyrate, allyl benzoate, monoallyl succinate, monoallyl phthalate, allyl methyl ether, allyl ethyl ether, allyl Glycidyl ether, p-allylbenzyl methyl ether, p-allylbenzyl glycidyl ether, and the like.

The unsaturated compound (b2) may be used alone or in admixture of two or more.

Examples of the unsaturated compound (b3) include an aromatic vinyl compound, an indene, an N-substituted maleimide, a macromonomer having a (meth) acryloyl group at one end of the polymer molecular chain, an unsaturated carboxylic acid ester, Unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides and aliphatic conjugated dienes are used. Examples of the unsaturated compound (b3) include styrene,? -Methylstyrene, p-styrenesulfonic acid, o-vinyltoluene, m- vinyltoluene, p- vinyltoluene, p- chlorostyrene, o- 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, aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether; Indene such as indene and 1-methylindene;

Hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-hydroxyphenylmaleimide, N-substituted maleimides such as methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide, and N-substituted maleimides such as N-cyclohexylmaleimide;

A macromonomer having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate or polysiloxane box);

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether Acrylate, propylene glycol monomethyl ether (meth) acrylate, (Meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- Unsaturated carboxylic acid esters such as cyproethyl (meth) acrylate and glycerol (meth) acrylate;

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

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

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

Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and the like;

(Meth) acrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide,? -Chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide;

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

And the like.

Among these unsaturated compounds (b3), styrene, macromonomer, N-substituted maleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl Acrylate, and glycerol mono (meth) acrylate. Among the macromonomers, polystyrene macromonomers, polymethyl (meth) acrylate macromonomers and the like are particularly preferred. Among the N-substituted maleimides, N-phenylmaleimide and N-cyclohexylmaleimide are particularly preferred .

The unsaturated compound (b3) may be used alone or in admixture of two or more.

In the present invention, more preferred examples of the copolymer (B1) include (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate and ω-carboxypolycaprolactone mono (B1) containing at least one member selected from the group consisting of polystyrene macromonomers, polymethyl (meth) acrylate macromonomers, polymethylmethacrylate macromonomers, At least one member selected from the group consisting of N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol mono (B3) containing at least one member selected from the group consisting of styrene, methyl (meth) acrylate and phenyl (meth) acrylate, and an unsaturated compound (B1) (hereinafter referred to as "copolymer (B1-1)"),

More preferred examples of the more preferable copolymer (B1) include unsaturated compounds (b1) containing (meth) acrylic acid as an essential component and optionally mono [2- (meth) acryloyloxyethyl] (Meth) acrylate as essential components and at least one monomer selected from the group consisting of polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (Meth) acrylate, benzyl (meth) acrylate, and glycerol mono (meth) acrylate, and may optionally contain at least one member selected from the group consisting of styrene, methyl ) And a copolymer (B1) (hereinafter referred to as "copolymer (B1-2)") of an unsaturated compound (b3) containing at least one member selected from the group consisting of acrylate and acrylate.

As specific examples of the copolymer (B1-2)

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

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

(Meth) acrylate / allyl (meth) acrylate / polymethyl (meth) acrylate macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylate / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

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

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

(Meth) acrylate / allyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

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

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

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

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

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

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

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

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

(Meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer / mono [2- (meth) acryloyloxyethyl]

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

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

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

(Meth) acrylate / stearic acid mono [2- (meth) acryloyloxyethyl] / allyl (meth) acrylate / N-cyclohexylmaleimide / benzyl

(Meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer (meth) acrylate / mono [2- (meth) acryloyloxyethyl] And the like.

Specific examples of the copolymer (B1-1) other than the copolymer (B1-2)

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

(Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / polystyrene macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / polymethyl (meth) acrylate macromonomer / benzyl

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

(Meth) acrylic acid /? - carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl

(Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / styrene copolymer,

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

(Meth) acrylic acid /? -Carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl

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

(Meth) acrylate / polymethyl (meth) acrylate macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate /? - carboxypolycaprolactone mono Acrylate copolymer,

(Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / styrene copolymer,

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

(Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer,

(Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,

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

(Meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate / mono [2- (meth) acryloyloxyethyl] / omega-carboxypolycaprolactone mono Meth) acrylate copolymer,

(Meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / styrene copolymer, mono [2- (meth) acryloyloxyethyl] / omega-carboxypolycaprolactone mono

(Meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / monosuccinate mono [2- (meth) acryloyloxyethyl] / omega -carboxypolycaprolactone mono Acrylate / styrene copolymer,

(Meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer (meth) acrylate / monosuccinate mono [2- (meth) acryloyloxyethyl] / omega-carboxypolycaprolactone mono ,

(Meth) acrylate / allyl (meth) acrylate / N-cyclohexylmaleimide / benzyl (meth) acrylate / monosuccinate mono [2- (meth) acryloyloxyethyl] / omega-carboxypolycaprolactone mono ) Acrylate / styrene copolymer,

(Meth) acrylate / allyl (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / monosuccinate mono [2- (meth) acryloyloxyethyl] / omega -carboxypolycaprolactone mono Acrylate / glycerol mono (meth) acrylate / styrene copolymer

And the like.

In the copolymer (B1), 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 unsaturated compound (b2) To 70% by weight, particularly preferably 5 to 40% by weight, and the copolymerization ratio of the unsaturated compound (b3) is preferably 1 to 80% by weight, particularly preferably 5 to 60% by weight.

In the present invention, the radiation-sensitive resin composition (I) having excellent sensitivity, substrate adhesion, solvent resistance and the like can be obtained by setting the copolymerization ratio of each unsaturated compound in the copolymer (B1) within the above range.

The Mw / Mn of the copolymer (B1) is 1.0 to 2.0, preferably 1.0 to 1.7, particularly preferably 1.0 to 1.4.

The Mw of the copolymer (B1) is preferably 1,000 to 45,000, more preferably 3,000 to 20,000, and particularly preferably 4,000 to 10,000.

By using the copolymer (B1) having such a ratio of Mw / Mn, preferably further having the above-mentioned specific Mw value, a radiation-sensitive resin composition (I) having excellent developability is obtained, It is possible to form a pixel having an edge and to prevent residues, background dirt, film residue and the like from being generated on the substrate of the unexposed portion and on the light shielding layer during development, and furthermore, It is possible to realize a high product yield without generating dry foreign matter at the time of manufacture and further effectively prevent "burning" of the color filter.

In the radiation-sensitive resin composition (I), the copolymer (B1) may be used alone or in combination of two or more.

The copolymer (B1) can be produced, for example, by polymerizing a polymerizable unsaturated compound in the presence of a radical polymerization initiator system for producing a living radical in a solvent.

In the living radical polymerization, in the case where the polymerizable unsaturated compound contains a compound having a functional group which may inactivate the living radical, such as a carboxyl group, in order to prevent the growth end from inactivating, The copolymer (B1) can be obtained by protecting the functional group by, for example, esterification or the like and then carrying out polymerization and deprotection.

Various radical polymerization initiator systems used for living radical polymerization have been proposed. For example, TEMPO system (MKGeorges, RPNVeregin, PMKazmaier, GKHamer, Macromolecules, 1993) proposed by Georges et al. (See Matyjaszewski, K. Coca, S. Gaynor, et al., Vol. 26, p. 2987), a combination of copper bromide and bromine-containing ester compounds proposed by Matyjaszewski et al. A system comprising a combination of carbon tetrachloride and ruthenium (II) complexes proposed by Hamasaki et al. (See, for example, G. Wei, M. Woodworth, BE Macromolecules, 1997, Vol. 30, , S. Kamigaito, M. Sawamoto, M. Macromolecules, 2002, Vol. 35, p.2934), Japanese Patent Publication No. 3639859 (Japanese Patent Publication No. 2000-515181), Japanese Patent Publication No. 2002 -500251 and Japanese Patent Laid-Open Publication No. 2004-518773 It is as described, and the like system comprising a combination of the thiocarbonyl compound and the radical initiator having a large chain transfer constant greater than 0.1.

As a preferable radical polymerization initiator system to be used for the living radical polymerization, a system in which the living radical which is the growth end is not inactivated is appropriately selected depending on the kind of the polymerizable unsaturated compound used. However, considering the polymerization efficiency and metal- A combination of a jane thiocarbonylthio compound and a radical initiator is preferred.

The combination of the thiocarbonylthio compound and the radical initiator is disclosed in Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181), Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication No. 2004-518773 In addition to Japanese Patent Application Laid-Open Nos. 2002-508409, 2002-512653, 2003-527458, and 3634843 (Japanese Patent Application Laid-Open No. 2003-536105) And Japanese Patent Laid-Open Publication No. 2005-503452.

