KR20050076759A - Radiation sensitive composition for color filters, process for preparing the same, color filter and color liquid crystal display - Google Patents

Abstract

The present invention relates to a radiation sensitive composition for color filters which can provide a red pixel having a high transmittance and contrast ratio and free of foreign substances or a trace amount in a high manufacturing yield.

The composition comprises a pigment, an alkali soluble resin, a polyfunctional monomer or a combination of a multifunctional monomer and a monofunctional monomer, and a radiation sensitive radical generator. At this time, the pigment contains 20 wt% or more of C.I.Pigment Red 175 and has an average particle diameter r of 50 to 300 nm. A pixel having a film thickness of 1.60 mu m formed of the composition provides a contrast ratio of 500 or more. The formed color filter is used for a liquid crystal display device.

Description

Radiation Sensitive Composition for Color Filters, Process for Preparing the Same, Color Filter and Color Liquid Crystal Display}

The present invention relates to a radiation sensitive composition for color filters, a color filter and a color liquid crystal display device. More specifically, the radiation-sensitive composition for color filters useful for the production of color filters used in transmissive and reflective color liquid crystal display devices and color image tube devices and the like, and the color having red pixels formed from the radiation-sensitive composition for color filters. A filter and a color liquid crystal display device including the color filter.

As a means for forming a color filter using a colored radiation-sensitive composition, a coating film of the colored radiation-sensitive composition is formed on a substrate or a substrate including a light shielding layer of a desired pattern, and then subjected to radiation through a mask having a desired pattern. A method of obtaining color pixels by exposing (hereinafter referred to as "exposure"), developing with an alkaline developer to dissolve and remove unexposed portions, and then post-baking using a clean oven or hot plate ( See JP-A 2-144502 No. 3-53201, the term "JP-A" as used herein means "unexamined Japanese Patent Laid-Open Publication".

Since the high brightness of the liquid crystal display device containing such a color filter is calculated | required, the demand for the color filter which has high transmittance | permeability is increasing gradually in recent years.

With the recent widespread use of digital video cameras and high-definition TVs, there is a demand for a color liquid crystal display device having a high color density enough to display a deep blue winter sea or a bright red sunset. When the "black" of the black display portion is not clearly displayed, an unclear and blurry image is generated. Therefore, in order to display high color density, a pixel or colored layer having a high color density and contrast ratio is required.

As disclosed in JP-A No. 10-260309, C.I. Pigment Red 254 is known to be effective as a pigment used in red pixels to satisfy the above requirement. However, when using the radiation sensitive composition containing this pigment, a foreign material generate | occur | produced on the pixel and manufacturing yield fell.

In order to solve this problem, in recent years, the development of a radiation sensitive composition for color filters that can provide a red pixel with little foreign matter on the pixel while meeting the requirements such as high transmittance and high contrast ratio is powerful. Is required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation sensitive composition for color filters which can provide a red pixel having high transmittance and contrast ratio and no foreign matter or a small amount in a high manufacturing yield.

Another object of the present invention is to provide an advantageous method for preparing the radiation sensitive composition of the present invention.

Still another object of the present invention is to provide a color filter made of the radiation-sensitive composition of the present invention and a liquid crystal display including the color filter.

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

First, the above objects and advantages of the present invention

(A) a pigment, (B) an alkali soluble resin, (C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and (D) a radiation sensitive radical generator, wherein the pigment (A) is 20 It is achieved by the radiation sensitive composition for color filters containing at least% by weight CI pigment red 175 and whose average particle diameter r is 50-300 nm.

Second, the above objects and advantages of the present invention

(A) a pigment, (B) an alkali soluble resin, (C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and (D) a radiation sensitive radical generator, wherein the pigment (A) is 20 It is achieved by the radiation sensitive composition for color filters which contains the CI pigment red 175 or more by weight, and the pixel of 1.60 micrometers formed from the said radiation sensitive composition provides a contrast ratio of 500 or more.

As used herein, "radiation" means visible light, ultraviolet light, deep ultraviolet light, electron beam or X-ray.

Third, the above objects and advantages of the present invention

(A) a pigment dispersion obtained by mixing and dispersing a pigment containing at least 20% by weight of CI Pigment Red 175 and an average particle diameter of more than 300 nm while grinding in a solvent, (B) alkali-soluble resin, (C) polyfunctional A mixture of monomeric or polyfunctional monomers and monofunctional monomers, and (D) a radiation-sensitive radical generator are mixed together to achieve a method of producing a radiation-sensitive composition.

Fourth, the above objects and advantages of the present invention are achieved by a color filter having red pixels formed of the radiation sensitive composition.

Fifth, the above objects and advantages of the present invention are achieved by a color liquid crystal display device including the color filter.

Hereinafter, the present invention will be described in detail.

(A) pigment

The pigment of the present invention contains C.I. Pigment Red 175 according to the color index (C.I .; published by The Society of Dyers and Colourists).

The pigments of the present invention may optionally further contain other pigments.

Although it does not restrict | limit especially as said other pigment, Organic pigment is preferable because a color filter requires high purity, high permeability color development, and heat resistance.

As an example of another organic pigment, the compound classified into a group of pigments according to a color index, specifically, the compound to which the following color index (C.I.) numbers are given.

