KR20090127218A - Colored composition for forming red pixel, color filter and color liquid crystal display device - Google Patents

Abstract

PURPOSE: A coloring composition for forming a red pixel, a color filter using the composition, and a colored LCD device containing the color filter are provided to reproduce the deep color near to CRT and to form a red pixel having a high contrast ratio. CONSTITUTION: A coloring composite for forming a red pixel comprises a colorant; a binder resin; and a multifunctional monomer, wherein the colorant comprises at least one selected from the group consisting of C.I. pigment red 177, and C.I. pigment red 242 and C.I. pigment orange 38, and the CIE chromaticity coordinate measured under the condition of the C light source and 2° view angle satisfies 0.61<=x<=0.67, and 0.31<=y<=0.35. The colorant comprises 30 ~ 80 mass % of C.I. pigment red 177; and 1 ~ 49 mass % of at least one selected from the group consisting of C.I. pigment red 242 and C I. pigment orange 38.

Description

Colored Composition for Forming Red Pixel, Color Filter and Color Liquid Crystal Display Device}

The present invention relates to a coloring composition for forming red pixels, a color filter, and a color liquid crystal display device, and more particularly, a coloring composition used for manufacturing a red pixel used in a transmissive or reflective color liquid crystal device, a color imaging tube element, and the like; The color filter which has a pixel formed from this coloring composition, and the color liquid crystal display element provided with this color filter.

BACKGROUND ART With the spread of digital video cameras, hi-vision televisions, and the like, liquid crystal display devices having color filters are required to expand the color reproduction area so that deep blue and red sunsets such as the winter sea can be displayed. In general, the color reproduction region of the liquid crystal display element is set on the basis of the CRT, and it is required to be as close to it as possible. As a standard color reproduction area of the CRT, for example, the color space defined by the color television system adopted in the United States, Japan, etc., which is proposed by the National Television System Committee (NTSC), the Internet, SRGB, which is a standard color space for digital images handled inside a personal computer, and a color space proposed by the European Broadcasting Union (EBU). In addition, red CIE chromaticity coordinates in these standard color reproduction areas are as follows.

NTSC: x = 0.670, y = 0.330

sRGB, EBU: x = 0.640, y = 0.330

In addition, in order to display a dark color as described above, if the "black" of the black display unit is not clearly displayed, the screen becomes a screen without blurring strength and weakness, and thus has a high contrast ratio at the same time as the color reproduction area is enlarged. Pixels are required.

By the way, about the coloring composition for red pixel formation, various proposals are made | formed in order to improve the color characteristic. For example, Patent Document 1 and Patent Document 2 below disclose C.I. Pigment Red 254 and C.I. It is proposed to use Pigment Red 177 in combination with various yellow pigments. However, such a combination of pigments was insufficient to obtain a red pixel having a high contrast ratio.

On the other hand, in the following Patent Document 3, the following Patent Document 4, C.I. Pigment Red 242 as the main pigment, C.I. Pigment Red 254, C.I. It is proposed to use Pigment Red 177 etc. as a coloring pigment. However, in such a pigment composition, it is sometimes difficult to reproduce the standard red reproduction region of the CRT described above, and at the same time, it is insufficient to obtain a red pixel having a high contrast ratio. In contrast, Patent Document 5 below discloses C.I. Pigment Red 254 as the main pigment, C.I. Although the purpose of improving color characteristics by using Pigment Red 242 together as a color pigment is disclosed, even the composition of such a pigment is inadequate for obtaining the red pixel which has high contrast ratio.

In addition, Patent Documents 6 to 8 disclose C.I. Pigment Red 254 and C.I. It is disclosed to use Pigment Orange 38 in combination. However, the combination of such pigments is sometimes insufficient to obtain a red pixel having a high contrast ratio, and at the same time it is difficult to reproduce the standard red reproduction region of the CRT described above.

In the background as described above, there is a strong demand for development of a coloring composition capable of reproducing a dark color close to the CRT and forming a red pixel having a high contrast ratio.