Japanese Patent Publication No. 3639859 (Japanese Patent Publication No. 2000-515181), Japanese Patent Publication No. 2002-500251, Japanese Patent Publication No. 2004-518773, and Japanese Patent Publication No. 2002-508409 As described above, a random copolymer or a block copolymer having a narrow molecular weight distribution can be obtained by living radical polymerization of a polymerizable unsaturated compound in the presence of a thiocarbonylthio compound and a radical initiator. Since the functional group derived from the thiocarbonylthio compound can be introduced into the obtained random copolymer and block copolymer, the copolymer can be dissolved in a water-soluble gel (see Japanese Patent Application Laid-Open No. 2002-512653), a photoresist (See Japanese Patent Application Laid-Open No. 2003-527458), and a surfactant (see Japanese Patent No. 3634843 (Japanese Patent Application Laid-open No. 2003-536105)).

In the present invention, preferred examples of the copolymer (B1) include a group represented by the following general formula (i) (hereinafter referred to as a "terminal group (i)") or a group represented by a general formula (Hereinafter referred to as "thiocarbonylthio-terminated copolymer (B1)") having a terminal group (hereinafter referred to as "terminal group (ii)").

(I)

In formula ( ¹⁾ , Z ¹ represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group, -OR, -SR, -N (R ) 2, -OC (= O) R, -C (= O) OR, -C (= O) N (R) 2, -P (= O) (OR) ₂ , -P (= O) (R) ₂ or a polymer chain, each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent heterocyclic group having 3 to 18 total atoms of a carbon atom and a bivalent atom and the alkyl group having 1 to 20 carbon atoms and the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , A monovalent heterocyclic group having 3 to 20 total atoms and R each may be substituted]

(Ii)

In formula (ii), Z ² represents an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a complex valency group having a total of 3 to 20 carbon atoms and a bidentate atom An m-valent group derived from a cyclic compound or an m-valent group having a polymer chain and having an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having a carbon number of 6 to 20, The m-valent groups derived from the heterocyclic compound of the formulas (1) to (20) each may be substituted, and m is an integer of 2 or more,

When the thiocarbonylthio-terminated copolymer (B1) has one polymer chain, usually the terminal group (i) is bonded to the terminal of one of the polymer chains, while the terminal group (i) , Terminal group (ii), or a chain terminator. This "chain stopper" is a group determined according to the reaction conditions during the living radical polymerization, and when the terminal group (ii) is bonded to the polymer chain, it is not bonded to the polymer chain in the terminal group (ii) -1) coupled hands (S-) are combined with a chain stop. On the other hand, chain-stopping groups may be the R ² in the formula (2) to be described later for R ¹ in formula (I) to be described later.

When two or more polymer chains constituting the polymer chain are two or more, usually each polymer chain is bonded to the terminal group (ii) at one end thereof, so that the copolymer (I) has a branched structure and the other polymer chains (I), a terminal group (ii) or a chain terminator may be bonded to the terminal end of the polymer. When the terminal group (ii) is bonded to the other terminal of the polymer chain, (m-1) bonding hands (S-) not bonded to the polymer chain in the terminal group (ii) (i), the terminal group (ii) or the chain terminator. On the other hand, chain-stopping groups may be the R ² in the formula (2) to be described later for R ¹ in formula (I) to be described later.

In formula (i), Z ¹ represents an alkyl group having 1 to 20 carbon atoms which may be substituted, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, a total of 3 to 20 , Examples of the monovalent group having a monovalent heterocyclic group, an optionally substituted R, and a polymer chain include the same ones as those of the corresponding groups of Z ¹ in the following formula (1) have.

In the formula ii, m-valent group derived from an alkane having 1 to 20 carbon atoms which may be substituted for Z ^2, group m-valent derived from an aromatic hydrocarbon which may be substituted having 6 to 20 carbon atoms which may be substituted with Examples of the m-valent group and the m-valent group having a polymer chain derived from the heterocyclic compound having the total number of atoms of the binomial atom of 3 to 20 include the preferable ones such as those represented by Z ² in the following formula May be the same as the corresponding groups.

The thiocarbonylthio-terminated copolymer (B1) can be produced, for example, by living radical polymerization using a thiocarbonylthio compound represented by the following formula (1) or (2) as a polymerizable unsaturated compound as a molecular weight controller. In this living radical polymerization, a radical initiation system is usually used.

Z ¹ represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a total of 3 to 20 a monovalent heterocyclic group, -OR, -SR, -N (R ) 2, -OC (= O) R, -C (= O) OR, -C (= O) N (R) 2, -P (= O) (OR) ₂ , -P (= O) (R) ₂ or a polymer chain, each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent heterocyclic group having 3 to 18 total atoms of a carbon atom and a bivalent atom and the alkyl group having 1 to 20 carbon atoms and the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , A monovalent heterocyclic group having a total of 3 to 20 atoms and R may be respectively substituted, p is an integer of 1 or more, and R ¹ is an alkyl group having 1 to 20 carbon atoms when p = 1, A monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a monovalent heterocyclic group of 3 to 20 atoms in total of a carbon atom and a bivalent atom, -OR, -SR, -N (R) ₂ or a monovalent group having a polymer chain, each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, And a pivalent group derived from an alkane having 1 to 20 carbon atoms and an aromatic hydrocarbon having 6 to 20 carbon atoms when p > = 2, and a pivalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms Group, a p-valent group derived from a heterocyclic compound having a total of 3 to 20 atoms of a carbon atom and a bidentate atom, or a p-valent group having a polymer chain, wherein the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic group having 3 to 20 carbon atoms Ebony A monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 total atoms, a pivalent group derived from R, an alkane having 1 to 20 carbon atoms, an aromatic hydrocarbon having 6 to 20 carbon atoms, The resulting p-valent group and the p-valent group derived from the heterocyclic compound having a total of 3 to 20 atoms can be respectively substituted]

Z ² represents an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having a total of 3 to 20 carbon atoms and a bidentate atom An m-valent group derived from a cyclic compound or an m-valent group having a polymer chain, the m-valent group derived from an alkane having a carbon number of 1 to 20, the m-valent group derived from an aromatic hydrocarbon having a carbon number of 6 to 20, To R < ² > each may be substituted, and R < ² > is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , carbon atoms and the total number of atoms of the binary atom represents a monovalent group having a monovalent heterocyclic ring of 3 to 20 dishes, -OR, -SR, -N (R ) 2, or a polymer chain, each R is, independently of each other An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 atoms in total of a carbon atom and a bivalent atom, A monovalent alicyclic hydrocarbon group having from 3 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having from 3 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having from 6 to 20 carbon atoms, a monovalent heterocyclic group having from 3 to 20 carbon atoms, Is an integer of 2 or more]

Examples of the alkyl group having 1 to 20 carbon atoms for Z ^{1 in} the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl- N-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and n-eicosyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms for Z ¹ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 9-anthracenyl group, Benzyl group,?,? - dimethylbenzyl group, and phenethyl group.

Examples of the monovalent heterocyclic group having 3 to 20 atoms in total of the carbon atom and the binomial atom of Z ¹ include oxiranyl group, aziridinyl group, 2-furanyl group, 3-furanyl group, 2-tetrahydro Pyrrolidinyl, 3-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrrolidinyl, Tetrahydrothiopyranyl group, 4-tetrahydropyranyl group, 2-thienyl group, 3-thienyl group, 4-thienyl group, A 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, a 2-piperidinyl group, a 3-piperidinyl group, a 4-piperidinyl group, a 2-morpholinyl group, .

Also, -OR, -SR, -N (R ) of the _{^{Z 1 2, -OC (= O}} ) R, -C (= O) OR, -C (= O) N (R) 2, -P (= O) (oR) _2, and -P (= O) (R) R alkyl group having 1 to 18 carbon atoms in the _second, the total number of atoms of the monovalent aromatic hydrocarbon group or a carbon atom and having from 6 to 18 carbon atoms of the binary 3 to examples of heterocyclic monovalent of 18, for example an alkyl group of 1 to 20 carbon atoms exemplified with respect to the Z ^1, of the C6 to C20 monovalent aromatic hydrocarbon group or a carbon atom and the total number of atoms of the binary atoms from 3 to 20 of the first Among the optionally substituted heterocyclic groups, a group having a carbon number or total atomic number of 18 or less is exemplified.

Examples of the alkenyl group having 2 to 18 carbon atoms of R include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, Pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group and 5-hexenyl group.

Examples of the substituent for the alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 carbon atoms and the total number of atoms of the carbon atom and the bivalent atom, and the substituent for R include, for example, , carboxylic acid base, sulfonic acid group, a sulfonic acid base, an isocyanate group, a cyano group, a vinyl group, an epoxy group, in addition to the silyl group, a halogen atom, an -OR, -SR, -N (R) illustrated with respect to Z ¹ _2, - OC (= O) R, -C (= O) oR, -C (= O) N (R) 2, -P (= O) (oR) 2 or -P (= O) (R) 2 , or, Examples of the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, the monovalent heterocyclic group having 3 to 18 atoms in total of the carbon atom and the bivalent atom, And can be appropriately selected from the same group. These substituents may be present in the substituted derivatives in one or more than one. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivatives do not exceed 20.