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

CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment CI Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI pigment orange 73 and CI pigment orange 74; And

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

Preference is given to using at least one pigment selected from the group consisting of C. I. Pigment Yellow 83, C. I. Pigment Yellow 139, C. I. Pigment Red 177 and C. I. Pigment Red 254 as said other organic pigment.

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

In the pigment of the present invention, the content of C.I.Pigment Red 175 is at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 50% by weight. By using such a pigment, a red pixel having a high contrast ratio and high transmittance and no foreign matter can be obtained.

In the present invention, C.I. Pigment Red 175 and other pigments can be optionally purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof.

The average particle diameter r of the pigment used for this invention is 50-300 nm, Preferably it is 50-200 nm. By using the pigment having the average particle diameter r, a red pixel having a high contrast ratio and high transmittance and no foreign matter can be obtained. As used herein, the term "average particle diameter" refers to the average particle diameter of secondary particles that are agglomerates of primary particles (single microcrystals) of pigments.

In the particle size distribution (hereinafter simply referred to as "particle size distribution") of the secondary particles of the pigment used in the present invention, the content of secondary particles having a particle size of ± 100 nm or less in average particle size is based on the total secondary particles. It is 70 weight% or more, Preferably it is 80 weight% or more.

Pigments such as the average particle diameter and particle size distribution are commercially available CI Pigment Red 175 (generally, the average particle diameter exceeds 300 nm) and optionally other pigments (generally, the average particle diameter exceeds 300 nm). ) May be prepared by mixing with a dispersant and a solvent, preferably as a pigment mixed solution, while grinding into a mill such as a bead mill or a roll mill, followed by mixing and dispersing in a solvent. The pigments obtained are generally in the form of pigment dispersions.

Dispersants used in the preparation of the pigment dispersions are suitably selected from cationic, anionic, amphoteric and nonionic dispersants. Among these, the dispersing agent (henceforth "urethane type dispersing agent") containing the compound which has a urethane bond is preferable.

The urethane bond is represented by the formula R-NH-COO-R ', wherein R and R' are monovalent or polyvalent organic groups of aliphatic, cycloaliphatic or aromatic, respectively, and the polyvalent organic groups are groups having different urethane bonds or other And lipophilic groups and / or hydrophilic groups contained in the urethane-based dispersant. It may also be present in the main and / or side chains of the urethane-based dispersant, and one or more urethane bonds may be present in the urethane-based dispersant. When two or more urethane bonds are present in the urethane-based dispersant, each urethane bond may be the same or different.

The urethane-based dispersant is a reaction product of diisocyanates and / or triisocyanates with polyesters having hydroxyl groups at one end and / or polyesters having hydroxyl groups at both ends.

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

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

These diisocyanate and triisocyanate can be used individually or in mixture of 2 or more types.

Further, polyesters having hydroxyl groups at one end and polyesters having hydroxyl groups at both ends are polycaprolactones having hydroxyl groups at one end or both ends, and hydroxyl groups at one end or both ends. Polylactones having a hydroxyl group at one or both ends, such as polyvalerolactone having a and polypropiolactone having a hydroxyl group at one or both ends; And polycondensed polyesters having hydroxyl groups at one or both ends, such as polyethylene terephthalate having hydroxyl groups at one or both ends, and polybutylene terephthalate having hydroxyl groups at one or both ends Selected from the group.

The said polyesters which have a hydroxyl group in one terminal, and the said polyesters which have a hydroxyl group in both terminal can be used individually or in mixture of 2 or more types.

As the urethane-based dispersant of the present invention, a reaction product of an aromatic diisocyanate with a polylactone having a hydroxyl group at one end and / or a polylactone having a hydroxyl group at both ends is preferable, and toluene diisocyanate is preferable. Particular preference is given to reaction products of the above-described products with polycaprolactone having hydroxyl groups at one end and / or polycaprolactone having hydroxyl groups at both ends.

Commercially available products of the urethane-based dispersant include EFKA (manufactured by EFKA Chemical BV) and Disperbyk (manufactured by BYK Chemie. Co., Ltd.) under a series of known brand names. And Disbaron (manufactured by Kusumoto Kasei Co., Ltd.).

The polystyrene reduced weight average molecular weight measured by gel permeation chromatography (GPC) of the urethane-based dispersant of the present invention is preferably 5,000 to 50,000, more preferably 7,000 to 20,000.

Said urethane type dispersing agent can be used individually or in mixture of 2 or more types.

The amount of the urethane-based dispersant for preparing the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, even more preferably 1 to 70 parts by weight, particularly preferably 10 based on 100 parts by weight of the pigment. To 50 parts by weight. If the amount of the urethane-based dispersant exceeds 100 parts by weight, developability may be impaired.

The solvent used for preparing the pigment dispersion may be the same as the solvent described later for the radiation sensitive composition for color filters of the present invention.

The amount of the solvent used for preparing the pigment dispersion is preferably 500 to 1,000 parts by weight, more preferably 700 to 900 parts by weight based on 100 parts by weight of the pigment.