Prior art literature

<Patent Documents>

<Patent Document 1> Japanese Patent Application Laid-Open No. 2000-131517

<Patent Document 2> Japanese Patent Application Laid-Open No. 2007-133131

<Patent Document 3> Japanese Patent Application Laid-Open No. 11-14824

<Patent Document 4> Japanese Patent Application Laid-Open No. 2006-47686

Patent Document 5: Japanese Unexamined Patent Publication No. 2002-372618

<Patent Document 6> Japanese Patent Application Laid-Open No. 11-217514

Patent Document 7: Japanese Unexamined Patent Publication No. 2003-183511

Patent Document 8: Japanese Unexamined Patent Publication No. 2006-30674

An object of the present invention is to provide a coloring composition capable of reproducing a dark color close to a CRT and forming a red pixel having a high contrast ratio.

Another object of this invention is to provide the color filter which has a red pixel formed from the said coloring composition, and the color liquid crystal display element provided with this color filter.

As a result of earnest examination, the present inventors found that C.I. Pigment Red 177 and C.I. Pigment Red 242 and C.I. It has been found that the above problems can be solved by using a combination of one or more selected from the group consisting of pigment orange 38, thus completing the present invention.

That is, the present invention firstly,

It is a coloring resin composition containing (A) a coloring agent, (B) binder resin, and (C) polyfunctional monomer, and (A) coloring agent as C.I. Pigment Red 177 and C.I. Pigment Red 242 and C.I. Pigment Orange 38 is used for formation of red pixels containing at least one selected from the group consisting of CIE chromaticity coordinates measured in a C light source and a 2-degree field of view of 0.61≤x≤0.67 and 0.31≤y≤0.35. It is to provide a coloring composition.

Secondly, the present invention

It is providing the color filter provided with the red pixel formed using the said coloring composition.

Thirdly, the present invention

It is to provide a color liquid crystal display device having the color filter.

The coloring composition of this invention can reproduce the dark color near CRT, and can also form the red pixel which has high contrast ratio. Moreover, the red pixel formed using the coloring composition of this invention is excellent in solvent resistance.

Therefore, the coloring composition of this invention can be used very favorably for manufacture of various color filters, including the color filter for color liquid crystal display devices in the electronic industry, and the color filter for color separation of a solid-state image sensor.

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

Color composition for red pixel formation

-(A) colorant-

The coloring agent in this invention is C.I. in the color index (C.I .; the issue of The Society of Dyers and Colorists. Pigment Red 177 and C.I. Pigment Red 242 and C.I. It is characterized by containing 1 or more types chosen from the group which consists of pigment orange 38. As disclosed in Japanese Patent Laid-Open No. 10-227911, Japanese Patent Laid-Open No. 11-231516, Japanese Patent Laid-Open No. 2000-131517, and the like, C.I. It is thought that the coloring composition containing pigment red 177 as a main pigment is not suitable for formation of a red pixel by the point that lightness (light transmittance) is low. On the contrary, the inventors have found that the red pigment and C.I. Pigment Red 242 and / or C.I. By combining Pigment Orange 38 in combination, it has been found that dark colors close to the CRT can be reproduced, and the contrast ratio is high, and the brightness (light transmittance) can also form red pixels comparable to the conventional ones.

The coloring composition of this invention is used in order to form a red pixel, and can contain the pigment of red, yellow, or orange other than the said pigment (henceforth a "other pigment"). Although it does not specifically limit as such a pigment of red, yellow, or orange, An organic pigment is preferable at the point which the color filter requires high light transmittance color development and heat resistance.

As said organic pigment of red among the said other pigments, the compound classified as pigment in a color index, for example, the thing with the following color index (C.I.) number is mentioned.

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 176, 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 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.

Moreover, as said yellow organic pigment among the said other pigments, the compound classified as a pigment in a color index, for example, the thing with the following color index (C.I.) number is mentioned.

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 180, C.I. Pigment Yellow 211.

Moreover, as said organic pigment of orange among the said other pigments, the compound classified as a pigment in a color index, for example, the thing with the following color index (C.I.) number is mentioned.

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 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.

Among these other pigments, C.I. C.I. Pigment Red 166, C.I. Pigment Red 224, C.I. Pigment Orange 71, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 and C.I. Pigment yellow 180 is one or more selected from the group consisting of C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 and C.I. Particularly preferred is one or more selected from the group consisting of Pigment Yellow 180.

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

In the present invention, C.I. Pigment Red 177, 30 to 80 mass%, C.I. Pigment Red 242 and C.I. It is preferable to contain 1-49 mass% of 1 or more types chosen from the group which consists of pigment orange 38, and C.I. Pigment Red 177, 50 to 70 mass%, C.I. Pigment Red 242 and C.I. It is especially preferable to contain 10-49 mass% of 1 or more types chosen from the group which consists of pigment orange 38. In addition, in this invention, when using another pigment, it is preferable that it is 1-50 mass% in all the coloring agents, and it is especially preferable that it is 1-40 mass%. Here, all the coloring agents are C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment orange 38 and all pigments containing other pigments. Therefore, the content rate in all the coloring agents means the content rate in all the pigments.