Examples of the monovalent group having a polymer chain of Z ¹ include? -Olefins such as ethylene and propylene; Aromatic vinyl compounds such as styrene and? -Methylstyrene; Vinyl halides such as vinyl fluoride, vinyl chloride and vinylidene chloride; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; Esters of unsaturated alcohols such as vinyl acetate and allyl acetate; Unsaturated carboxylic acids such as (meth) acrylic acid and p-vinylbenzoic acid; (Meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t- (Meth) acrylic acid esters such as hexyl and cyclohexyl (meth) acrylate; (Meth) acrylamides such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; Unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; Butadiene, isoprene, and other unsaturated compounds such as isobutylene, butadiene, isoprene, and the like, besides monovalent groups having an addition polymerization type polymer chain formed from at least one kind of unsaturated compounds such as polyoxyethylene A polyether such as propylene, and a monovalent group having a polyvalent polymer chain such as polyester, polyamide, and polyimide, a polycondensation polymer chain, and the like. In the monovalent group having these polymer chains, the polymer chain may be directly bonded to the carbon atom of the thiocarbonyl group in the formula (1), for example, -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ May be bonded to the carbon atom of the thiocarbonyl group in the general formula (1) through a connecting hand such as CH ₂ -COO-.

In formula (1), a plurality of Z ^{1 s} present may be the same or different from each other.

In formula (1), when p = 1, R ¹ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, A monovalent heterocyclic group having a total of 3 to 20 atoms, a monovalent heterocyclic group having -OR, -SR, -N (R) ₂ or a polymer chain, and the alkyl group having 1 to 20 carbon atoms, the monovalent group having 3 to 20 carbon atoms An alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total of a carbon atom and a bivalent atom, and R may be substituted, respectively.

An alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 total atoms, -OR, -SR, -N (R) ₂ , The monovalent group having a polymer chain includes, for example, the same groups as those exemplified for the corresponding groups of the above Z ¹ . R ¹ (However, p = 1) In the monovalent groups having a polymer chain and in which the polymer chain can be bonded directly to the sulfur atom in the general formula (1), for _{example, -CH 2 -COO-, -C (CH} 3 (CN) CH ₂ CH ₂ --COO--, and the like.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, and a cyclohexenyl group.

Examples of the substituent for the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms represented by Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, The monovalent heterocyclic group of 3 to 20, and the group exemplified for the substituent for R, and these substituents may be present in one or more of the substituted derivatives or in one or more of them. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivatives do not exceed 20.

When p > = 2, R &^lt; 1 > is a pivalent group derived from an alkane having 1 to 20 carbon atoms, a pivalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, A p-valent group derived from a heterocyclic compound having a total of 3 to 20 carbon atoms, a p-valent group derived from an alkane, a p-valent group derived from an aromatic hydrocarbon and a p-valent group derived from an aromatic hydrocarbon, Each of the resulting p-valent groups may be substituted.

Examples of the alkane having 1 to 20 carbon atoms include methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, n-hexane, -Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane and the like.

Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include benzene and 1,4-dimethylbenzene (for example, carbon atoms of the respective methyl groups in the 1,4-position are bonded to sulfur atoms in the formula (1)), 1 , 2,4,5-tetramethylbenzene (for example, the carbon atom of each methyl group in the 1,2,4,5-position is bonded to the sulfur atom in the formula (1)), 1,2,3,4,5, 6-hexamethylbenzene (for example, the carbon atom of each methyl group in the 1,2,3,4,5,6-position is bonded to the sulfur atom in formula (1)), 1,4-di-i-propylbenzene For example, the carbon atom at the 2-position of each i-propyl group in the 1,4-position is bonded to the sulfur atom in the formula (1)), naphthalene, and anthracene.

Examples of the heterocyclic compound having 3 to 20 atoms in total include oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thian, pyridine, piperidine , Morpholine, and the like.

Examples of the substituent for the p-substituted group derived from the above-mentioned p-substituted group derived from an alkane having 1 to 20 carbon atoms, the p-substituted group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms and the heterocyclic compound having 3 to 20 atoms in total include Examples of the alkyl group having 1 to 20 carbon atoms represented by Z ^1, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total of carbon atoms and bivalent atoms, And these substituents may be present in the substituted derivatives in one or more, or in one or more. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivatives do not exceed 20.

Examples of the polymer chain providing the p-valent group of R < ¹ > include the same addition polymer chains as those described above for the monovalent group having the polymer chain of Z < ^{1 &} gt ;, the middle part polymer chain and the polycondensation polymer chain. In p-valent groups having a polymer chain of the R ^1, wherein the polymer chain may be bonded directly to the sulfur atom in the formula (1), for example _{-CH 2 -COO-, -C (CH 3} ) (CN) CH 2 CH _{2 >} -COO < - > and the like.

Next, that in the general formula (2), as the C 1 -C 20 alkane to provide an m-valent of Z ^2, for example the same as compounds exemplified for the alkane group having 1 to 20 carbon atoms to provide an p-valent of the R ¹ .

Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms for providing the m-valent group of Z ² include the same ones as those exemplified for the aromatic hydrocarbon having 6 to 20 carbon atoms for providing the p-valent group of R ¹ .

Also, as the total of the heterocyclic compounds of the atom number of 3 to 20 carbon atoms and the binary atoms to provide an m-valent of Z ^2, for example, the number g total atoms of carbon and binary atoms to provide an p-valent of the R ¹ 3 To 20 of the heterocyclic compound.

As the substituent for the m-valent group derived from the m-valent group derived from an alkane having 1 to 20 carbon atoms of Z ² , the m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms and the m-valent group derived from a heterocyclic compound having a total of 3 to 20 atoms, for example, with respect to the substituent for the C 1 -C 20 alkyl group, having 6 to a monovalent aromatic hydrocarbon group of 20, a monovalent heterocyclic ring of the total number of atoms of carbon atoms and binary atoms of 3 to 20 dishes and R of the Z ¹ And the substituent groups may be present in the substituted derivatives in an amount of one or more, or one or more. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivatives do not exceed 20.

Examples of the polymer chain providing the m-valent group of Z ² include the same addition polymer chain as exemplified for the monovalent group having the polymer chain of Z ¹ above, the polymer chains of the central portion and the polycondensation polymer chain have. In the m-valent group having a polymer chain of Z ² , the polymer chain may be directly bonded to the carbon atom of the thiocarbonyl group in the general formula (2), for example, -CH ₂ -COO-, -C (CH ₃ ) ₂ CH ₂ -COO-, or the like, to the carbon atom of the thiocarbonyl group in the general formula (2).

In the formula 2, the number of carbon atoms of R ^2, 1 to 20 alkyl group, having 6 to a monovalent aromatic hydrocarbon group of 20 carbon atoms and the total number of atoms of 3 to 20 atoms binary monovalent heterocyclic tableware, -OR, -SR , -N (R) ₂ and a polymer chain, or a substituted derivative thereof, can be exemplified by the same groups as those exemplified for the corresponding groups in the above Z ¹ . In the monovalent group having a polymer chain of R ² , the polymer chain may be directly bonded to a sulfur atom in the formula (2), for example, -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ CH ₂ -COO < - > and the like.

Furthermore, R ² of the monovalent alicyclic having 3 to 20 carbon atoms group hydrocarbon group or as their substituted derivatives, such as the R ¹ (However, p = 1) having a carbon number of 3 monovalent aliphatic of 1 to 20 group of the hydrocarbon group or the His-substituted derivative May be the same as the groups exemplified above.

In the formula (2), a plurality of R ^{2 s} present may be the same or different from each other.

In the formula (2), when the connecting part between Z ² and -C (= S) -SR ² is an aliphatic carbon atom, the aliphatic carbon atom in Z ^{2 is} bonded to -C (= S) -SR ² , When the aromatic carbon atom is an aromatic carbon atom, an aromatic carbon atom in Z ^{2 is} bonded to -C (= S) -SR ^2, and when the connecting portion is a sulfur atom, the sulfur atom in -SR representing Z ² is -C ) -SR < ² >.

Particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (3) to (22).

These thiocarbonylthio compounds may be used alone or in combination of two or more.

In the present invention, in the living radical polymerization, one or more of other thiolcarbonylthio compounds and other molecular weight control agents such as? -Methylstyrene dimer and t-dodecylmercaptan may be used in combination.

The radical initiator used in the living radical polymerization is not particularly limited and those known as radical polymerization initiators can be used, and for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis Azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, 1,1'-bis (t-butylperoxy) cyclohexane, and t-butyl peroxypivalate; Hydrogen peroxide; And redox initiators including peroxides and reducing agents of these.

These radical initiators may be used alone or in combination of two or more.

The solvent used in the living radical polymerization is not particularly limited as long as the living radical is not inactivated, and examples thereof include propylene glycol monoalkyl ether such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;

Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Poly) alkylene glycol alkyl ether acetates such as acetate;

(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether; ;

Other ethers such as tetrahydrofuran;

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

Ketoalcohols such as diacetone alcohol (i.e., 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4-methylhexan-2-one;

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

Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n Propyl butyrate, n-butyl butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-butyl acetate, isobutyl acetate, n-butyl acetate, n- Propyl acetate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide

And the like.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3 Methyl 3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, formic acid n-propyl acetate, n-butyl methoxyacetate, Pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate are preferable Do.

