JP5402158B2 - Color composition for forming red pixel, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a coloring composition for forming a red pixel, a color filter, and a color liquid crystal display device. More specifically, the present invention is used for manufacturing a red pixel used in a transmissive or reflective color liquid crystal device, a color image pickup tube element, and the like. The present invention relates to a colored composition, a color filter having pixels formed from the colored composition, and a color liquid crystal display device including the color filter.

With the spread of digital video cameras and high-definition televisions, liquid crystal display elements equipped with color filters are required to expand the color reproduction area so that deep blue or bright sunsets like the winter sea can be displayed. Yes. In general, the color reproduction region of a liquid crystal display element is set on the basis of a CRT and is required to be as close as possible. The standard color reproduction area of CRT includes, for example, the color space defined by the color television system adopted in the United States, Japan, etc., which is presented by the National Television System Committee (NTSC), the Internet, and the interior of a personal computer And sRGB, which is a standard color space for digital images handled in, and the color space presented by European Broadcasting Union (EBU). The red CIE chromaticity coordinates in these standard color reproduction regions 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 hue as described above, if the “blackness” of the black display is not clearly displayed, the screen will have a sharp outline and no sharpness. At the same time, a pixel having a high contrast ratio is desired.

By the way, about the coloring composition for red pixel formation, various proposals are made in order to improve the color characteristics. For example, in Patent Document 1 and Patent Document 2, C.I. I. Pigment red 254 and C.I. I. It has been proposed to use Pigment Red 177 in combination with various yellow pigments. However, such a combination of pigments is insufficient for obtaining a red pixel having a high contrast ratio.
On the other hand, in Patent Document 3 and Patent Document 4, C.I. I. Pigment Red 242 as a main pigment, C.I. I. Pigment red 254, C.I. I. It has been proposed to use together CI Pigment Red 177 and the like as a toning pigment. However, such a pigment composition may itself be difficult to reproduce the standard red color reproduction region of the CRT described above, and is insufficient for obtaining a red pixel having a high contrast ratio. In contrast, in Patent Document 5, C.I. I. Pigment Red 254 as a main pigment, C.I. I. Although it is disclosed that the color characteristics can be improved by using Pigment Red 242 as a toning pigment, even the composition of such a pigment is insufficient for obtaining a red pixel having a high contrast ratio.
Furthermore, in Patent Documents 6 to 8, C.I. I. Pigment red 254 and C.I. I. The use of a combination of CI Pigment Orange 38 is disclosed. However, such a combination of pigments is insufficient for obtaining a red pixel having a high contrast ratio, and it may be difficult to reproduce the standard red color reproduction region of the CRT described above.
From the background as described above, there is a strong demand for the development of a coloring composition that can reproduce a dark hue close to that of a CRT and that can form a red pixel having a high contrast ratio.

JP 2000-131517 A JP 2007-133131 A Japanese Patent Laid-Open No. 11-14824 JP-A-2006-47686 JP-A-2002-372618 JP 11-217514 A JP 2003-183511 A JP 2006-30664 A

An object of the present invention is to provide a coloring composition capable of reproducing a dark hue close to that of a CRT and forming a red pixel having a high contrast ratio.
Another object of the present invention is to provide a color filter having red pixels formed from the colored composition, and a color liquid crystal display device comprising the color filter.

  As a result of intensive studies, the present inventors have determined that C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The present inventors have found that the above problem can be solved by using at least one selected from the group consisting of CI Pigment Orange 38 in combination, and have completed the present invention.

That is, the present invention firstly
A colored resin composition comprising (A) a colorant, (B) a binder resin, and (C) a polyfunctional monomer, wherein (A) C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. At least one selected from the group consisting of CI Pigment Orange 38, and CIE chromaticity coordinates measured with a C light source and a 2-degree field of view are 0.61 ≦ x ≦ 0.67, 0.31 ≦ y ≦ 0.35 The present invention provides a coloring composition for forming a red pixel in the range described above.

The present invention secondly,
The present invention provides a color filter comprising a red pixel formed using the colored composition.
Third, the present invention
A color liquid crystal display device including the color filter is provided.

