JP2010092014A - Radiation sensitive coloring composition, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive coloring composition which forms green pixels high in brightness and contrast without lowering the contrast over aging. <P>SOLUTION: The radiation sensitive coloring composition contains (A) a coloring agent, (B) an alkali-soluble polymer resin, (C) a polyfunctional monomer, (D) a radiation sensitive polymerization initiator, and (E) a solvent. It contains C.I. pigment green 58 as (A) the coloring agent, and two acetoxy groups as (E) the solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored radiation-sensitive composition, a color filter, and a color liquid crystal display element. More specifically, the present invention relates to a transmissive or reflective color liquid crystal display device, a color imaging tube element, an organic EL display element, electronic paper, and the like. RADIATION-SENSITIVE COMPOSITION USED FOR FORMATION OF COLORED LAYER USEFUL FOR COLOR FILTER USED, COLOR FILTER HAVING COLORED LAYER FORMED USING THE RADIATION-SENSITIVE COMPOSITION, AND COLOR LIQUID CRYSTAL DISPLAY DEVICE HAVING THE COLOR FILTER About.

  As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (for example, patent documents) 1 and Patent Document 2).

A liquid crystal display device having such a color filter is required to have higher brightness and an expanded color reproduction region. For this reason, color filters are required to have higher light transmittance and higher color purity in recent years. ing.
For green pixels, a pigment composition containing a polyhalogenated zinc phthalocyanine pigment is known as a material capable of providing a color filter having high luminance and a wide color reproduction region (for example, patents). Reference 3). However, the pigment composition containing the polyhalogenated zinc phthalocyanine pigment has a problem that the contrast ratio decreases with time when the contrast ratio is increased.
From the background as described above, there is a strong demand for the development of a radiation-sensitive composition that can form a green pixel having a high luminance and contrast ratio and that does not decrease with time.

JP-A-2-144502 JP-A-3-53201 JP 2007-284589 A

An object of the present invention is to provide a radiation-sensitive composition capable of forming a green pixel having a high luminance and contrast ratio and in which the contrast ratio does not decrease with time.
Furthermore, the objective of this invention is providing the color liquid crystal display element which comprises the color filter provided with the green pixel formed from the said radiation sensitive composition, and the said color filter.

  In view of such circumstances, the present inventors have conducted extensive research and surprisingly found that C.I. which is a polyhalogenated zinc phthalocyanine pigment. I. The present invention has been completed by finding that the above-mentioned problems can be solved by dispersing Pigment Green 58 in combination with a specific solvent.

That is, the present invention relates to a colored radiation sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation sensitive polymerization initiator, and (E) a solvent. A composition comprising (A) C.I. I. The present invention provides a colored radiation-sensitive composition containing Pigment Green 58 and (E) a solvent having two acetoxy groups as a solvent.
The “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

The present invention also relates to a colored radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent. A colored radiation-sensitive composition comprising (A) brominated chlorinated zinc phthalocyanine as a colorant and (E) a solvent having two acetoxy groups as a solvent. Is to provide.
The present invention also provides C.I. I. It is intended to provide a colorant dispersion characterized by containing Pigment Green 58 and a solvent having two acetoxy groups.

  The present invention also provides a color filter including a green pixel formed using the colored radiation-sensitive composition, and a color liquid crystal display element including the color filter.

The colored radiation-sensitive composition of the present invention can form green pixels with high brightness and contrast ratio, and the contrast ratio does not decrease with time.
Therefore, a color filter including a green pixel formed using the colored radiation-sensitive composition of the present invention includes, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and an organic EL. It is extremely useful for display elements, electronic paper, and the like.

  In the colored radiation-sensitive composition of the present invention (hereinafter sometimes simply referred to as “radiation-sensitive composition”), (A) the colorant is C.I. I. Pigment Green 58 is contained. C. I. Pigment Green 58 is brominated chlorinated zinc phthalocyanine and preferably has a structure represented by the following formula (1).