These solvents may be used alone or in combination of two or more.

In the living radical polymerization, the amount of the thiocarbonylthio compound to be used is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 16 parts by weight, based on 100 parts by weight of the polymerizable unsaturated compound. The amount of the radical polymerization initiator to be used is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymerizable unsaturated compound.

The polymerization temperature is preferably 0 to 150 ° C, more preferably 50 to 120 ° C, and the polymerization time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 6 hours.

The copolymer (B1) can also be produced by subjecting a polymerizable unsaturated compound to radical polymerization and then refining through a reprecipitation method using two or more kinds of organic solvents having different polarities.

The radical polymerization for producing the copolymer (hereinafter referred to as "crude copolymer") to be provided in the tablet is not particularly limited, and can be carried out by conventional methods.

When the solvent used in the polymerization is a two-solvent solution in the following reprecipitation method, the crude polymer after polymerization can be supplied to the purification treatment as a polymer solution as it is or after the concentration is adjusted, The crude copolymer can be isolated by conventional methods and provided as a solid for purification.

After the radical polymerization, the obtained crude copolymer is purified by a reprecipitation method using two kinds of organic solvents having different polarities. That is, after insoluble impurities are removed by filtration or centrifugation as necessary, the solution of the crude copolymer in a good solvent is poured into a large amount, for example, 5 to 10 times the volume of the polymer solution in a precipitant (poor solvent) The copolymer is purified by reprecipitation. At this time, of the impurities remaining in the polymer solution, the impurities soluble in the precipitant remain in the liquid phase and are separated from the purified copolymer (B1).

Examples of the combination of the positive solvent and the precipitant used in the reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / Ethyl ketone / n-heptane and the like.

It is preferable to add the polymer solution as little as possible while agitating the precipitant vigorously before reprecipitating the crude copolymer, whereby the amount of the impurities introduced into the precipitate can be minimized. By repeating the reprecipitation treatment a plurality of times, the purity of the copolymer (B1) can be further increased. On the other hand, if the precipitated copolymer (B1) is too fine to be suitable for filtration, it can be separated by centrifugation or the like.

When more strict purification is required, the fractional precipitation method which is a variation of the reprecipitation method is preferable. That is, the purified copolymer (B1) is obtained by dissolving the crude copolymer in a good solvent and precipitating the crude copolymer as a solute while slightly changing the solvent condition, for example, the type, composition and temperature of the solvent, Is divided into a plurality of fractions slightly different in solubility and collected. For this method, it is preferred to add a precipitant to the polymer solution. The composition of the positive solvent and the precipitant may be changed in sequence, for example, the mixing ratio of the good solvent at a certain temperature, or the temperature may be changed by keeping the mixing ratio of the good solvent constant. By using this fractional precipitation method, the copolymer (B1) in a narrow molecular weight range can be collected at a good yield. Each fraction of the copolymer (B1) collected by the fractional precipitation method can be obtained as a solid by concentrating and drying one or more fractions according to the Mw value thereof.

Further, the copolymer (B1) obtained by the reprecipitation method may be further purified by adsorption / affinity chromatography or dialysis, if necessary.

The amount of the alkali-soluble resin in the radiation-sensitive resin composition (I) is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight, per 100 parts by weight of the (A) colorant. If the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, alkali developability may be deteriorated or background contamination or film residue may be formed on the substrate or the light-shielding layer of the unexposed portion. On the other hand, , The relative density of the pigment is lowered, so that it may be difficult to achieve the intended color density as a thin film.

- (C) Multifunctional monomer -

The multifunctional monomer in the radiation sensitive resin composition (I) is a monomer having two or more polymerizable unsaturated bonds. As such a polyfunctional monomer, for example,

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

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

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylol propane, pentaerythritol and dipentaerythritol, and dicarboxylic acid-modified products thereof; (Meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin;

Di (meth) acrylate of a polymer having a hydroxyl group at both ends such as poly-1,3-butadiene having hydroxyl groups at both terminals, polyisoprene having hydroxyl groups at both terminals, and polycaprolactone having hydroxyl groups at both terminals, Tris [2- (meth) acryloyloxyethyl] phosphate

And the like.

Of these polyfunctional monomers, poly (meth) acrylates of polyvalent alcohols having three or more valences and dicarboxylic acid-modified products thereof are preferable. Specific examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable, and trimethylolpropane triacrylate, pentaerythritol tetra Lithotri triacrylate and dipentaerythritol hexaacrylate have high pixel intensity and excellent smoothness of the pixel surface and are free from background contamination and film residue on the substrate of the unexposed portion and on the light shielding layer desirable.

The polyfunctional monomers may be used singly or in combination of two or more.

The amount of the polyfunctional monomer used in the radiation-sensitive resin composition (I) is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight, based on 100 parts by weight of the copolymer (B1). If the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be lowered. On the other hand, if the amount of the polyfunctional monomer exceeds 500 parts by weight, for example, alkali developability may deteriorate, There is a tendency that background contamination, film residue, and the like are likely to occur on the surface.

In the present invention, a monofunctional monomer having one polymerizable unsaturated bond may be used together with a polyfunctional monomer.

Examples of the monofunctional monomer include, in addition to the unsaturated compound (b1), the unsaturated compound (b2) and the unsaturated compound (b3) exemplified for the copolymer (B1), N-vinylsuccinimide, N- N-vinylpyrrolidone, N-vinylimidazole, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrolidine, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinyl nitrogen-containing heterocyclic compounds such as phenoxazine; M-5300, M-5400 and M-5600 (trade names, manufactured by Toagosei Co., Ltd.) under the trade names of N- (meth) acryloylmorpholine.

These monofunctional monomers may be used singly or in combination of two or more.

The use ratio of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less, based on the sum of the polyfunctional monomer and the monofunctional monomer. If the proportion of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the pixel tend to decrease.

- (D) Photopolymerization initiator -

The photopolymerization initiator in the radiation sensitive resin composition (I) can be obtained by exposure of radiation such as visible light, ultraviolet light, ultraviolet light, electron beam and X-ray to the polyfunctional monomer (C) and the monofunctional monomer Lt; RTI ID = 0.0 > of < / RTI >

Examples of such a photopolymerization initiator include a carbazole-based compound, an acetophenone-based compound, a nonimidazole-based compound, a triazine-based compound, a benzoin-based compound, a benzophenone-based compound, an -diketone-based compound, a polynuclear quinone- Based compounds, diazo compounds and the like.

As the photopolymerization initiator in the present invention, at least one selected from the group consisting of a carbazole-based compound, an acetophenone-based compound, a nonimidazole-based compound and a triazine-based compound is preferable, and a carbazole-based compound is particularly preferable .

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more.

In the radiation-sensitive resin composition (I), the amount of the photopolymerization initiator generally used is preferably 0.01 to 100 parts by weight based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer (if used, 80 parts by weight, more preferably 1 to 60 parts by weight. If the amount of the photopolymerization initiator is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the pixel patterns are arranged in a predetermined arrangement. If the amount exceeds 80 parts by weight, Tends to be easily removed from the substrate at the time of development.

Examples of the carbazole compound include compounds represented by the following formula (23) (hereinafter referred to as "carbazole compound (1)"), compounds represented by the following formula (hereinafter referred to as "carbazole compound ) ") And the like

Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 1 to 8 carbon atoms, a phenyl group which may be substituted, or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms , An alkoxyl group having 1 to 12 carbon atoms or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ^{6 s} may be the same or different, and R ⁷ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, A monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms, the plurality of R ^{7 s} may be the same or different from each other, and a Is an integer of 0 to 5, b is an integer of 0 to 5, and (a + b)? 5,

[Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 1 to 8 carbon atoms, a phenyl group which may be substituted, or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms , represents a cycloalkyloxy group having 1 to 12 carbon atoms, an alkoxyl group or a C 3 -C 8, and R ⁶ in the presence of a plurality of the same or different, R ⁷ is summoned oxygen-containing monovalent 4 to 20 carbon atoms clothing tableware , a monovalent sulfur-containing heterocyclic group of 4 to 20 carbon atoms or a monovalent nitrogen-containing heterocyclic group having 4 to 20, R ⁷ when there is a plurality of the same or different And, c is an integer from 0 to 5, d is from 1 to 5 being an integer, (c + d) ≤5, e is an integer of from 0 to 6;

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ³ in formulas (23) and (24) include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, , n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

Examples of the cycloalkyl group having 3 to 8 carbon atoms for R ³ include a cyclopentyl group and a cyclohexyl group.

In the formulas (23) and (24), examples of R ³ include a methyl group and an ethyl group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ in formulas (23) and (24) include a methyl group, an ethyl group, a n-propyl group, an i- -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

Examples of the cycloalkyl group having 3 to 8 carbon atoms for R ⁴ and R ⁵ include a cyclopentyl group and a cyclohexyl group.

Examples of the substituent for the phenyl group of R ⁴ and R ⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec- An alkyl group having 1 to 6 carbon atoms such as a hexyl group; A cycloalkyl group having 3 to 6 carbon atoms such as a cyclopentyl group and a cyclohexyl group; Alkoxyl groups having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy and t-butoxy; A cycloalkyloxy group having 3 to 6 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; A phenyl group; Halogen atoms such as a fluorine atom and a chlorine atom, and the like.