The coloring composition of the present invention can reproduce a dark hue close to CRT and can form a red pixel having a high contrast ratio. And the red pixel formed using the coloring composition of this invention is excellent in solvent resistance.
Therefore, the colored composition of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state imaging devices in the electronic industry. .

Hereinafter, the present invention will be described in detail.
Color composition for forming red pixel- (A) Colorant-
The colorant in the present invention is a C.I. color index (CI; issued by The Society of Dyers and Colorists, the same applies hereinafter). I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. And at least one selected from the group consisting of CI Pigment Orange 38. As disclosed in JP-A-10-227911, JP-A-11-231516, JP-A-2000-131517, etc., C.I. I. It has been considered that a coloring composition containing Pigment Red 177 as a main pigment is not suitable for forming red pixels because of its low brightness (light transmittance). On the other hand, the present inventors have found that the red pigment and C.I. I. Pigment red 242 and / or C.I. I. It has been found that by combining colors with Pigment Orange 38, a dark hue close to that of a CRT can be reproduced, a contrast ratio is high, and a red pixel having a brightness (light transmittance) comparable to that of a conventional one can be formed. It is a thing.

  The coloring composition of the present invention is used to form a red pixel, and other red, yellow or orange pigments (hereinafter sometimes referred to as “other pigments”) other than the above pigments. Furthermore, it can contain. Such a red, yellow or orange pigment is not particularly limited, but an organic pigment is preferred because the color filter is required to have high purity and high light transmission color development and heat resistance.

  Among the other pigments, the red organic pigment is, for example, a compound classified as a pigment in the color index, specifically, a color index (CI) number as shown below. Can be mentioned.

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

  Among the other pigments, the yellow organic pigment is, for example, a compound classified as a pigment in the color index, specifically, a color index (CI) number as shown below. You can list what you have.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 211.

  Among the other pigments, the orange organic pigment is, for example, a compound classified as a pigment in the color index, specifically, a color index (CI) number as shown below. You can list what you have.

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

Among these other pigments, C.I. is from the point of reproducing a dark hue close to CRT and obtaining a high contrast ratio. I. Pigment red 166, C.I. I. Pigment red 224, C.I. I. Pigment orange 71, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. Preferably at least one selected from the group consisting of CI Pigment Yellow 180; I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. Particularly preferred is at least one selected from the group consisting of CI Pigment Yellow 180.
The other pigments can be used alone or in admixture of two or more.

  In the present invention, from the viewpoint of obtaining a hue close to CRT and obtaining a high contrast ratio, C.I. I. Pigment Red 177 in an amount of 30 to 80% by mass, C.I. I. Pigment red 242 and C.I. I. It is preferable to contain 1 to 49% by mass of at least one selected from the group consisting of CI Pigment Orange 38. I. Pigment Red 177 in an amount of 50 to 70% by mass, C.I. I. Pigment red 242 and C.I. I. It is particularly preferable to contain 10 to 49% by mass of at least one selected from the group consisting of CI Pigment Orange 38. Moreover, in this invention, when using another pigment, it is preferable that the content rate is 1-50 mass% in all the coloring agents, and it is especially preferable that it is 1-40 mass%. Here, the total colorant is C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. All pigments including Pigment Orange 38 and other pigments. Therefore, the content ratio in all colorants means the content ratio in all pigments.

In addition, C.I. I. Pigment red 177 (A1), C.I. I. Pigment red 242 and C.I. I. The content mass ratio (A1: A2) to at least one (A2) selected from the group consisting of CI Pigment Orange 38 is preferably 30:70 to 90:10, and more preferably 50:50 to 80:20. In addition, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The total content of at least one selected from the group consisting of CI Pigment Orange 38 is preferably 60 to 100% by mass, and more preferably 75 to 100% by mass.
By using such a colorant, a dark hue close to that of a CRT can be reproduced, and a red pixel having a high contrast ratio can be formed.

  In the present invention, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment Orange 38 and other pigments can be purified and used by recrystallization method, reprecipitation method, solvent washing method, sublimation method, vacuum heating method, or a combination thereof, if necessary.

  In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876 and various commercially available pigment-dispersing polymers or oligomers.