In addition, C.I. Pigment Red 177 (A1) and C.I. Pigment Red 242 and C.I. As for content mass ratio (A1: A2) with 1 or more types (A2) chosen from the group which consists of pigment orange 38, 30: 70-90: 10, 50: 50-80: 20 are preferable. In addition, C.I. Pigment Red 177 and C.I. Pigment Red 242 and C.I. As for the 1 or more types of sum total content chosen from the group which consists of pigment orange 38, 60-100 mass%, 75-100 mass% is preferable.

By using such a colorant, a dark color close to the CRT can be reproduced, and a red pixel having a high contrast ratio can be formed.

In the present invention, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Orange 38 and other pigments may be purified by recrystallization, reprecipitation, solvent cleaning, sublimation, vacuum heating, combinations thereof, or the like as necessary.

In the present invention, each of the pigments may be used by modifying the particle surface thereof with a polymer if desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., the polymer or oligomer for disperse | distributing various pigments commercially available etc. are mentioned, for example.

In this invention, a coloring composition can be manufactured by a suitable method, For example, although it can manufacture by mixing a component (A) and (B)-(D) component mentioned later with a solvent and an additive, a pigment is used. In the solvent, in the presence of a dispersing agent and a dispersing aid to be added if necessary, with a part of component (B), for example, by mixing and dispersing with a bead mill, a roll mill or the like while grinding to obtain a pigment dispersion. It is preferable to manufacture by adding (B)-(D) component and further solvent and additive further as needed, and mixing.

As the dispersant, for example, a suitable dispersant such as cationic, anionic, nonionic or zwitterionic can be used, but a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, acrylic copolymer, polyurethane, polyester, alkylammonium salt or phosphate ester salt of a high molecular copolymer, cationic comb graft polymer, etc. are mentioned. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branch polymers are graft-bonded to one molecule of a stem polymer having a plurality of basic groups (cationic functional groups), and for example, the stem polymer moiety is polyethyleneimine or eggplant. The polymer which a polymer part consists of a ring-opening polymer of (epsilon) -caprolactone is mentioned. Of these dispersants, modified acrylic copolymers, polyurethanes, and cationic comb graft polymers are preferred.

Such dispersants are commercially available, for example, as a modified acrylic copolymer, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation), polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Corporation), Solsperth 76500 (manufactured by Lubrizol Co., Ltd.), cationic comb graft polymer, 24000, Solspersper 37500 (manufactured by Lubrizol Co., Ltd.), azisper PB821, azisper PB822, azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

These dispersants can be used individually or in mixture of 2 or more types. Since content of a dispersing agent improves developability, it is 100 mass parts or less normally with respect to 100 mass parts of pigments, Preferably it is 0.5-100 mass parts, More preferably, it is 1-70 mass parts, Especially preferably, 10 to 50 parts by mass.

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

Content of the solvent at the time of manufacturing a pigment dispersion liquid is 200-1,200 mass parts normally with respect to 100 mass parts of pigments from a dispersibility of a pigment, Preferably it is 300-1,000 mass parts.

As a dispersion adjuvant used for manufacture of the said pigment dispersion liquid, a blue pigment derivative, a yellow pigment derivative, etc. are mentioned, for example, A copper phthalocyanine derivative etc. are mentioned specifically ,.

(B) binder resin

Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is a polymer which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group is preferable, and especially the ethylenically unsaturated monomer which can copolymerize another ethylenically unsaturated monomer (henceforth "carboxyl group-containing unsaturated monomer") which has one or more carboxyl groups (henceforth "copolymerization property"). Copolymer (hereinafter referred to as "carboxyl group-containing copolymer") is preferred.

As a carboxyl group-containing unsaturated monomer, for example

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

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

Mono ((meth) acryloyloxyalkyl] of a divalent or higher polyhydric carboxylic acid such as monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;

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

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

In the present invention, as the carboxyl group-containing unsaturated monomer, (meth) acrylic acid, monosuccinate [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, and the like are preferable, and in particular (meth) Acrylic acid is preferred.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. When this copolymerization ratio is too small, there exists a tendency for the solubility with respect to the alkaline developing solution of the coloring composition obtained to fall, while when too much, the solubility with respect to an alkaline developing solution will become excessive, and when developing with alkaline developing solution, It tends to be easy to cause dropout and film roughness of the pixel surface.