Examples of the monovalent alicyclic group having 7 to 20 carbon atoms (except for the cycloalkyl group) of R ⁴ and R ⁵ include a group having a 1-alkylcycloalkane skeleton, a group having a bicycloalkane skeleton, A group having a tricycloalkane skeleton, a group having a spiroalkane skeleton, a group having a terpene skeleton, a group having an adamantane skeleton, and the like.

In formulas (23) and (24), R ⁴ and R ⁵ are preferably a hydrogen atom, a methyl group, or an ethyl group.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{6 in} the general formulas (23) and (24) include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, , n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

Examples of the cycloalkyl group having 3 to 8 carbon atoms for R ⁶ include a cyclopentyl group and a cyclohexyl group.

Examples of the alkoxyl group having 1 to 12 carbon atoms for R ⁶ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a n-butoxy group, , n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group and n-dodecyloxy group.

Examples of the cycloalkyloxy group having 3 to 8 carbon atoms for R ⁶ include a cyclopentyloxy group and a cyclohexyloxy group.

In the general formulas (23) and (24), R ^{6 is preferably a} methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, methoxy group or ethoxy group.

Formula 23 and in formula 24, R ⁷ as having 4 to oxygen monovalent of 20-containing heterocyclic group, having 4 to a monovalent nitrogen-containing heterocyclic 20 group or a monovalent sulfur-containing heterocyclic ring of 4 to 20 carbon atoms tableware Such as a thiolanyl group, an azepinyl group, a dihydrorazepinyl group, a dioxolanyl group, a triazinyl group, an oxathianyl group, a thiazolyl group, an oxadiazinyl group, a dioxaindaninyl group, a dithianaphthalenyl group A thiazolyl group, an isothiazolyl group, a pyrazolyl group, a furanyl group, a pyranyl group, a pyridinyl group, a pyridazinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, An isoindolyl group, a benzofuranyl group, a benzothiophenyl group, an indolidinyl group, a chromenyl group, a quinolyl group, a quinolyl group, a quinolyl group, a quinolyl group, a quinolyl group, An isoquinolinyl group, a pyridyl group, a quinazolinyl group, a ne A phenanthridinyl group, a phenoxazinyl group, a phenoxazinyl group, a phenoxazinyl group, a phenoxazinyl group, a phenoxazinyl group, a phenanthridinyl group, a phenanthridinyl group, Thienyl group, thianthrenyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like.

In formulas (23) and (24), R ⁷ is preferably a tetrahydrofuranyl group, a tetrahydropyranyl group or the like.

In formula (23), a is preferably 0, 1 or 2, more preferably 1, and b is preferably 0 or 1, more preferably 0.

In the formula (24), c is preferably 0, 1 or 2, more preferably 1, d is preferably 1, and e is preferably 0, 1 or 2, more preferably 1.

Specific examples of the carbazole-based compound (1) include 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -1,2- -Carbazol-3-yl] -1,2-pentane-2-oxime-O-acetate, 1- [ 1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Yl] -ethan-1-one oxime-O-acetate, 1- [9-n-butyl (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-0-benzoate,

(9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol- - [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- (9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl} )

And the like.

Specific examples of the carbazole-based compound (2)

(9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9H-carbazol-3-yl] (9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9H-carbazol- -1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol- 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9H-carbazol- Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol- (O-acetyloxime), and the like.

Among these carbazole compound (1) and carbazole compound (2), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- -9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl- 4- (2,2- dimethyl- 1, 3- dioxolanyl) methoxybenzoyl} -9H. Ethyl] -6- {2-methyl-4- (2,2-dimethyl-1-oxo- , 3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime).

These carbazole-based compounds may be used singly or in combination of two or more.

When the carbazole-based compound is used as the photopolymerization initiator in the radiation-sensitive resin composition (I), the amount of the carbazole-based compound to be used is preferably 0.01 to 100 parts by weight based on 100 parts by weight of the (C) polyfunctional monomer or monofunctional monomer. To 80 parts by weight, more preferably 1 to 60 parts by weight, still more preferably 1 to 30 parts by weight. If the amount of the carbazole-based compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the pixel patterns are arranged in a predetermined arrangement. If the amount exceeds 80 parts by weight, The pixel tends to be easily detached from the substrate at the time of development.

Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) 2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- 1-one, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime).

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino- Phenyl] butanone-1, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime).

These acetophenone compounds may be used singly or in combination of two or more.

When the acetophenone-based compound is used as the photopolymerization initiator in the radiation sensitive resin composition (I), the amount of the acetophenone-based compound to be used is preferably 100 parts by weight or less based on 100 parts by weight of the polyfunctional monomer or monofunctional monomer (C) Preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight, and still more preferably 1 to 30 parts by weight. If the amount of the acetophenone compound used is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the pixel patterns are arranged in a predetermined arrangement. If the amount exceeds 80 parts by weight, The pixel tends to be easily detached from the substrate at the time of development.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2 -Imidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl- , 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis -Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and the like.

Among these imidazole-based compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferable, and 2,2'-bis (2,4-dichlorophenyl) -Tetraphenyl-1,2'-biimidazole is preferred.

These non-imidazole-based compounds are excellent in solubility in solvents, do not generate foreign substances such as untreated products and precipitates, have a high sensitivity and sufficiently accelerate the curing reaction by exposure with a small energy amount, Since the curing reaction does not occur, the coated film after exposure is clearly divided into a cured portion insoluble in the developing solution and an uncured portion having high solubility with respect to the developing solution, so that pixel patterns without undercuts are arranged in a predetermined arrangement A high-precision fine color filter can be formed.

These imidazole-based compounds may be used alone or in combination of two or more.

In the case of using a nonimidazole-based compound as the photopolymerization initiator in the radiation sensitive resin composition (I), the amount of the non-imidazole-based compound to be used is preferably 100 parts by weight or less per 100 parts by weight of the polyfunctional monomer (C) 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 1 to 20 parts by weight. When the amount of the imidazole-based compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the pixel patterns are arranged in a predetermined arrangement. If the amount exceeds 40 parts by weight, There is a tendency that the developed pixel is likely to come off from the substrate or to cause film roughness on the pixel surface.

In the present invention, when a non-imidazole-based compound is used as a photopolymerization initiator, it is preferable to use the following hydrogen donor in view of further improving the sensitivity.

The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole-based compound by exposure.

As the hydrogen donor in the present invention, a mercaptan-based compound, an amine-based compound and the like, which are defined below, are preferable.

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

The amine compound is a compound having a benzene ring or a heterocyclic ring as a base and having at least one, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as & System hydrogen donor ").

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

Hereinafter, the hydrogen donor will be described in more detail.

The mercaptan-based hydrogen donor may have at least one benzene ring or at least one heterocyclic ring, and may have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring can be formed.

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

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

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

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

In addition, the amine-based hydrogen donor may have at least one benzene ring or at least one heterocyclic ring, and may have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring can be formed.

The amine-based hydrogen donor may have at least one of the amino groups substituted with an alkyl group or a substituted alkyl group, and at a position other than the amino group, a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, And the like.

Specific examples of such amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 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, Benzophenone is preferred.

On the other hand, the amine-based hydrogen donor has an action as a sensitizer even in the case of a photopolymerization initiator other than the imidazole-based compound.

In the present invention, the hydrogen donors may be used singly or in combination of two or more, but it is preferable to use at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor in combination, And is also preferable in terms of high pixel intensity and high sensitivity.

Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / (Diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'- And the like. A more preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (diethylamino) A 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.

When the hydrogen donor is used in combination with the imidazole-based compound in the radiation-sensitive resin composition (I), the amount of the hydrogen donor to be used is preferably 0.01 to 100 parts by weight based on 100 parts by weight of the total amount of (C) the polyfunctional monomer or monofunctional monomer thereof. To 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, if the amount of the hydrogen donor is more than 40 parts by weight, the formed pixel tends to be detached from the substrate during development.

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) - And triazine-based compounds having a halomethyl group such as 4,6-bis (trichloromethyl) -s-triazine.

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

The triazine-based compounds may be used alone or in combination of two or more.

When the triazine-based compound is used as the photopolymerization initiator in the radiation sensitive resin composition (I), the amount of the triazine-based compound to be used is preferably 0.01 to 100 parts by weight, based on 100 parts by weight of the total amount of the (C) polyfunctional monomer or monofunctional monomer. 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the triazine compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the pixel patterns are arranged in a predetermined arrangement. If the amount exceeds 40 parts by weight, Tends to be easily removed from the substrate at the time of development.

- Other additives -

The radiation sensitive resin composition (I) contains the above components (A) to (D) as essential components, but may further contain other additives as required.

Examples of the other additives include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as nonionic surface active agents, cationic surface active agents, and anionic surface active agents; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; 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; And an anti-aggregation agent such as sodium polyacrylate.

Preparation of liquid composition

The radiation sensitive resin composition (I) is usually prepared as a liquid composition by mixing a solvent.