When preparing a pigment dispersion with a bead mill, the pigment mixture solution is mixed and dispersed using glass beads or titania beads having a diameter of about 0.5 to 10 mm while cooling with cooling water or the like.

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

When producing a pigment dispersion with a roll mill, it can process it using a triaxial roll mill or a biaxial roll mill, cooling a pigment mixture solution with cooling water etc.

It is preferable that a roll spacing is 10 micrometers or less, and a shear force is 10 ⁸ dyn / sec. The processing time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

The average particle diameter and particle size distribution of the pigment in the pigment dispersion liquid prepared as mentioned above can be measured by the dynamic light scattering method.

(B) alkali soluble resin

As alkali-soluble resin of this invention, if it acts as a binder with respect to pigment (A), and it has solubility with respect to the developing solution (preferably alkaline developing solution) used for the developing step for color filter manufacture, it will not specifically limit. For example, alkali-soluble resins are copolymers of polymerizable unsaturated monomers having acid functional groups such as carboxyl groups, phenolic hydroxyl groups or sulfonic acid groups with other copolymerizable unsaturated monomers (hereinafter referred to as "copolymerizable unsaturated monomers").

Examples of the polymerizable unsaturated monomer having a carboxyl group (hereinafter referred to as "carboxyl group-containing unsaturated monomer") include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids and anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Unsaturated polycarboxylic acids having three or more carboxyl groups and anhydrides thereof; Mono [(meth) acrylic of polycarboxylic acids having two or more carboxyl groups such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate Iloxyalkyl] esters; And mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as? -Carboxypolycaprolactone mono (meth) acrylates.

Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate and ω-carboxypolycaprolactone mono (meth) acrylate are preferred.

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

Examples of the polymerizable unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methyl Styrene, p-hydroxy-α-methylstyrene, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide.

Such polymerizable unsaturated monomers having a phenolic hydroxyl group can be used alone or in combination of two or more thereof.

Examples of the polymerizable unsaturated monomer having a sulfonic acid group include isoprene sulfonic acid and p-styrene sulfonic acid.

Such polymerizable unsaturated monomers having a sulfonic acid group may be used alone or in combination of two or more thereof.

Examples of copolymerizable unsaturated monomers include macromonomers having (meth) acryloyl groups at one end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and Polysiloxanes (hereinafter referred to as "macromonomers"); N- (substituted) aryl maleimides such as N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -Methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide, and N-substituted maleimides such as N-cyclohexyl Maleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy Styrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; Indenes such as indene and 1-methylindene; Unsaturated carboxylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenolciethyl (meth) acrylate, methoxydiethylene glycol (meth Acrylate, methoxytriethylene glycol (meth) arc Relate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate and glycerol (meth) acrylate; Unsaturated aminoalkyl carboxylates such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) Acrylate, 3-aminopropyl (meth) acrylate and 3-dimethylaminopropyl (meth) acrylate; Unsaturated glycidyl carboxylates such as glycidyl (meth) acrylate; Vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; And aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

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

Among the copolymerizable unsaturated monomers, macromonomers, N-substituted maleimides, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate are preferable. Among the macromers, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer are particularly preferred, and among N-substituted maleimides, N-phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

As alkali-soluble resin in this invention, the copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (henceforth "a carboxyl group-containing copolymer") is preferable.

The carboxyl group-containing copolymer includes (a) a carboxyl group-containing unsaturated monomer component and (b) a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxy At least one compound selected from the group consisting of ethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate and optionally (c) styrene, methyl (meth) acrylate, allyl (meth) acrylate And copolymers of monomer mixtures containing one or more compounds selected from the group consisting of phenyl (meth) acrylates (hereinafter referred to as "carboxyl group-containing copolymers (I)").

In particular, (a) a carboxyl group-containing unsaturated monomer component containing (meth) acrylic acid as an essential component and optionally mono [2- (meth) acryloyloxyethyl] succinate, (b) polystyrene macromonomer, polymethyl ( Meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate A copolymer consisting of at least one compound and optionally a monomer mixture containing (c) at least one compound selected from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate (Hereinafter referred to as "carboxyl group-containing copolymer (II)").

Examples of carboxyl group-containing copolymers (II) include copolymers consisting of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, benzyl (meth) acrylate and glycerol mono (meth) acrylate ; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-phenylmaleimide, styrene and allyl (meth) acrylate; Copolymers consisting of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-phenylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-cyclohexylmaleimide, styrene and allyl (meth) acrylate; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-cyclohexylmaleimide, benzyl (meth) acrylate and styrene; Copolymers consisting of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-phenylmaleimide, benzyl (meth) acrylate, glycerol mono (meth) acrylate and styrene; Copolymers consisting of (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, N-phenylmaleimide, benzyl (meth) acrylate, glycerol mono (meth) acrylate and styrene; Copolymers of (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate; Copolymers consisting of (meth) acrylic acid, polystyrene macromers and benzyl (meth) acrylates; Copolymers consisting of (meth) acrylic acid, polymethyl (meth) acrylate macromonomers and benzyl (meth) acrylates; Copolymers consisting of (meth) acrylic acid, benzyl (meth) acrylate, and glycerol mono (meth) acrylate; Copolymers consisting of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; Copolymers consisting of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and phenyl (meth) acrylate; Copolymers consisting of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and styrene; Copolymers consisting of (meth) acrylic acid, N-cyclohexylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, polystyrene macromonomers, 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; Copolymers of (meth) acrylic acid, polymethyl (meth) acrylate macromonomers, 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; Copolymers consisting of (meth) acrylic acid, N-phenylmaleimide, benzyl (meth) acrylate and styrene; And (meth) acrylic acid, N-phenylmaleimide, benzyl (meth) acrylate, glycerol mono (meth) acrylate, and styrene.