  In the present invention, the coloring composition can be prepared by an appropriate method. For example, the coloring composition is prepared by mixing the component (A) and the components (B) to (D) described later together with a solvent and additives. While being pulverized in a solvent, in the presence of a dispersing agent and, if necessary, a dispersing aid, optionally with a part of the component (B), for example, using a bead mill, a roll mill or the like. It is preferably prepared by mixing and dispersing to obtain a pigment dispersion, and adding (B) to (D) components to this, and further adding an additional solvent or additive as necessary, and mixing.

  As the dispersant, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, an alkylammonium salt or a phosphate ester salt of a polymer copolymer, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

  Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161 as polyurethane, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and cationic comb-type graft polymer Solsperse 24000, Solsperse 37500 (manufactured by Lubrizol Corporation), Addisper PB821, Addispar PB822, Addisper PB880 (Ajinomoto Fine Techno Co., Ltd.) And the like can be given.

These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by mass or less, preferably 0.5 to 100 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the pigment from the viewpoint of improving developability. Especially preferably, it is 10-50 mass parts.
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent illustrated about the liquid composition of the coloring composition mentioned later can be mentioned, for example.
The content of the solvent when preparing the pigment dispersion is usually 200 to 1,200 parts by mass, preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment from the viewpoint of the dispersibility of the pigment. is there.

  Examples of the dispersion aid used for the preparation of the pigment dispersion include a blue pigment derivative and a yellow pigment derivative. Specifically, for example, a copper phthalocyanine derivative can be used.

-(B) Binder resin-
The binder resin (B) in the present invention is not particularly limited, but is preferably a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) and other copolymers. A copolymer with a possible ethylenically unsaturated monomer (hereinafter referred to as “copolymerizable unsaturated monomer”) (hereinafter referred to as “carboxyl group-containing copolymer”) is preferred.

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-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, the carboxyl group-containing unsaturated monomer is preferably (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, Particularly preferred is (meth) acrylic acid.

  In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. If the copolymerization ratio is too small, the solubility of the resulting colored composition in an alkaline developer tends to be reduced. On the other hand, if the copolymerization ratio is too large, the solubility in an alkaline developer becomes excessive, and when developing with an alkaline developer. In addition, the pixel tends to drop off from the substrate and the pixel surface becomes rough.

Examples of the copolymerizable unsaturated monomer include:
Maleimide;
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- N-substituted maleimides such as succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinyl Phenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether , Aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Unsaturated carboxylic acid esters such as glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, 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, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  In the present invention, examples of the copolymerizable unsaturated monomer include N-position substituted maleimide, aromatic vinyl compound, unsaturated carboxylic acid ester, macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain, and the like. In particular, 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 paracumylphenol , Polystyrene macromonomer, polymethylmethacrylate macromonomer and the like are preferable.

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

The weight average molecular weight in terms of polystyrene (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. Particularly preferred is 3,000 to 30,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the binder resin in the present invention is preferably 1 to 5, more preferably 1 to 4.
If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

  The binder resin in the present invention is prepared by, for example, using an unsaturated monomer as a constituent component of 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl) in a suitable solvent. Valeronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like, and can be produced by polymerization in the presence of a radical polymerization initiator.

The binder resin in the present invention can be produced by radical polymerization of an unsaturated monomer as described above and then purifying through a reprecipitation method using two or more organic solvents having different polarities. That is, after removing insoluble impurities from the solution in a good solvent after polymerization by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution) of a precipitant (poor) Purification by pouring into the solvent) and reprecipitation of the copolymer. At that time, out of 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.
Examples of the good solvent / precipitant combination used in this reprecipitation method include 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. Can be mentioned.

  In the binder resin of the present invention, each unsaturated monomer that is a constituent component of the binder resin includes the above radical polymerization initiator, pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and pyrazole-1-dithiocarboxylic 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-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bis Thiobenzoyl In the presence of a molecular weight control agent that acts as an iniferter such as sulfide, the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C. in an inert solvent, and can be produced by living radical polymerization. .

  Further, the binder resin in the present invention is a radical polymerization of each unsaturated monomer as a constituent component in an appropriate solvent in the presence of the radical polymerization initiator and a polyvalent thiol compound that acts as a chain transfer agent. Can be manufactured. Here, the polyvalent thiol compound means a compound having two or more thiol groups in one molecule, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropio). Nate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryl) Oxy) 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. If the content of the binder resin is too small, for example, alkali developability may decrease or the storage stability of the resulting colored composition may decrease. On the other hand, if the content is too large, the pigment concentration relatively decreases. Therefore, it may be difficult to achieve a target color density as a thin film.