The solvent is appropriately selected so long as it does not react with the components (A) to (D) constituting the radiation-sensitive resin composition (I) or other additive components while dispersing or dissolving them, and has appropriate volatility Can be used.

As such a solvent, for example,

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;

Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Poly) alkylene glycol alkyl ether acetates such as acetate;

(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether; ;

Other ethers such as tetrahydrofuran;

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

Ketoalcohols such as diacetone alcohol (i.e., 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4-methylhexan-2-one;

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

Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n Propyl butyrate, n-butyl butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-butyl acetate, isobutyl acetate, n-butyl acetate, n- Propyl acetate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide

.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether, propylene glycol monomethyl ether acetate and the like are preferable from the viewpoints of solubility, pigment dispersibility, Ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, butyric acid i-butyl acetate, isopropyl myristate, isopropyl myristate, isopropyl myristate, Propyl, n-butyl butyrate, ethyl pyruvate and the like are preferable.

These solvents may be used alone or in combination of two or more.

The solvent may also be used in combination with a solvent such as benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, A high boiling solvent such as diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate may be used in combination.

The high-boiling solvent may be used alone or in combination of two or more.

Although the amount of the solvent to be used is not particularly limited, the total concentration of each component excluding the solvent of the liquid composition is preferably 5 to 50% by weight, particularly preferably 10 to 10% by weight, By weight to 40% by weight.

Method of forming color filter

Next, a method of forming the color filter of the present invention using the radiation sensitive resin composition (I) will be described.

A method for forming a color filter includes at least the following steps (1) to (4).

(1) a step of forming a coating film of a radiation-sensitive resin composition (I) on a substrate,

(2) a step of exposing at least a part of the coating film,

(3) a step of developing the coating film after exposure,

(4) a step of subjecting the coated film after development to a heat treatment (hereinafter referred to as "post baking").

Hereinafter, these steps will be described in order.

- (1) Process -

First, a light-shielding layer is formed on the surface of a substrate so as to divide a portion for forming a pixel if necessary, and a liquid composition of the radiation-sensitive resin composition (I) containing, for example, After the coating, prebaking is performed and the solvent is evaporated to form a coating film.

Examples of the substrate used in this step include ring-opening polymers of cyclic olefins and hydrogenated products thereof, as well as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and polyether sulfone have.

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

When the liquid composition is applied to the substrate, a suitable application method such as spin coating (application by spin coating), soft coating, roll coating, or application with a slit nozzle can be employed. The radiation sensitive resin composition (I) of the present invention has high solubility in a cleaning solvent even after drying, and is preferable for application by a slit nozzle.

The condition of prebaking is preferably about 70 to 110 DEG C for about 2 to 4 minutes.

The coating thickness is preferably 0.1 to 10 탆, more preferably 0.2 to 8.0 탆, and still more preferably 0.2 to 6.0 탆, as a film thickness after solvent removal.

- (2) Process -

Thereafter, at least a part of the formed coating film is exposed through, for example, a photomask having an appropriate pattern. As the radiation used in this step, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. Radiation with a wavelength in the range of 190 to 450 nm is preferred.

The exposure dose of the radiation is preferably about 10 to 10,000 J / m < ^{2 &} gt ;.

- (3) Process -

Thereafter, the exposed coated film is preferably developed using an alkaline developer, and the unexposed portion of the coated film is dissolved and removed to form a pattern.

Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- undecene, Cyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added in an appropriate amount to the alkali developing solution. On the other hand, after alkaline development, it is usually washed several times.

As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid deposition) development method and the like can be applied.

The developing condition is preferably about 5 to 300 seconds at room temperature.

- (4) Process -

Thereafter, the coated film after development is post-baked to obtain a substrate on which red pixel patterns including a cured product of the radiation sensitive resin composition (I) are arranged in a predetermined arrangement.

The post-baking condition is preferably about 180 to 230 ° C for about 20 to 40 minutes.

The film thickness of the thus formed pixel is preferably 0.5 to 5.0 mu m, more preferably 1.5 to 3.0 mu m.

Further, the above steps (1) to (4) are repeated using each liquid composition of the radiation-sensitive resin composition (I) containing a green or blue pigment so that the green pixel pattern and the blue pixel pattern are the same A coloring layer in which pixel patterns of three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on a substrate. However, the order of forming the pixel patterns of the respective colors in the present invention is not limited to this order.

Further, the black matrix can be formed in the same manner as in the case of the above-described pixels by using the radiation-sensitive resin composition (I) containing a black pigment.

Color filter

The color filter of the present invention is formed using the radiation-sensitive resin composition (I) of the present invention.

The color filter of the present invention is very useful for, for example, a transmissive or reflective color liquid crystal display device, a color image pickup tube device, and a color sensor.

Color liquid crystal display

The color liquid crystal display device of the present invention includes the color filter of the present invention.

The color liquid crystal display device of the present invention can take an appropriate structure. For example, a color filter may be formed on a substrate separate from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which a driving substrate and a color filter are formed may face the liquid crystal layer And a substrate on which a color filter is formed on a driving substrate on which a thin film transistor (TFT) is disposed and a substrate on which an ITO (indium-doped indium oxide) electrode is formed are opposed to each other through a liquid crystal layer. The latter structure can further improve the aperture ratio and has an advantage that a bright and highly precise fine liquid crystal display element can be obtained.

As described above, the radiation-sensitive resin composition (I) of the present invention is excellent in the solvent remelting property of the dried coating film and does not cause color unevenness in the coating film after exposure and development, A color filter excellent in reliability can be formed with high product yield.

Accordingly, the radiation sensitive resin composition (I) of the present invention can be used preferably in the production of various color filters including color filters for color liquid crystal displays in the field of electronics.

<Examples>

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Mw and Mn of the resins obtained in the following Synthesis Examples were measured by gel permeation chromatography (GPC) according to the following specifications.

Device: GPC-101 (trade name, manufactured by Showa Denko K.K.).

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

Mobile phase: tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 4 parts by weight of dipropylene glycol dimethyl ether , 20 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenylmaleimide, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene and 10 parts by weight of 2-methacryloyloxyethyl succinate were charged , The reaction solution was heated to 80 ° C while gently stirring, and polymerization was carried out at this temperature for 3 hours. Thereafter, the solution (S-1) of the copolymer (B1) was obtained by heating the reaction solution to 100 占 폚, adding 1 part by weight of 2,2'-azobisisovaleronitrile, (Solid concentration = 33.0 wt%). The copolymer (B1) had Mw = 6,000 and Mw / Mn = 1.4. This copolymer (B1) was referred to as "copolymer (S-1) ".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 4 parts by weight of dipropylene glycol dimethyl ether , 20 parts by weight of methacrylic acid, 18.8 parts by weight of N-phenylmaleimide, 20 parts by weight of allyl methacrylate, 11.2 parts by weight of styrene, 10 parts by weight of 2-methacryloyloxyethyl succinate, 10 parts by weight of 2-hydroxyethyl methacrylate was introduced and replaced with nitrogen. The reaction solution was heated to 80 占 폚 while gently stirring, and polymerization was carried out at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚, 1 part by weight of 2,2'-azobisisovaleronitrile was added, and the polymerization (S-2) of the copolymer (B1) (Solid concentration = 33.0 wt%). The copolymer (B1) had Mw = 6,500 and Mw / Mn = 1.5. This copolymer (B1) was referred to as "copolymer (S-2) ".

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 4 parts by weight of dipropylene glycol dimethyl ether , 20 parts by weight of methacrylic acid, 18.8 parts by weight of N-phenylmaleimide, 30 parts by weight of allyl methacrylate, 11.2 parts by weight of styrene and 10 parts by weight of 2-methacryloyloxyethyl succinate were charged , The reaction solution was heated to 80 ° C while gently stirring, and polymerization was carried out at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚, 1 part by weight of 2,2'-azobisisovaleronitrile was added, and the polymerization (S-3) of the copolymer (B1) (Solid concentration = 33.0 wt%). The copolymer (B1) had Mw = 6,000 and Mw / Mn = 1.4. This copolymer (B1) was referred to as "copolymer (S-3) ".

Synthesis Example 4

2 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of dipropylene glycol dimethyl ether were fed into a flask equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of methacrylic acid, , 31.2 parts by weight of allyl methacrylate, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 10 parts by weight of 2-methacryloyloxyethyl succinate and 4 parts by weight of? -Methylstyrene dimer (molecular weight control agent) , The temperature of the reaction solution was raised to 80 占 폚 while gently stirring, and polymerization was carried out at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚, 1 part by weight of 2,2'-azobisisovaleronitrile was added, and the polymerization was further continued for 1 hour to obtain a solution (S-4) of a copolymer = 33.0 wt%). The copolymer had Mw = 46,000 and Mw / Mn = 4.7. This copolymer was referred to as "copolymer (S-4) ".