The content of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the content is less than 5% by weight, the solubility in the alkaline developer of the obtained radiation sensitive composition may be lowered. When the content is more than 50% by weight, the solubility in the alkaline developer of the composition becomes so high that the pixel may fall from the substrate or the film surface of the pixel may be rough when the composition is developed with the alkaline developer.

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

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

By using an alkali-soluble resin having such a specific Mw or Mn, a radiation-sensitive composition excellent in developability is obtained, whereby the edges of the pattern can form sharp pixels, upon development or on the substrate of the unexposed portion. Residue, background contamination and film residue hardly occur on the light shielding layer.

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

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

The amount of the alkali-soluble resin of the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight based on 100 parts by weight of the pigment (A). When the amount of the alkali-soluble resin is less than 10 parts by weight, alkali developability may be lowered, or background contamination and film residue may occur on the substrate or the light shielding layer of the unexposed part. When the amount exceeds 1,000 parts by weight, it may be difficult to achieve the target color density of the thin film because the pigment concentration is lowered.

(C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer

The multifunctional monomer of the present invention is a monomer having two or more polymerizable unsaturated bonds.

Examples of polyfunctional monomers include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol having two or more ethyleneoxy groups and polypropylene glycol having two or more propyleneoxy groups; Poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups, such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol, and their dicarboxylic acid modifications; Oligo (meth) acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins and spiran resins; Polymers having hydroxyl groups at both ends, such as poly-1,3-butadiene having hydroxyl groups at both ends, polyisoprene having hydroxyl groups at both ends, and polycaprolactone having hydroxyl groups at both ends Di (meth) acrylates; And tris [2- (meth) acryloyloxyethyl] phosphate.

Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups and their dicarboxylic acid modifications, such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri ( Preferred are meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Among them, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high intensity and surface smoothness of the obtained pixel, and have background contamination and film residue on the substrate and the light shielding layer of the unexposed part. It is particularly preferable in that it hardly occurs. The said functional monomer can be used individually or in mixture of 2 or more types.

The amount of the multifunctional monomer of the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the alkali-soluble resin (B). When the amount of the polyfunctional monomer is less than 5 parts by weight, the intensity and surface smoothness of the obtained pixel may be lowered. When the amount exceeds 500 parts by weight, alkali developability may be lowered, or background contamination and film residue may easily occur on the substrate or the light shielding layer of the unexposed part.

In the present invention, a part of the polyfunctional monomer can be substituted with a monofunctional monomer having one polymerizable unsaturated bond.

Examples of the monofunctional monomers include the carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the alkali-soluble resin (B), N-vinylsuccinimide, N-vinylpyrrolidone, and N-vinylphthalimide , N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole N-vinyls such as N-vinylindolin, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylpiperidine, N-vinylpiperazine, N-vinylmorpholine and N-vinylphenoxazine Nitrogen heterocyclic compounds, N- (meth) acryloyl morpholine, and commercially available M-5300, M-5400, and M-5600 (trade names of Toagosei Chemical Industry Co., Ltd.) Can be mentioned.

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

The amount of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer. When the amount of monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting pixel may be lowered.

(D) radiation-sensitive radical generator

The radiation sensitive radical generators of the present invention (hereinafter simply referred to as "radical generators") will initiate the polymerization of component (C) upon exposure to radiation such as visible, ultraviolet, far ultraviolet, electron or X-rays. It is a compound capable of forming radicals.

Examples of the radical generator include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, and diazo compounds. Can be mentioned.

In the present invention, the radical generator may be used alone or in combination of two or more thereof. The radical generator of the present invention is preferably at least one compound selected from the group consisting of acetophenone compounds, biimidazole compounds, and triazine compounds.

The amount of the radical generator of the present invention is preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight based on 100 parts by weight of the component (C). When the amount of the radical generator is less than 0.01 part by weight, it is difficult to obtain a color filter having a predetermined pixel pattern because curing by exposure is insufficient. If the amount exceeds 80 parts by weight, the formed pixels may fall off the substrate during development.

Examples of the acetophenone-based compounds in the preferred radical generator of the present invention include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholino propanoone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- 1,2-diphenylethan-1-one, 1,2-octanedione, and 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butanone-1, 1,2-octanedione and 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) are particularly preferred.

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

When using an acetophenone-based compound as the radical generator of the present invention, the amount of the acetophenone-based compound is preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of component (C), Especially preferably, it is 1-30 weight part. When the amount of the acetophenone-based compound is less than 0.01 part by weight, curing by exposure is insufficient, so that it may be difficult to obtain a color filter having a predetermined pixel pattern. If the amount exceeds 80 parts by weight, the formed pixels may fall off the substrate during development.