As the copolymerizable unsaturated monomer, for example,

Maleimide;

N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3 -Maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (acridy N-position substituted maleimide, such as nil) maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, aromatic vinyl compounds such as m-vinylbenzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) arcrelate , sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylic Rate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxyprop Alkylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, 2 Unsaturated carboxes such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and ethylene oxide modified (meth) acrylate of paracumylphenol Acid ester;

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, allyl glycidyl ether;

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

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

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

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

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

In the present invention, the copolymerizable unsaturated monomer is preferably an N-position substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, and the like. N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, Ethylene oxide modified (meth) acrylate of a paracumyl phenol, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, etc. are preferable.

In the present invention, for example, unsaturated isocyanates such as 2- (meth) acryloyloxyethyl isocyanate to a copolymer obtained by copolymerizing a copolymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. By reacting a compound, the carboxyl group-containing copolymer which has a polymerizable unsaturated bond in a side chain can be used as binder resin.

The polystyrene reduced weight average molecular weight (hereinafter sometimes referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is preferably 1,000 to 45,000. And particularly preferably 3,000 to 30,000.

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

If Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical characteristics may be deteriorated. If the Mw is too large, the resolution is reduced or the pattern shape is damaged, Moreover, there exists a possibility that a dry foreign material may generate easily at the time of application | coating by a slit nozzle system.

The binder resin in the present invention is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvalle) in an appropriate solvent for the unsaturated monomer which is a constituent thereof. It can be manufactured by polymerizing in presence of radical polymerization initiators, such as ronitrile) and 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile).

The binder resin in this invention can be manufactured by refine | purifying via the reprecipitation method using 2 or more types of organic solvents of different polarity, after radically polymerizing an unsaturated monomer as mentioned above. That is, the solution in the good solvent after polymerization is removed, if necessary, by infiltration, centrifugation or the like, and then poured into a large amount (usually 5 to 10 times the volume of the polymer solution) in a precipitant (poor solvent) to give a copolymer. Purify by reprecipitation. At that time, among the impurities remaining in the copolymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified binder resin.

As a good solvent / precipitator combination used for this reprecipitation method, for example, diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, methyl Ethyl ketone / n-heptane; and the like.

In addition, the binder resin in this invention uses each radical monomer which becomes the component as the said radical polymerization initiator, the pyrazole-1- dithiocarboxylic acid cyano (dimethyl) methyl ester, and the pyrazole-1- dithiocar Acid benzyl ester, tetraethylthiuram disulfide, bis (pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4- Methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (5-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-yl In the presence of a molecular weight controlling agent that acts as an inipher such as thiocarbonyl) disulfide, bis (pyrrole-1-ylthiocarbonyl) disulfide, bisthiobenzoyldisulfide, and the like, the reaction temperature is usually 0 to 0 in an inert solvent. It can be manufactured by living radical polymerization as 150 degreeC, Preferably it is 50-120 degreeC.

In addition, the binder resin in this invention can be manufactured by radically polymerizing each unsaturated monomer which becomes the structural component in the presence of the said radical polymerization initiator and the polyhydric thiol compound which acts as a chain transfer agent in a suitable solvent. Here, a polyvalent thiol compound means the compound which has two or more thiol groups in 1 molecule, For example, trimethylol propane tris (3-mercapto propionate) and pentaerythritol tetrakis (3-mercapto propionate) ), Tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycorate), 1,4-bis (3 Mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5, -tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2 , 4,6 (1H, 3H, 5H) -trione and the like.

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

In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. When there is too little content of binder resin, there exists a possibility that alkali developability may fall, for example, or the storage stability of the coloring composition obtained may fall, and when too much, the pigment concentration will fall relatively, and it is aimed as a thin film. There is a fear that it is difficult to achieve the color density.

-(C) polyfunctional monomer-

The polyfunctional monomer in the present invention 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 and polypropylene glycol;

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

Oligo (meth) acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, and spiran resins;

Di (meth) acrylates of both terminal hydroxyl polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactones;

Tris [2- (meth) acryloyloxyethyl] phosphate,

Isocyanurate ethylene oxide modified triacrylate;

Poly (meth) acrylate with urethane structure

Etc. can be mentioned.