Synthesis Example 5

12 parts by weight of 2,2'-azobisisovaleronitrile and 200 parts by weight of dipropylene glycol dimethyl ether were fed into a flask equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of methacrylic acid, 31.2 parts by weight of allyl methacrylate, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 10 parts by weight of 2-methacryloyloxyethyl succinate and 10 parts by weight of? -Methylstyrene dimer (molecular weight control agent) , The temperature of the reaction solution was raised to 70 占 폚 while gently stirring, and polymerization was carried out at this temperature for 2 hours. Thereafter, 3 parts by weight of 2,2'-azobisisovaleronitrile was added while maintaining the reaction solution at 70 占 폚, and the polymerization (S-5) (solids concentration = 32.4% by weight). The copolymer had Mw = 6,000 and Mw / Mn = 2.5. This copolymer was referred to as "copolymer (S-5) ".

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 4 parts by weight of dipropylene glycol dimethyl ether 20 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenylmaleimide, 30 parts by weight of benzylmethacrylate and 18.8 parts by weight of styrene were charged and replaced with nitrogen, and the reaction solution was stirred at 80 Lt; 0 &gt; C, and polymerization was carried out at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚, 1 part by weight of 2,2'-azobisisovaleronitrile was added, and the polymerization was further continued for 1 hour to obtain a solution (S-6) of a copolymer = 33.0 wt%). The copolymer had Mw = 6,000 and Mw / Mn = 1.4. This copolymer was referred to as "copolymer (S-6) &quot;.

solvent Re-soluble  evaluation

Example 1

(A) as a colorant; Pigment Red 254 and C.I. 40 parts by weight of a 50/50 (by weight) mixture of Pigment Yellow 139, 10 parts by weight of Disperbyk 2001 as a dispersing agent and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent were dispersed in a diamond pine mill (trade name: Mitsubishi Matrix Co., (Bead diameter: 1.0 mm) manufactured by Mitsubishi Rayon Co., Ltd.) for 12 hours to prepare a pigment dispersion.

Subsequently, 100 parts by weight of this pigment dispersion, (B) the amount of the solution (S-1) as the alkali-soluble resin was added so that the amount of the copolymer (S-1) was 70 parts by weight, (C) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator (D) and 1,000 parts by weight of propylene glycol monomethyl ether acetate Were mixed to prepare a liquid composition (r-1).

Subsequently, the liquid composition (r-1) was spin-coated on a soda glass substrate having a diameter of 4 inches, on which a SiO ₂ film was formed to prevent elution of sodium ions, and then left to stand in a clean room at 23 캜 for 12 hours Thereby forming a coating film.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 2

A liquid composition (r-2) was prepared in the same manner as in Example 1 except that the solution (S-2) was used in an amount of 70 parts by weight of the copolymer (S-2) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 3

A liquid composition (r-3) was prepared in the same manner as in Example 1 except that the solution (S-3) was used in an amount of 70 parts by weight of the copolymer (S-3) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 4

The photopolymerization initiator of the liquid composition (r-1) prepared in Example 1 was changed to ethanone-1- [9-ethyl-6- (2-methyl- (R-4) was obtained in the same manner as in Example 1, except that the amount of the liquid composition (r-4) was changed to 50 parts by weight of methoxybenzoyl) methoxybenzoyl} -9H-carbazol-3-yl] And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Comparative Example 1

A liquid composition (r-5) was prepared in the same manner as in Example 1 except that the solution (S-4) was used in an amount of 70 parts by weight of the copolymer (S-4) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes. As a result, the coating film was not completely dissolved and a large amount of foreign matter was observed in the liquid.

Comparative Example 2

A liquid composition (r-6) was prepared in the same manner as in Example 1 except that the solution (S-5) was used in an amount of 70 parts by weight of the copolymer (S-5) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Comparative Example 3

A liquid composition (r-7) was prepared in the same manner as in Example 1 except that the solution (S-6) was used in an amount of 70 parts by weight of the copolymer (S-6) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 5

(A) as a pigment; Pigment Blue 15: 6 and C.I. 40 parts by weight of a 90/10 (weight ratio) mixture with Pigment Violet 23, 10 parts by weight of Disperbyk 2001 as a dispersing agent and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent were dispersed in a diamond peen mill (trade name: Mitsubishi Matte Co., (Bead diameter: 1.0 mm) manufactured by Rial Co., Ltd.) for 12 hours to prepare a pigment dispersion.

Subsequently, 100 parts by weight of the pigment dispersion, (B) the amount of the solution (S-1) as the alkali-soluble resin to 80 parts by weight of the copolymer (S-1), (C) 30 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one as a photopolymerization initiator (D) and 30 parts by weight of propylene glycol monomethyl ether acetate Were mixed to prepare a liquid composition (b-1).

Subsequently, the liquid composition (b-1) was spin-coated on a 4-inch diameter soda glass substrate having an SiO ₂ film formed on its surface to prevent the dissolution of sodium ions, and then dried in a clean room at 23 ° C for 12 hours Thereby forming a coating film.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 6

A liquid composition (b-2) was prepared in the same manner as in Example 5 except that the solution (S-2) was used in an amount so that 80 parts by weight of the copolymer (S-2) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 7

A liquid composition (b-3) was prepared in the same manner as in Example 5 except that the solution (S-3) was used in an amount of 80 parts by weight of the copolymer (S-3) A coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 8

The photopolymerization initiator of the liquid composition (b-1) prepared in Example 5 was changed to ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2- (B-4) was obtained in the same manner as in Example 5, except that the amount of the liquid composition (b-4) was changed to 50 parts by weight, And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Comparative Example 4

A liquid composition (b-5) was prepared in the same manner as in Example 5 except that the solution (S-4) was used in an amount of 80 parts by weight of the copolymer (S-4) A coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes. As a result, the coating film was not completely dissolved and a large amount of foreign matter was observed in the liquid.

Comparative Example 5

A liquid composition (b-6) was prepared in the same manner as in Example 5 except that the solution (S-5) was used in an amount of 80 parts by weight of the copolymer (S-5) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Comparative Example 6

A liquid composition (b-7) was prepared in the same manner as in Example 5 except that the solution (S-6) was used in an amount of 80 parts by weight of the copolymer (S-6) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 9

(A) as a pigment; Pigment Green 36 and C.I. 40 parts by weight of a 50/50 (by weight) mixture of Pigment Yellow 150, 10 parts by weight of Disperbyk 2001 as a dispersing agent and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed using a diamond pine mill (trade name: Mitsubishi Matrial (Bead diameter: 1.0 mm) manufactured by Mitsubishi Rayon Co., Ltd.) for 12 hours to prepare a pigment dispersion.

Subsequently, 100 parts by weight of the pigment dispersion, (B) the amount of the solution (S-1) as the alkali-soluble resin is 80 parts by weight of the copolymer (S-1), (C) 30 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one as a photopolymerization initiator (D) and 30 parts by weight of propylene glycol monomethyl ether acetate Were mixed to prepare a liquid composition (g-1).

Subsequently, the liquid composition (g-1) was spin-coated on a soda glass substrate having a diameter of 4 inches and a SiO ₂ film formed on its surface to prevent elution of sodium ions, and then left to stand in a clean room at 23 캜 for 12 hours To form a coating film.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 10

A liquid composition (g-2) was prepared in the same manner as in Example 9 except that the solution (S-2) was used in an amount such that the amount of the copolymer (S-2) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 11

A liquid composition (g-3) was prepared in the same manner as in Example 9 except that the solution (S-3) was used in an amount of 80 parts by weight of the copolymer (S-3) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Example 12

The photopolymerization initiator of the liquid composition (g-1) prepared in Example 9 was changed to ethanone-1- [9-ethyl-6- (2-methyl- (G-4) was obtained in the same manner as in Example 9, except that the amount of the liquid composition (g-4) was changed to 50 parts by weight. And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Comparative Example 7

A liquid composition (g-5) was prepared in the same manner as in Example 9 except that the solution (S-4) was used in an amount of 80 parts by weight of the copolymer (S-4) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes. As a result, the coating film was not completely dissolved and a large amount of foreign matter was observed in the liquid.

Comparative Example 8

A liquid composition (g-6) was prepared in the same manner as in Example 9 except that the solution (S-5) was used in an amount of 80 parts by weight of the copolymer (S-5) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Comparative Example 9

A liquid composition (g-7) was prepared in the same manner as in Example 9 except that the solution (S-6) was used in an amount of 80 parts by weight of the copolymer (S-6) , And a coating film was formed on the soda glass substrate.

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and as a result, the coating film was completely dissolved.

Evaluation of voltage holding ratio

Example 13

The liquid composition (r-1) prepared in Example 1 was applied onto a soda glass substrate having an SiO ₂ film formed on its surface to prevent elution of sodium ions and further deposited with ITO (indium-tin oxide) And then prebaked in a clean oven at 90 占 폚 for 10 minutes to form a coating film having a thickness of 2.0 占 퐉.

Subsequently, using a high-pressure mercury lamp, the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 5,000 J / m ² without passing through the photomask. Thereafter, this substrate was immersed in a developing solution containing 0.04 wt% aqueous potassium hydroxide solution at 23 캜 for 1 minute, developed and then air-dried by air cleaning with ultrapure water and further baked at 250 캜 for 30 minutes to cure Thereby forming red pixels on the substrate. The film thickness of this pixel was 1.60 mu m.