-(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 polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol, and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both end hydroxyl polymers such as both end hydroxypoly-1,3-butadiene, both end hydroxypolyisoprene, both end hydroxypolycaprolactone;
Tris [2- (meth) acryloyloxyethyl] phosphate,
Isocyanuric acid ethylene oxide modified triacrylate;
Examples thereof include poly (meth) acrylate having a urethane structure.

Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols, their dicarboxylic acid-modified products, and poly (meth) acrylates having a urethane structure are preferred. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate and succinic acid Monoesterified product with dipentaerythritol Monoesterified products of acrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Monoesterified product of hexaacrylate, pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of colored layer, excellent surface smoothness of colored layer, and unexposed This is preferable in that ground stains, film residue, and the like hardly occur on the substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The content of the polyfunctional monomer in the present invention is preferably 100 to 500 parts by mass, more preferably 110 to 400 parts by mass with respect to 100 parts by mass of the (B) binder resin. If the content of the polyfunctional monomer is too small, the solvent resistance of the pixel tends to be lowered. On the other hand, if the content is too large, for example, alkali developability is lowered, the substrate on the unexposed area or the light shielding layer. There is a tendency that stains, film residue, etc. are likely to occur on the top.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] ester of acid; mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinyl Indole, N-vinylindoline, N-vinylbenzimidazole, N-vinylcal N-vinyl nitrogen-containing heterocyclic compounds such as azole, N-vinyl piperidine, N-vinyl piperazine, N-vinyl morpholine, N-vinyl phenoxazine; in addition to N- (meth) acryloyl morpholine, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more.

  The content ratio of the monofunctional monomer in the present invention is preferably 90% with respect to the total of the polyfunctional monomer and the monofunctional monomer from the viewpoint of improving the strength and surface smoothness of the pixel. It is at most 50% by mass, more preferably at most 50% by mass.

-(D) Photopolymerization initiator-
By adding a photopolymerization initiator to the colored composition of the present invention, radiation sensitivity can be imparted to the colored composition. The term “radiation” as used herein means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The photopolymerization initiator in the present invention is a compound that generates an active species capable of initiating polymerization of the (C) polyfunctional monomer and optionally used monofunctional monomer by exposure to radiation. .
Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a diazo type compound etc. can be mentioned.

  In the present invention, the photopolymerization initiators can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, thioxanthone compounds, acetophenone compounds, biimidazole compounds, It is preferable to contain at least one selected from the group of triazine compounds and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

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

  Specific examples of the biimidazole compound include 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, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole 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, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine 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 (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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 the present invention, when a photo radical generator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  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. If the content of the photopolymerization initiator is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. The developed pixels tend to drop off from the substrate during development.

-Other additives-
Although the coloring composition of this invention contains the said (A)-(D) component, it can further contain another additive as needed.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulation agents such as sodium acrylate; alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

-Solvent-
The colored composition of the present invention contains the components (A) to (C), the optionally added component (D), and other additives, but usually a liquid composition containing a solvent. It is prepared as a product.
As the solvent, as long as the components (A) to (D) and other additive components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as 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, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, 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 oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid - propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together 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, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually 5 to 5 from the viewpoints of applicability and stability of the resulting colored composition. The amount is 50% by mass, preferably 10 to 40% by mass.

Color filter The colored composition of the present invention is suitable for forming a red pixel capable of reproducing the standard red color reproduction region of the CRT described above. Specifically, a red pixel having a CIE chromaticity coordinate measured in a range of 0.61 ≦ x ≦ 0.67 and 0.31 ≦ y ≦ 0.35, particularly 0.63, measured with a C light source and a two-degree field of view. It is suitable for forming red pixels in the range of ≦ x ≦ 0.67 and 0.32 ≦ y ≦ 0.34. The color filter of the present invention includes a red pixel formed from the colored composition of the present invention.
As a method for forming a color filter, first, a photomask having a predetermined pattern is formed by forming a coating film of a colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. There is known a method of obtaining pixels of each color by exposing to radiation, developing, dissolving and removing unexposed portions, and then post-baking.
Specifically, first, on the surface of the substrate, if necessary, a light-shielding layer is formed so as to partition a portion for forming pixels, and the red pigment of the present invention to which radiation sensitivity is imparted is provided on this substrate. After applying the liquid composition of the colored composition in which is dispersed, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each coloring composition in which a green or blue pigment is dispersed, application of each liquid composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a red pixel. By sequentially forming the array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