As an example of a biimidazole type compound,

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

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

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

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

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

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

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

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

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4'5,5'-tetraphenyl- 1,2'-biimidazole is particularly preferred.

The non-imidazole compound has excellent solubility in a solvent, does not generate foreign matters such as undissolved products and precipitates, has high sensitivity, and can sufficiently proceed the curing reaction even by exposure of a small amount of energy. It does not cause a curing reaction. Therefore, the coating film after exposure is clearly divided into a hardened part insoluble in the developer and an uncured part having high solubility in the developer, thereby forming a high quality color filter having a predetermined pixel pattern without undercut. .

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

In the case of using the biimidazole compound as the radical generator in the present invention, the amount of the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight based on 100 parts by weight of component (C). Parts, particularly preferably 1 to 20 parts by weight. When the amount of the biimidazole-based compound is less than 0.01 part by weight, it is difficult to obtain a color filter having a predetermined pixel pattern because curing by exposure is insufficient. When the amount exceeds 40 parts by weight, the formed pixel may fall off the substrate during development or the film surface of the pixel may be rough.

Hydrogen donor

When using a biimidazole type compound as a radical generator in this invention, it is preferable to further improve a sensitivity by using the following hydrogen donor together.

As used herein, the term "hydrogen donor" refers to a compound capable of providing hydrogen atoms to radicals formed from biimidazole-based compounds upon exposure.

It is preferable that the hydrogen donor of this invention is a mercaptan type compound or an amine compound defined below.

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

The amine compound is a compound having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the benzene ring or heterocycle as the mother nucleus and the mother nucleus in the molecule (hereinafter, “ Amine-based hydrogen donors ".

The hydrogen donor may also have a mercapto group and an amino group at the same time.

The hydrogen donor will be described in more detail below.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles in the molecule, or both. In the case of having two or more of these rings, a fused ring may or may not be formed.

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

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

Examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2 -Mercapto-2,5-dimethylaminopyridine.

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

The amine hydrogen donor may have one or more benzene rings or heterocycles in the molecule, or both. In the case of having two or more of these rings, a fused ring may or may not be formed.

One or more amino groups of the amine-based hydrogen donor may be substituted by an alkyl group or a substituted alkyl group. The amine-based hydrogen donor may be substituted by a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, or nitrile group at a position other than the amino group.

Examples of the amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoate and 4-dimethylaminobenzonitrile.

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

When radical generators other than nonimidazole compounds are used, the amine hydrogen donor acts as a sensitizer.

In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof. Since the formed pixels do not fall off from the substrate during development and have high strength and sensitivity, it is preferable to use a combination of at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor.

Examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include a combination of 2-mercaptobenzothiazole and 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole and 4,4 '. -A combination of bis (diethylamino) benzophenone, a combination of 2-mercaptobenzoxazole and 4,4'-bis (dimethylamino) benzophenone, and a 4,4'-bis (2-mercaptobenzoxazole) And combinations of diethylamino) benzophenones. A combination of 2-mercaptobenzothiazole and 4,4'-bis (diethylamino) benzophenone, and a combination of 2-mercaptobenzooxazole and 4,4'-bis (diethylamino) benzophenone are preferred. Particularly preferred are combinations of 2-mercaptobenzothiazole and 4,4'-bis (diethylamino) benzophenone.

The weight ratio of mercaptan-based hydrogen donor to amine-based hydrogen donor in the combination of mercaptan-based hydrogen donor and 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 biimidazole compound in the present invention, the amount of the hydrogen donor is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably based on 100 parts by weight of component (C). Preferably from 1 to 20 parts by weight. When the amount of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity may be lowered. If the amount exceeds 40 parts by weight, the formed pixels may fall off the substrate during development.

Examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2 -[2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloro Rhomethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4, The triazine type compound which has a halomethyl group like 6-bis (trichloromethyl) -s-triazine is mentioned.

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

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

When using a triazine-based compound as the radical generator in the present invention, the amount of the triazine-based compound is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably based on 100 parts by weight of component (C). Preferably from 1 to 20 parts by weight. If the amount of the triazine-based compound is less than 0.01 part by weight, curing by exposure is insufficient, so that it may be difficult to obtain a color filter having a predetermined pixel pattern. If the amount exceeds 40 parts by weight, the formed pixels may fall off the substrate during development.

Other additives

The radiation sensitive composition for color filters of this invention contains the said components (A)-(D) and optionally another additive component.

The additive component may include a filler such as glass or alumina; Polymeric compounds such as polyvinyl alcohol or poly (fluoroalkylacrylates); Nonionic, cationic or anionic surfactants; Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane or 3-mercaptopropyl Adhesion accelerators such as trimethoxysilane; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) or 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole or alkoxybenzophenone; And cohesion inhibitors such as sodium polyacrylate.

menstruum

The radiation sensitive composition for color filters of this invention contains the said components (A)-(D) and optionally another addition component, and it is preferable to manufacture a liquid composition by adding a solvent.

The solvent may be appropriately selected and used as long as it disperses or dissolves the components (A) to (D) and other additive components constituting the radiation sensitive composition, and does not react with these components.