Subsequently, the substrate on which the pixel was formed and the substrate on which the ITO electrode was simply vapor-deposited in a predetermined shape were bonded to each other with a sealant mixed with 0.8 mm glass beads, and then a liquid crystal MLC6608 (trade name) manufactured by Merck & .

Subsequently, the liquid crystal cell was placed in a constant temperature layer at 60 占 폚, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention rate measuring system VHR-1A (trade name) manufactured by Toyo Technica. The applied voltage at this time is 5.5 V square wave, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of a voltage applied to the liquid crystal cell after 16.7 milliseconds / 0 milliseconds. As a result, the voltage holding ratio was 95%.

When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell can not maintain the applied voltage at a predetermined level for 16.7 milliseconds, which makes it impossible to orient the liquid crystal sufficiently. Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-1) is unlikely to cause "baking. &Quot;

Example 14

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (r-2) prepared in Example 2 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-2) is unlikely to cause "baking ".

Example 15

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (r-3) prepared in Example 3 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-3) is unlikely to cause "scorch. &Quot;

Example 16

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (r-4) prepared in Example 4 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-4) scarcely causes "baking".

Comparative Example 10

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (r-5) prepared in Comparative Example 1 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-5) is unlikely to cause "baking. &Quot;

Comparative Example 11

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (r-6) prepared in Comparative Example 2 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-6) is likely to cause "baking. &Quot;

Comparative Example 12

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (r-7) prepared in Comparative Example 3 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (r-7) is unlikely to cause "baking. &Quot;

Example 17

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-1) prepared in Example 5 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-1) is unlikely to cause "baking. &Quot;

Example 18

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-2) prepared in Example 6 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-2) is unlikely to cause "baking ".

Example 19

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-3) prepared in Example 7 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-3) is unlikely to cause "baking. &Quot;

Example 20

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-4) prepared in Example 8 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-4) scarcely causes "baking".

Comparative Example 13

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-5) prepared in Comparative Example 4 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-5) is unlikely to cause "baking ".

Comparative Example 14

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-6) prepared in Comparative Example 5 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-6) is likely to cause "baking. &Quot;

Comparative Example 15

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (b-7) prepared in Comparative Example 6 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (b-7) is unlikely to cause "baking. &Quot;

Example 21

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-1) prepared in Example 9 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-1) is unlikely to cause "baking. &Quot;

Example 22

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-2) prepared in Example 10 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-2) is unlikely to cause "baking ".

Example 23

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-3) prepared in Example 11 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-3) is unlikely to cause "baking ".

Example 24

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-4) prepared in Example 12 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-4) scarcely causes "baking".

Comparative Example 16

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-5) prepared in Comparative Example 7 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-5) is unlikely to cause "baking. &Quot;

Comparative Example 17

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-6) prepared in Comparative Example 8 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-6) is likely to cause "baking. &Quot;

Comparative Example 18

A liquid crystal cell was produced in the same manner as in Example 13 except that the liquid composition (g-7) prepared in Comparative Example 9 was used instead of the liquid composition (r-1). Therefore, the liquid crystal display device provided with the color filter formed using the liquid composition (g-7) is unlikely to cause "baking. &Quot;

Evaluation of color unevenness

Example 25

A coating film was formed on a soda glass substrate by using the liquid composition (r-1) prepared in Example 1.

Subsequently, using a high-pressure mercury lamp, radiation containing each wavelength of 365 nm, 405 nm and 436 nm was exposed to an exposure dose of 5,000 J / m ² through a 90-micrometer stripe pattern photomask. Thereafter, this substrate was immersed in a developer consisting of 0.04 wt% aqueous potassium hydroxide solution at 23 캜 for one minute for development, washed with ultrapure water, and air-dried to form a film.

Subsequently, the surface of the film was observed using an optical microscope, and no color unevenness was observed.

Example 26

A coating film was formed in the same manner as in Example 25 except that the liquid composition (r-2) prepared in Example 2 was used instead of the liquid composition (r-1), and the surface of the coating film was observed with an optical microscope. No color spots were observed.

Example 27

A coating film was formed in the same manner as in Example 25 except that the liquid composition (r-3) prepared in Example 3 was used instead of the liquid composition (r-1), and the surface of the coating film was observed with an optical microscope. No color spots were observed.

Example 28

A coating film was formed in the same manner as in Example 25 except that the liquid composition (r-4) prepared in Example 4 was used in place of the liquid composition (r-1), and the surface of the coating film was observed using an optical microscope. No color spots were observed.

Comparative Example 19

A coating film was formed in the same manner as in Example 25 except that the liquid composition (r-5) prepared in Comparative Example 1 was used instead of the liquid composition (r-1), and the surface of the coating film was observed with an optical microscope. No color spots were observed.

Comparative Example 20

A coating film was formed in the same manner as in Example 25 except that the liquid composition (r-6) prepared in Comparative Example 2 was used instead of the liquid composition (r-1), and the surface of the coating film was observed using an optical microscope. No color spots were observed.

Comparative Example 21

A coating film was formed in the same manner as in Example 25 except that the liquid composition (r-7) prepared in Comparative Example 3 was used instead of the liquid composition (r-1), and the surface of the coating film was observed using an optical microscope. Color speckles were observed.

Color irregularity is observed, which causes stagnation in a foreign matter tester in the color filter manufacturing process, and there is a great possibility that product yield is lowered.

The main results are shown in Table 1 below.

In Table 1, "polymerized form" is a polymerization method for producing a copolymer, "living" means "living radical polymerization ", and" radical "means" radical polymerization ". In addition, " o "in" solvent remelting property "means that the coating film is completely dissolved, and" x "means that a large amount of foreign substances are observed in the liquid.

Claims (7)

(B) a radiation-sensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) (B2) an allyl group-containing compound; (b3) at least one member selected from the group consisting of an aromatic vinyl compound, an indene, an N-substituted maleimide, and a polymer molecular chain (Meth) acryloyl groups at one end, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides and aliphatic (B1) and (b2), which are selected from the group consisting of conjugated dienes and conjugated dienes, and which are measured by gel permeation chromatography (GPC) (Mw / Mn) of a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) to a polystyrene reduced number average molecular weight (Mn) of 1.0 to 1.7. Resin composition. The radiation-sensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) is a copolymer produced by living radical polymerization. The radiation sensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator (D) is at least one selected from the group consisting of a compound represented by the following formula (23) and a compound represented by the following formula (24). &Lt; Formula 23 >

Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 1 to 8 carbon atoms, a phenyl group which may be substituted, or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms , represents a cycloalkyloxy group having 1 to 12 carbon atoms, an alkoxyl group or a C 3 -C 8, and R ⁶ in the presence of a plurality of the same or different, R ⁷ is summoned oxygen-containing monovalent 4 to 20 carbon atoms clothing tableware , a monovalent sulfur-containing heterocyclic group of 4 to 20 carbon atoms or a monovalent nitrogen-containing heterocyclic group having 4 to 20, R ⁷ when there is a plurality of the same or different And, a is an integer from 0 to 5, b is an integer of 0 to 5, (a + b) ≤5 Im; &Lt; EMI ID =

[Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 1 to 8 carbon atoms, a phenyl group which may be substituted, or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms , represents a cycloalkyloxy group having 1 to 12 carbon atoms, an alkoxyl group or a C 3 -C 8, and R ⁶ in the presence of a plurality of the same or different, R ⁷ is summoned oxygen-containing monovalent 4 to 20 carbon atoms clothing tableware , a monovalent sulfur-containing heterocyclic group of 4 to 20 carbon atoms or a monovalent nitrogen-containing heterocyclic group having 4 to 20, R ⁷ when there is a plurality of the same or different And, c is an integer from 0 to 5, d is from 1 to 5 being an integer, (c + d) ≤5, e is an integer of from 0 to 6; A color filter formed by using the radiation sensitive resin composition according to claim 1. A color liquid crystal display device comprising the color filter according to claim 4. The positive resist composition according to claim 1, wherein the copolymerization ratio of the unsaturated compounds (b1) to (b3) in the alkali-soluble resin (B) is from 5 to 30% by weight, (b2) To 60% by weight of the radiation-sensitive resin composition. The radiation-sensitive resin composition according to claim 1, wherein (D) the photopolymerization initiator is a compound represented by the following formula (24). &Lt; EMI ID =

[Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R ⁴ and R ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 1 to 8 carbon atoms, a phenyl group which may be substituted, or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms , represents a cycloalkyloxy group having 1 to 12 carbon atoms, an alkoxyl group or a C 3 -C 8, and R ⁶ in the presence of a plurality of the same or different, R ⁷ is summoned oxygen-containing monovalent 4 to 20 carbon atoms clothing tableware , a monovalent sulfur-containing heterocyclic group of 4 to 20 carbon atoms or a monovalent nitrogen-containing heterocyclic group having 4 to 20, R ⁷ when there is a plurality of the same or different And, c is an integer from 0 to 5, d is from 1 to 5 being an integer, (c + d) ≤5, e is an integer of from 0 to 6;