Examples of the substrate used when forming the pixel include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, 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, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition of the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method is used. In particular, spin coating and slit die coating are preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is generally a 10~10,000J / m ^2. According to the coloring composition of the present invention, it is possible to form a pixel having an exposure amount of 800 J / m ² or less, and even an exposure amount of 600 J / m ² or less and excellent solvent resistance.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

As a second method of forming a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 is also known.
The color filter of the present invention thus obtained can reproduce a dark hue close to that of a CRT and has a high contrast ratio. Therefore, it is extremely useful for a liquid crystal display application having a wide color reproduction region such as a TV. It is.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that faces each other via the The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Examples 12 and 16 are reference examples and are not included in the scope of the claims.

Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Red 242, 7.2 parts by mass, C.I. I. 7.8 parts by mass of Pigment Red 177, 5 parts by mass of Ajisper PB880 (manufactured by Ajinomoto 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 by a bead mill. A pigment dispersion (M-1) was prepared.

Preparation Examples 2-17
Pigment dispersions (M-2) to (M-17) were prepared in the same manner as in Preparation Example 1 except that the colorant was changed as shown in Table 1 in Preparation Example 1.

Preparation Example 18
(A) C.I. I. 9 parts by mass of CI Pigment Orange 38, C.I. I. 6 parts by weight of Pigment Red 177, 5 parts by weight of Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and 80 parts by weight of propylene glycol monomethyl ether acetate as a solvent are mixed and dispersed by a bead mill for 12 hours to disperse the pigment. A liquid (M-18) was prepared.

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

  In Tables 1 and 2, for example, “R242” means C.I. I. Pigment Red 242, “O38” means C.I. I. Pigment Orange 38, “Y83” is C.I. I. Each means CI Pigment Yellow 83.

(B) Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 0.5 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid and N-phenylmaleimide 20 1 part by mass, 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, and 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMPII-20P, manufactured by Sakai Chemical Industry Co., Ltd.) as a molecular weight regulator And replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a resin solution (solid content concentration = 33.3% by mass). The 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 parts by mass of a pigment dispersion (M-1) as a colorant, (B) 10 parts by mass (in terms of solid content) of a resin solution (B-1) as an alkali-soluble resin, (C) a polyfunctional monomer 15 parts by mass of dipentaerythritol hexaacrylate, and (D) 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator and 4,4′- Bis (diethylamino) benzophenone 1 part by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R-1) having a solid content concentration of 25%.
About the liquid composition (R-1), the board | substrate for evaluation was created and evaluated according to the following procedure. The evaluation results are shown in Table 3.

Substrate preparation The liquid composition (R-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater with variable number of rotations. After that, prebaking was performed for 4 minutes on a 90 ° C. hot plate to form three coating films with different film thicknesses.
Next, after these substrates were cooled to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 400 J / m ² using a high-pressure mercury lamp. Thereafter, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) on these substrates, Post-baking was performed at 220 ° C. for 30 minutes to prepare an evaluation substrate on which a red cured film was formed.

Evaluation of Chromaticity Characteristics For the obtained substrate, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), C light source, chromaticity coordinate value (x, y) and stimulus in the CIE color system with a 2 degree visual field The value (Y) was measured. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. From the measurement results, the chromaticity coordinate value y and the stimulus value (Y) at which the chromaticity coordinate value x becomes 0.630, 0.650, and 0.670 were obtained. The evaluation results are shown in Table 3. The larger the stimulus value (Y), the higher the light transmittance (brightness).

Evaluation of contrast ratio The substrate obtained by the above evaluation of chromaticity characteristics is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and transmitted. The maximum value and the minimum value were measured with a luminance meter LS-100 (Minolta Co., Ltd.). A value obtained by dividing the maximum value by the minimum value was evaluated as the contrast ratio. From the measurement results, the contrast ratios at chromaticity coordinate values x of 0.630, 0.650, and 0.670 were obtained. The evaluation results are shown in Table 3.