Examples of such solvents include propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; (Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Ketoalcohols such as diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4-methylhexan-2-one; Alkyl lactates such as methyl lactate and ethyl lactate; Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n -Propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-butyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And 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, diethylene glycol dimethyl ether, diethylene glycol from the viewpoint of solubility, pigment dispersibility and applicability Methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3 -Methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl Pyruvate is preferred.

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

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate together with the solvent And high boiling point solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate may be used in combination.

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

The amount of the solvent is not particularly limited, but from the viewpoint of the applicability and stability of the resulting radiation-sensitive composition, the sum of all components except for the solvent of the composition is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight. The amount to be% is preferable.

Formation method of the color filter

Next, the method to form the color filter of this invention using the radiation sensitive composition for color filters of this invention is demonstrated.

The method for forming the color filter includes the steps (1) to (4) performed at least in the following order.

(1) forming a coating film of the radiation sensitive composition of the present invention on a substrate;

(2) exposing at least a portion of the coating film;

(3) developing the coating film after exposure; And

(4) A step of heating the coating film after development (hereinafter referred to as "post-baking").

Hereinafter, each step will be described in detail in sequence.

Step (1)

A light shielding layer is formed on the substrate surface so as to define a portion for forming a pixel as necessary, the radiation-sensitive liquid composition of the present invention is applied onto the substrate, prebaking is carried out to evaporate the solvent, and the coating film is formed. Form.

The substrate used in this step is made of a ring-opening polymer of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, polyimide, polyether sulfone, and cyclic olefin or its hydrogenated additives.

The substrate may also be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction or vacuum deposition.

In order to apply a liquid composition to a board | substrate, the suitable application | coating method, such as rotational coating, casting | flow_spreading, or roll application | coating, can be used.

As for the conditions of prebaking, it is preferable to prebak the resin composition for 2 to 4 minutes at 70-110 degreeC.

The coating film thickness of the resin composition is preferably 0.1 to 10 µm, more preferably 0.2 to 8.0 µm, and particularly preferably 0.2 to 6.0 µm after solvent removal.

Step (2)

Next, it exposes through the photomask which has a suitable pattern in the formed coating film.

The radiation used in this step may be visible light, ultraviolet light, far ultraviolet rays, electron beams or X-rays. Preference is given to radiations having a wavelength of 190 to 450 nm.

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

Step (3)

Thereafter, the coating film is preferably developed using an alkali developer, and the unexposed portions of the coating film are removed.

The alkaline developer is sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene or 1,5-diazabicyclo- [4.3 Preference is given to aqueous solutions of .0] -5-nonene.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer. After alkali development, a coating film is wash | cleaned normally.

Shower development, spray development, dip development, puddle development, and the like can be used.

The developing conditions are preferably developed for 5 to 300 seconds at room temperature.

Step (4)

By postbaking the developed coating film, a substrate having a predetermined red pixel pattern made of a cured product of the radiation sensitive composition for color filters can be obtained.

As for the postbaking conditions, it is preferable to heat a coating film for 20 to 40 minutes at 180-230 degreeC.

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

In addition, by repeating steps (1) to (4) equally by using a liquid composition in which green and blue pigments are dispersed, a blue pixel pattern and a green pixel pattern are formed on the same substrate, whereby A colored layer having red, green and blue pixel patterns can be formed.

In this invention, the formation order of the pixel pattern of each color is not limited to said order.

Color filter

The color filter of this invention has a red pixel formed from the radiation sensitive composition of this invention.

The red pixel of the color filter of this invention has a high light transmittance when the film thickness is 1.60 micrometers, and contrast ratio is 500 or more, Preferably it is high as 1,000 or more.

In addition, the red pixel of the color filter of the present invention contains little or no foreign matter thereon.

A color filter having a high contrast ratio of 500 or more and a red pixel in which foreign matter does not occur on the pixel cannot be obtained from the radiation sensitive composition for color filters of the prior art.

The color filter of the present invention is very useful for transmissive and reflective color liquid crystal display devices, color imaging tube devices, color sensors and the like.

Color liquid crystal display

The color liquid crystal display device of this invention contains the color filter of this invention.

The color liquid crystal display device of this invention can take a suitable structure. For example, a color filter is formed on a substrate separate from the driving substrate having a thin film transistor (TFT), and the driving substrate and the color filter substrate are connected to each other in an opposite structure through a liquid crystal layer interposed therebetween. do. Alternatively, a substrate manufactured by forming a color filter on a driving substrate having a thin film transistor (TFT) formed thereon and a substrate having an ITO (indium oxide doped tin) electrode are opposed through a liquid crystal layer interposed therebetween. do. The latter structure can significantly improve the numerical aperture, thereby obtaining a bright high definition liquid crystal display device.

The radiation-sensitive composition of the present invention may provide a red pixel having a high transmittance and contrast ratio and no foreign matter or a trace amount in a high manufacturing yield.

<Example>

The following examples are provided for the purpose of further illustrating the invention, but should not be construed as limiting in any way.