Among these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols, their dicarboxylic acid modified substances, and poly (meth) acrylates having a urethane structure are preferable. Examples of the poly (meth) acrylates of the trihydric or higher polyhydric alcohols and their dicarboxylic acid modified substances include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacryl. Late, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate , Monoesters of pentaerythritol triacrylate and succinic acid, monoesters of pentaerythritol trimethacrylate and succinic acid, monoesters of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol penta Monoester of methacrylate and succinic acid A fluoride is preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate and monoester of succinic acid are particularly preferred. The monoesters of the cargo and dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, excellent surface smoothness of the colored layer, and ground contamination and film remaining on the substrate and the light shielding layer of the unexposed part. It is preferable at the point which hardly generate | occur | produces water etc.

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

Content of the polyfunctional monomer in this invention becomes like this. Preferably it is 100-500 mass parts, More preferably, it is 110-400 mass parts with respect to 100 mass parts of (B) binder resins. If the content of the polyfunctional monomer is too small, the solvent resistance of the pixel tends to be lowered, while if the content of the polyfunctional monomer is too large, for example, alkali developability is lowered, or the background contamination or the film remains on the substrate or the light shielding layer of the unexposed part. It tends to be easy to generate water.

In this invention, a part of polyfunctional monomer can also be substituted by the monofunctional monomer which has one polymerizable unsaturated bond.

As said monofunctional monomer, mono [of bivalent or more polyvalent carboxylic acids, such as monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl], for example, (Meth) acryloyloxyalkyl] ester; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends such as? -carboxypolycaprolactone mono (meth) acrylate; N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrolidin, N-vinylpyrrolidin , N-vinylimidazole, N-vinylimidazolidine, N-vinylindole, N-vinylindolin, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylpiperidine, N-vinyl N-vinyl nitrogen-containing heterocyclic compounds such as piperazine, N-vinylmorpholine, and N-vinylphenoxazine; In addition to N- (meth) acryloyl morpholine, M-5400, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

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

Since the content ratio of the monofunctional monomer in this invention makes the intensity | strength and surface smoothness of a pixel favorable, with respect to the sum total of a polyfunctional monomer and a monofunctional monomer, Preferably it is 90 mass% or less, More preferably, it is 50 It is mass% or less.

-(D) photoinitiator-

Radiation sensitivity can also be provided to a coloring composition by mix | blending a photoinitiator to the coloring composition of this invention. "Radiation" as used here means including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like.

The photoinitiator in this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of the said (C) polyfunctional monomer and the monofunctional monomer used depending on a case by exposure of a radiation.

As such a photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds and the like.

Although the photoinitiator can be used individually or in mixture of 2 or more types, as a photoinitiator in this invention, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, and a triazine type It is preferable to contain 1 or more types chosen from the group of a compound and O-acyl oxime type compound.

As a specific example of a thioxanthone type compound among the preferable photoinitiators in this invention, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thi Orcanthone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

Specific examples of the acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Moreover, as a specific example of the said biimidazole type compound, 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 etc. are mentioned.

Moreover, when using a biimidazole type compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis ( Amine hydrogen donors, such as diethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof, but the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may further improve sensitivity. It is preferable at the point.

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

In addition, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), and the like.

In this invention, when using radical radicals other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, content of a photoinitiator is 0.01-120 mass parts normally with respect to 100 mass parts of (C) polyfunctional monomers, Preferably it is 1-100 mass parts. When there is too little content of a photoinitiator, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to the predetermined | prescribed arrangement, On the other hand, when too much, the formed pixel at the time of image development There is a tendency to fall off from the substrate.

Other additives

Although the coloring composition of this invention contains the said (A)-(D) component, it may further contain other additives as needed.

As said other additive, For example, fillers, such as glass and an alumina; Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate) s; Surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors such as sodium polyacrylate; And alkali solubility improving agents such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

-menstruum-

Although the coloring composition of this invention contains the said (A)-(C) component, the (D) component optionally added, and another additive, Usually, a solvent is mix | blended and it is manufactured as a liquid composition.

As said solvent, as long as it disperse | distributes or dissolves the component (A)-(D) which comprises a coloring composition, or another additive component, and does not react with these components, and has suitable volatility, it can select suitably and can use.