Evaluation of solvent resistance The liquid composition (R-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 4 minutes to form a coating film having a film thickness of 2.5 μm after pre-baking.
Next, after these substrates were cooled to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² through a photomask using a high-pressure mercury lamp. Thereafter, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) on these substrates, Post baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm red pixel pattern on the substrate.
The obtained substrate was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes, and the dot patterns before and after the immersion were observed with a scanning electron microscope. ○, when the pattern having a good edge shape is formed and the film thickness ratio before and after immersion (film thickness after immersion x 100 / film thickness before immersion) is 95% or more, film thickness before and after immersion A case where the ratio was less than 95% or a portion of the pattern was found to be chipped was evaluated as Δ, and a case where the pattern was all peeled off from the substrate after immersion was evaluated as ×. The evaluation results are shown in Table 3.

Examples 2-27 and Comparative Examples 1-11
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 in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (R-2) to (R-38) were used in place of the liquid composition (R-1). The evaluation results are shown in Table 3 and Table 4. In the evaluation of the solvent resistance of Example 16, a film residue was observed in the unexposed portion of the substrate.

  In Tables 3 and 4, “B / C (parts by mass)” means the content (parts by mass) of (B) an alkali-soluble resin and (C) a polyfunctional monomer.

From Tables 1 to 4, Pigment Red 177 and C.I. I. Pigment red 242 or C.I. I. It can be seen that if Pigment Orange 38 is used, a dark hue close to CRT can be reproduced and a high contrast ratio can be obtained.
In contrast, C.I. I. Pigment red 254 and C.I. I. When trying to reproduce a hue close to CRT using Pigment Red 177, the contrast ratio is low (Comparative Examples 1 and 7), and even when toning using a yellow pigment, the contrast ratio is insufficient and the stimulation value It can be seen that (Y) also decreases (Comparative Examples 2, 3, 8, 9). Pigment Red 254 as a colorant, and C.I. I. Pigment red 242 or C.I. I. When using CI Pigment Orange 38, the stimulation value (Y) is high, but C.I. I. When Pigment Red 254 is the main pigment, the contrast ratio is low (Comparative Examples 4, 5, and 10). I. Pigment red 242 or C.I. I. It can be seen that when Pigment Orange 38 is used as the main pigment, the contrast ratio is insufficient and it is difficult to reproduce the hue close to that of CRT (Comparative Examples 6 and 11).
Further surprisingly, the pixel pattern formed using the coloring composition of the present invention has been mainly used in the C.I. I. It can also be seen that the solvent resistance is superior to a pixel pattern formed using a coloring composition containing CI Pigment Red 254.

Claims (6)

A coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polyfunctional monomer, wherein (A) C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. And at least one selected from the group consisting of CI Pigment Orange 38, (C) the content of the polyfunctional monomer is 100 to 500 parts by mass with respect to 100 parts by mass of (B) binder resin, C A colored composition for forming a red pixel having a CIE chromaticity coordinate measured in a range of 0.61 ≦ x ≦ 0.67 and 0.31 ≦ y ≦ 0.35 measured with a light source and a two-degree field of view.   C. in all colorants I. Pigment Red 177 in an amount of 30 to 80% by mass, C.I. I. Pigment red 242 and C.I. I. The coloring composition according to claim 1, comprising 1 to 49% by mass of at least one selected from the group consisting of CI Pigment Orange 38.   As a colorant, C.I. I. Pigment red 166, C.I. I. Pigment red 224, C.I. I. Pigment orange 71, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. The coloring composition according to claim 1 or 2, comprising at least one selected from the group consisting of CI Pigment Yellow 180. Furthermore, (D) The coloring composition of any one of Claims 1-3 containing a photoinitiator. Claim 1 is formed by using the coloring composition according to any of 4, C light source, CIE chromaticity coordinates measured in 2-degree field of view is 0.61 ≦ x ≦ 0.67,0.31 ≦ y A color filter comprising red pixels in a range of ≦ 0.35. A color liquid crystal display device comprising the color filter according to claim 5 .