Synthesis Example 1

1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate were fed to a flask equipped with a cooling tube and a stirrer, and then 15 parts by weight of methacrylic acid. 25 parts by weight of N-phenylmaleimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight of styrene and 2.5 parts by weight of α-methylstyrene dimer as a chain transfer agent to the flask, The inside of the solution was replaced with nitrogen, and the resulting solution was slowly stirred, and the solution was polymerized by raising the temperature of the reaction solution to 80 ° C. and maintaining this temperature for 3 hours. Thereafter, the temperature of the reaction solution was further increased to 100 ° C, 0.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for another 1 hour to give a resin solution (solid content 33.1% by weight). Obtained. Mw of the obtained resin was 30,000 and Mn was 10,000. This resin was named Resin (B-1).

Synthetic Example 2

2.7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate were fed to a flask equipped with a cooling tube and a stirrer, and then 15 parts by weight of methacrylic acid , 10 parts by weight of ω-carboxypolycaprolactone monoacrylate, 18.75 parts by weight of N-phenylmaleimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 11.25 parts by weight of styrene and α- as a chain transfer agent. 5 parts by weight of methyl styrene dimer was fed to the flask, the inside of the flask was replaced with nitrogen, the resulting solution was stirred slowly, the temperature of the reaction solution was raised to 80 ° C. and maintained at this temperature for 3 hours to polymerize the solution. . Thereafter, the temperature of the reaction solution was further increased to 100 ° C, 0.3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for another 1 hour to give a resin solution (solid content of 33.0% by weight). Obtained. Mw of the obtained resin was 15,000 and Mn was 7,000. This resin was named Resin (B-2).

<Example 1>

40 parts by weight of a 50/50 (weight ratio) mixture of CI Pigment Red 175 and CI Pigment Yellow 254 as pigment (A), 10 parts by weight of EFKA-47 as a dispersant and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent The resulting mixed solution was mixed and dispersed with each other for 12 hours in a diamond fine mill (trade name of a bead mill with a bead diameter of 1.0 mm, manufactured by Mitsubishi Materials Co., Ltd.) to give pigments. A dispersion was prepared.

It was 140 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

100 weight part of obtained pigment dispersion liquid, 70 weight part of resin (B-1) as alkali-soluble resin (B), 80 weight part of dipentaerythritol hexaacrylate as a polyfunctional monomer (C), 2 as a radical generator (D) 50 parts by weight of -benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed with each other to prepare a liquid composition (R1).

Thereafter, the liquid composition (R1) was applied with a spin coater to the surface of the soda-lime glass substrate having a SiO ₂ film for preventing the elution of sodium ions formed on the surface, and the clean oven heated at 90 ° C. It prebaked for 10 minutes within and formed the coating film of thickness 2.0micrometer.

The substrate was then cooled to room temperature and the coating film on the substrate was exposed through a photomask to 5,000 J / m ² radiation (wavelength: 365 nm, 405 nm and 436 nm) using a high pressure mercury lamp. Subsequently, the substrate was immersed for 1 minute in 0.04% by weight of an aqueous potassium hydroxide solution as a developing solution having a temperature of 23 ° C, washed and air-dried with ultrapure water, and postbaked at 250 ° C for 30 minutes to form a red striped pixel pattern on the substrate. Formed. The film thickness of this pixel pattern was 1.60 micrometers.

Evaluation of Foreign Matter and Chromaticity

When the formed pixel pattern was observed through an optical microscope, no foreign matter was observed on the pixel.

The chromaticity of the pixels was evaluated with a color analyzer TC-1800M (manufactured by Tokyo Denshoku Co., Ltd.), and it was (x, y, Y) = (0.650, 0.340, 20.0).

Evaluation of Contrast Ratio

The obtained board | substrate was sandwiched between two deflection plates, and the front side deflection plate was rotated and the maximum value and minimum value of the light intensity which were transmitted by illuminating with a fluorescent lamp (wavelength 380-780 nm) from the back side were measured. The contrast ratio obtained by dividing the maximum value by the minimum value was 1,800.

<Example 2>

A liquid composition (R2) was prepared in the same manner as in Example 1, except that 40 parts by weight of C.I. Pigment Red 175 as the pigment (A) and 10 parts by weight of BYK-2001 were used as the dispersant.

It was 140 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (R2), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate similarly to Example 1.

As a result, no foreign matter was observed on the pixel. The chromaticity of the pixel was (x, y, Y) = (0.650, 0.345, 19.0), and the contrast ratio was 2,500.

<Example 3>

40 parts by weight of a 40/60 (weight ratio) mixture of CI Pigment Red 175 and CI Pigment Yellow 254 as pigment (A) and 70 parts by weight of resin (B-2) as alkali-soluble resin (B) were mixed and dispersed. A liquid composition (R3) was prepared in the same manner as in Example 1 except that the pigment dispersion was prepared by carrying out for 4 hours. It was 250 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (R3), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate in the same manner as Example 1.

As a result, no foreign matter was observed on the pixel. The chromaticity of the pixel was (x, y, Y) = (0.650, 0.338, 18.0), and the contrast ratio was 500.