As such a solvent, for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

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

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

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

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n- formate Amyl, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 Other esters such as ethyl oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

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

Etc. can be mentioned.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, and the like in terms of solubility, pigment dispersibility, and coating properties Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n -Butyl, ethyl pyruvate, etc. are preferable.

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

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

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

Although content of a solvent is not specifically limited, From a viewpoint of the coating property, stability, etc. of the coloring composition obtained, the total concentration of each component except the solvent of the said composition is 5-50 mass% normally, Preferably it is 10-40 mass%. The amount which becomes is preferable.

Color filter

The coloring composition of this invention is suitable for formation of the red pixel which can reproduce the standard color reproduction area | region of said CRT. Specifically, the CIE chromaticity coordinates measured in the C light source and the 2-degree field of view are in the range of red pixels in the range of 0.61≤x≤0.67, 0.31≤y≤0.35, particularly in the range of 0.63≤x≤0.67, 0.32≤y≤0.34. It is suitable for the formation of red pixels present. The color filter of this invention is equipped with the red pixel formed from the coloring composition of this invention.

As a method of forming a color filter, first, the coating film of a colored radiation-sensitive composition is formed on a board | substrate or the board | substrate with which the light shielding layer of the desired pattern was previously formed, the radiation is exposed through the photomask which has a predetermined pattern, and image development is carried out. By dissolving and removing the unexposed part, and post-baking after that, the method of obtaining the pixel of each color is known. Specifically, first, on the surface of the substrate, a light shielding layer is formed so as to partition a portion forming a pixel, if necessary, and the liquid composition of the coloring composition in which the red pigment of the present invention, which gives radiation sensitivity, is dispersed on the substrate. After apply | coating, prebaking is performed and the solvent is evaporated and a coating film is formed. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and post-bakes, and then the pixel array in which the red pixel pattern was arrange | positioned in the predetermined | prescribed array is obtained. Form.

Then, using the liquid composition of each coloring composition in which the green or blue pigment was disperse | distributed, application | coating, prebaking, exposure, image development, and postbaking of each liquid composition were performed as mentioned above, and the red pixel array and blue By sequentially forming pixel arrays on the same substrate, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

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

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

When applying the liquid composition of a coloring composition to a board | substrate, the appropriate coating methods, such as spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet method, can be employ | adopted, Especially, Spin coating and slit die coating are preferred.

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

As the radiation used when forming the pixel, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The exposure dose of radiation is generally 10 to 10,000 J / m 2. According to the coloring composition of this invention, even the exposure amount of 800 J / m <2> or less and the exposure amount of 600 J / m <2> or less can form the pixel excellent also in solvent resistance.

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

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. In addition, after alkali development, water washing is normally performed.

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

Moreover, as a 2nd method of forming a color filter, the method of obtaining the pixel of each color by the inkjet method currently disclosed by Unexamined-Japanese-Patent No. 7-318723, 2000-310706, etc. is also known.

The color filter of the present invention thus obtained can reproduce a dark color close to the CRT and has a high contrast ratio, which is very useful for a liquid crystal display application having a wide color reproduction area such as a TV.

Color liquid crystal display element

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

The color liquid crystal display element of this invention can take a suitable structure. For example, the color filter may be formed on a substrate separate from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may have a structure opposite to each other via the liquid crystal layer. The substrate in which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate in which the ITO (indium oxide doped with tin) electrode is formed via the liquid crystal layer face each other. You can also take The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high definition liquid crystal display element is obtained.

<Example>

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

Preparation of Pigment Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Red 242 is 7.2 parts by mass, C.I. 7.8 parts by mass of Pigment Red 177, 5 parts by mass of Azisper PB880 (manufactured by Ajino Moto Fine Techno Co., Ltd.) as a dispersant, and 80 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours with a bead mill. To prepare a pigment dispersion (M-1).

Preparation Examples 2 to 17

In Production Example 1, pigment dispersion liquids (M-2) to (M-17) were prepared in the same manner as in Production Example 1 except that the colorant was changed as shown in Table 1 below.

Preparation Example 18

(A) As a coloring agent, C.I. Pigment Orange 38 to 9 parts by mass, C.I. 6 parts by mass of Pigment Red 177, 5 parts by mass of Azisper PB822 (manufactured by Ajino Moto Fine Techno Co., Ltd.) as a dispersant, and 80 parts by mass of propylene glycol monomethyl ether acetate as a solvent for 12 hours by mixing and dispersing To prepare a pigment dispersion (M-18).