<Example 4>

40 parts by weight of an 80/20 (weight ratio) mixture of CI Pigment Red 175 and CI Pigment Red 177 as pigment (A), 70 parts by weight of resin (B-2) as alkali-soluble resin (B) and BYK-2000 as a dispersant A liquid composition (R4) was prepared in the same manner as in Example 1, except that 10 parts by weight of the pigment dispersion was prepared by mixing and dispersing for 16 hours.

It was 80 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (R4), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate in the same manner as Example 1.

As a result, no foreign matter was observed on the pixel. The chromaticity of the pixel was (x, y, Y) = (0.650, 0.342, 18.0), and the contrast ratio was 2,200.

Example 5

40 parts by weight of a 35/65 (weight ratio) mixture of CI Pigment Red 175 and CI Pigment Red 177 as pigment (A) and 10 parts by weight of BYK-165 as a dispersant, and mixing and dispersing was carried out for 8 hours to give a pigment dispersion. A liquid composition (R5) was prepared in the same manner as in Example 1 except that was prepared. It was 200 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (R5), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate in the same manner as Example 1.

As a result, no foreign matter was observed on the pixel. The chromaticity of the pixel was (x, y, Y) = (0.650, 0.323, 16.0), and the contrast ratio was 1,000.

Comparative Example 1

Liquid in the same manner as in Example 1, except that 40 parts by weight of a 15/85 (weight ratio) mixture of CI Pigment Red 175 and CI Pigment Red 254 was used as the pigment (A), and 10 parts by weight of BYK-2001 was used as the dispersant. Composition (r1) was prepared.

It was 140 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (r1), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate similarly to Example 1.

The chromaticity of the pixel was (x, y, Y) = (0.650, 0.336, 19.0), and the contrast ratio was 940. However, the number of foreign matters on the pixel was an average of 20 at an area of 100 μm × 100 μm, which meant that the obtained product could not be used as a color filter.

Comparative Example 2

The same manner as in Example 1, except that a pigment dispersion was prepared by using a mixture of 40 parts by weight of CI Pigment Red 254 as pigment (A) and 10 parts by weight of BYK-2000 as a dispersant and mixing and dispersing for 16 hours. To prepare a liquid composition (r2).

It was 100 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (r2), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate similarly to Example 1.

The chromaticity of the pixel was (x, y, Y) = (0.650, 0.335, 18.0), and the contrast ratio was 1,500. However, the number of foreign matters on the pixel was 80 on average in an area of 100 μm × 100 μm, which meant that the obtained product could not be used as a color filter.

Comparative Example 3

A liquid composition (r3) was prepared in the same manner as in Example 1, except that 40 parts by weight of C.I. Pigment Red 208 as the pigment (A) and 10 parts by weight of SOLSPERSE 24000 as a dispersant were used.

It was 140 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (r3), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate in the same manner as Example 1.

As a result, no foreign matter was observed on the pixel. The chromaticity of the pixel was (x, y, Y) = (0.650, 0.306, 12.5), and the contrast ratio was 250.

<Comparative Example 4>

A liquid composition (r4) was prepared in the same manner as in Example 2 except that the pigment dispersion was prepared by mixing and dispersing for 30 minutes.

It was 400 nm when the average particle diameter of the pigment contained in the obtained pigment dispersion liquid was measured by the dynamic light scattering method.

Except having used the liquid composition (r4), the red stripe type pixel pattern with a film thickness of 1.60 micrometers was formed and evaluated on the board | substrate in the same manner as Example 1.

As a result, no foreign matter was observed on the pixel. The chromaticity of the pixel was (x, y, Y) = (0.650, 0.343, 15.0), and the contrast ratio was 350.

According to the present invention, there is provided a radiation-sensitive composition for a color filter having a high transmittance and contrast ratio and capable of providing a red pixel having no foreign matter or a small amount in a high production yield, a color filter having a colored layer formed therefrom, and a method of forming the color A liquid crystal display device including a filter can be obtained.

Claims (6)

A radiation-sensitive composition comprising (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and (D) a radiation sensitive radical generator, Said pigment (A) contains 20 weight% or more of C.I. pigment red 175 and the average particle diameter r is 50-300 nm, The radiation sensitive composition for color filters. A radiation-sensitive composition comprising (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and (D) a radiation sensitive radical generator, The pigment (A) comprises at least 20% by weight of CI Pigment Red 175, wherein the pixel having a film thickness of 1.60 µm formed of the radiation sensitive composition provides a contrast ratio of 500 or more, wherein the radiation sensitive composition for color filters . 3. The pigment according to claim 1 or 2, wherein the pigment (A) further comprises at least one pigment selected from the group consisting of CI Pigment Yellow 83, CI Pigment Yellow 139, CI Pigment Red 177 and CI Pigment Red 254. A radiation sensitive composition to be. (A) a pigment dispersion obtained by mixing and dispersing a pigment containing at least 20% by weight of CI Pigment Red 175 and an average particle diameter of more than 300 nm while grinding in a solvent, (B) alkali-soluble resin, (C) polyfunctional A method of preparing the radiation sensitive composition of claim 1, comprising mixing a monomer or polyfunctional monomer with a monofunctional monomer, and (D) a radiation sensitive radical generator. The color filter which has a red pixel formed from the radiation sensitive composition of any one of Claims 1-3. A color liquid crystal display device comprising the color filter of claim 5.