Preparation Examples 19 to 33

In Production Example 19, pigment dispersion liquids (M-19) to (M-33) were prepared in the same manner as in Production Example 18 except that the colorant was changed as shown in Table 2 below.

In Table 1 and Table 2, for example, "R242" means C.I. Pigment Red 242 is &quot; O38 &quot; Pigment Orange 38 is C.I. with "Y83". It means pigment yellow 83, respectively.

(B) Synthesis of Alkali-Soluble Resin

Synthesis Example 1

0.5 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by mass of methacrylic acid and 20 parts of N-phenylmaleimide. 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.) as a mass part, 55 mass parts of benzyl methacrylate, 10 mass parts of styrene, and a molecular weight regulator. The part was added and nitrogen-substituted. Then, it stirred gently, raised the temperature of the reaction solution to 80 degreeC, hold | maintained this temperature for 5 hours, and superposed | polymerized, and obtained the resin solution (solid content concentration = 33.3 mass%). Obtained resin was Mw = 25,000 and Mn = 12,000. This resin solution is referred to as "resin solution (B-1)".

Example 1

(A) 100 mass parts of pigment dispersion liquid (M-1) as a coloring agent, (B) 10 mass parts (solid content conversion) of a resin solution (B-1) as alkali-soluble resin, (C) dipentaerythritol hexa as a polyfunctional monomer 15 parts by mass of acrylate, (D) 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4,4'-bis (diethyl as photopolymerization initiator 1 mass part of amino) benzophenone and propylene glycol monomethyl ether acetate were mixed as a solvent, and the liquid composition (R-1) of 25% of solid content concentration was prepared.

About the liquid composition (R-1), the board | substrate for evaluation was produced and evaluated in accordance with the following procedure. The evaluation results are shown in Table 3 below.

Manufacture of substrate

The liquid composition (R-1) was applied onto the soda glass substrate on which a SiO ₂ film was formed to prevent elution of sodium ions on the surface thereof by using a spin coater at a variable speed, and then applied to three sheets, followed by a hot plate at 90 ° C. for 4 minutes. Prebaking was performed to form three coating films having different film thicknesses.

Subsequently, after cooling these board | substrates to room temperature, the radiation which contained each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film by the exposure amount of 400 J / m <2> using the high pressure mercury lamp. Subsequently, after developing a shower by discharging the developing solution containing a 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with respect to these board | substrates at developing pressure of 1 kgf / cm <2> (nozzle diameter 1mm), it posts further at 220 degreeC for 30 minutes. Baking was performed and the board | substrate for evaluation in which the red cured film was formed was manufactured.

Evaluation of Chromaticity Characteristics

About the obtained board | substrate, chromaticity coordinate value (x, y) and stimulus value (Y) in the CIE colorimeter were measured by C color light source (MCPD2000 by Otsuka Denshi Co., Ltd.). In addition, the film thickness of the obtained cured film was measured using the alpha step IQ by KLA-Tencor. From the measurement result, chromaticity coordinate value y and stimulus value Y which chromaticity coordinate values x become 0.630, 0.650, 0.670 were calculated | required. The evaluation results are shown in Table 3. The larger the magnetic pole value Y, the higher the light transmittance (luminance).

Evaluation of Contrast Ratio

The substrate obtained by evaluating the chromaticity characteristics is sandwiched by two deflection plates, the deflection plate on the front side is rotated while irradiating with a fluorescent lamp (wavelength range 380 to 780 nm) from the rear side, and the light intensity transmitted is measured by the luminance meter LS. Maximum value and minimum value were measured at -100 (manufactured by Minolta Co., Ltd.). And the value which divided the maximum value by the minimum value was evaluated as contrast ratio. From the measurement results, contrast ratios at chromaticity coordinate values x of 0.630, 0.650, and 0.670 were determined. The evaluation results are shown in Table 3.

Evaluation of solvent resistance

The liquid composition (R-1) was applied onto a soda glass substrate on which a SiO ₂ film was formed to prevent elution of sodium ions on the surface using a spin coater, followed by prebaking for 4 minutes with a hot plate at 90 ° C. The coating film whose thickness is set to 2.5 micrometers was formed.

Subsequently, after cooling these board | substrates to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film by the high pressure mercury lamp at the exposure amount of 400 J / m <2>. Then, after shower-development by discharging the developing solution containing the 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with respect to these board | substrates at developing pressure of 1 kgf / cm <2> (nozzle diameter of 1 mm), after 30 minutes at 220 degreeC, Post-baking was carried out to form a 200 × 200 μm red pixel pattern on the substrate.

The obtained board | substrate was immersed in 60 degreeC N-methylpyrrolidone for 30 minutes, and the dot pattern before and behind immersion was observed with the scanning electron microscope. ○ When the pattern which has a favorable edge shape is formed, and the film thickness ratio (film thickness after immersion x 100 / film thickness before immersion) before and after immersion is 95% or more, (circle) the film thickness ratio before and behind immersion is less than 95%, Or (triangle | delta) and the case where all the patterns peel from a board | substrate after immersion were evaluated as a case where a distortion appears in a part of pattern as x. The evaluation results are shown in Table 3.

Examples 2 to 27 and Comparative Examples 1 to 11

In Example 1, liquid compositions (R-2) to (R-38) were prepared in the same manner as in Example 1 except that the pigment dispersion was changed as shown in Tables 3 and 4 below.

Next, it evaluated similarly to Example 1 except having used liquid compositions (R-2)-(R-38) instead of liquid composition (R-1), respectively. The evaluation results are shown in Tables 3 and 4. In addition, in the evaluation of the solvent resistance of Example 16, a film residue appeared in the unexposed part of the board | substrate.

In Table 3 and Table 4, "B / C (mass part)" means content (mass part) of (B) alkali-soluble resin and (C) polyfunctional monomer.

From Tables 1 to 4, Pigment Red 177 and C.I. Pigment Red 242 or C.I. When Pigment Orange 38 was used, it was found that dark colors close to the CRT can be reproduced, and a high contrast ratio can be obtained.

On the other hand, as a coloring agent, C.I. Pigment Red 254 and C.I. Attempting to reproduce a color close to the CRT using Pigment Red 177 showed a low contrast ratio (Comparative Examples 1 and 7), and even contrasting with yellow pigments resulted in insufficient contrast ratio and lowered stimulus value (Y). (Comparative Examples 2, 3, 8, 9). Pigment Red 254 and C.I. Pigment Red 242 or C.I. When Pigment Orange 38 was used, the irritation value (Y) was high, but C.I. When Pigment Red 254 is the main pigment, the contrast ratio is low (Comparative Examples 4, 5, 10), and C.I. Pigment Red 242 or C.I. When Pigment Orange 38 was used as the main pigment, it was found that the contrast ratio was insufficient and it was difficult to reproduce the color close to the CRT itself (Comparative Examples 6 and 11).

Surprisingly, the pixel pattern formed using the coloring composition of the present invention is a C.I. It turned out that it is excellent in solvent resistance compared with the pixel pattern formed using the coloring composition containing pigment red 254.

Claims (7)

It is a coloring composition containing (A) a coloring agent, (B) binder resin, and (C) polyfunctional monomer, As (A) coloring agent, it is C.I. Pigment Red 177 and C.I. Pigment Red 242 and C.I. Pigment Orange 38 is used for formation of red pixels containing at least one selected from the group consisting of CIE chromaticity coordinates measured in a C light source and a 2-degree field of view of 0.61≤x≤0.67 and 0.31≤y≤0.35. Coloring composition. The method of claim 1, wherein C.I. Pigment Red 177, 30 to 80 mass%, C.I. Pigment Red 242 and C.I. The coloring composition containing 1-49 mass% of 1 or more types chosen from the group which consists of pigment orange 38. The method of claim 1 or 2, further comprising C.I. Pigment Red 166, C.I. Pigment Red 224, C.I. Pigment Orange 71, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 and C.I. Pigment Yellow The coloring composition containing 1 or more types chosen from the group which consists of 180. The coloring composition as described in any one of Claims 1-3 whose content of the (C) polyfunctional monomer is 100-500 mass parts with respect to 100 mass parts of (B) binder resins. The coloring composition according to any one of claims 1 to 4, further comprising (D) a photopolymerization initiator. The red pixel in which the CIE chromaticity coordinates measured by the C light source and the 2 degree visual field formed using the coloring composition of any one of Claims 1-5 are in the range of 0.61 <= x <0.67 and 0.31 <= y <0.35. A color filter comprising a. The color liquid crystal display element provided with the color filter of Claim 6.