(In Formula (1), X shows a hydrogen atom, a chlorine atom, or a bromine atom mutually independently, 10-15 pieces of all X are a bromine atom, and 1-6 are a chlorine atom. )
The radiation-sensitive composition of the present invention includes C.I. I. Other colorants other than CI Pigment Green 58 can be further contained. Other colorants are not particularly limited, and any of pigments, dyes, and natural pigments can be used, but color filters are required to have high purity and high light transmission color and heat resistance. Therefore, an organic pigment is preferable.
In the present invention, C.I. I. The content ratio of Pigment Green 58 is preferably 20 to 100% by mass, and particularly preferably 35 to 75% by mass in the total colorant in the sense of obtaining a green pixel with high luminance.
Examples of the other colorant include compounds classified as pigments in the color index, specifically, pigments having the following color index (CI) names. .

C. I. Pigment green 7, C.I. I. Pigment green 36;
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, C.I. I. Pigment yellow 219;

  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 38, 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;

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 177, 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 242, 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.
These other colorants can be used alone or in admixture of two or more.

  Among these other colorants, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 219 and the like are preferable.

In the present invention, C.I. I. Pigment Green 58 and other colorants 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 addition, C.I. I. Pigment Green 58 and other colorants 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 polymers or oligomers for dispersing pigments.
In the present invention, the content ratio of (A) the colorant is preferably 5 to 70% by mass, particularly preferably 5 to 60% by mass in the total solid content in the sense that a green pixel having high luminance and color purity is formed. It is. Here, solid content is components other than the solvent mentioned later.

  The (B) alkali-soluble resin contained in the radiation-sensitive composition of the present invention is particularly limited as long as it is soluble in the alkali developer used in the development processing step when forming the colored layer. Although not intended, it is usually a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, those containing a polymer having a carboxyl group are 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 copolymerizable ethylenically unsaturated monomers (hereinafter sometimes referred to as “copolymerizable unsaturated monomers”) (hereinafter “carboxyl group-containing copolymers”). Is sometimes 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.
These carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

  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. In this case, if the copolymerization ratio is too small, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, while if too large, the solubility in an alkaline developer becomes excessive and alkali development is caused. When developing with a liquid, the pixel tends to drop off from the substrate or the surface of the pixel 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, as the copolymerizable unsaturated monomer, an N-substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, or a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain. Those containing at least one selected from the group consisting of 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, paracumylfe What contains at least 1 sort (s) chosen from the group which consists of an ethylene oxide modified | denatured (meth) acrylate of a polyol, a polystyrene macromonomer, and a polymethylmethacrylate macromonomer is preferable.

  In the present invention, for example, as disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-2008-181095, etc., a (meth) acryloyl group or the like is present in the side chain. The carboxyl group-containing copolymer having a polymerizable unsaturated bond can also be used as an alkali-soluble resin.

The weight average molecular weight in terms of polystyrene (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 1,000 to 45,000. Preferably it is 3,000-20,000. If the Mw is too small, the remaining film ratio of the resulting coating may decrease, the pattern shape and heat resistance may be impaired, and the electrical characteristics may deteriorate. On the other hand, if the Mw is too large, the resolution may be reduced. There is a possibility that the shape is damaged, and that dry foreign matter is likely to be generated at the time of application by the slit nozzle method.
In addition, the ratio (Mw / Mn) of Mw of the alkali-soluble resin in the present invention to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is , Preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

  The alkali-soluble resin in the present invention includes, for example, an unsaturated monomer such as (meth) acrylic acid, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be produced by polymerization in the presence of a radical polymerization initiator.

The alkali-soluble resin in the present invention can be purified through a reprecipitation method using two or more organic solvents having different polarities after radical polymerization of an unsaturated monomer as described above. 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, of the impurities remaining in the polymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified alkali-soluble 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, and methyl ethyl ketone / n-heptane. Can be mentioned.

  In addition, the alkali-soluble resin in the present invention comprises 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) as the unsaturated monomer as the copolymer component. ), Radical polymerization initiators such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, 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) di In the presence of a molecular weight regulator that acts as an iniferter such as rufide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide In the inert solvent, the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and can be produced by living radical polymerization.

  Furthermore, the alkali-soluble resin in the present invention is prepared by mixing each unsaturated monomer serving as a copolymerization component in a suitable solvent in the presence of the radical polymerization initiator and a polyvalent thiol compound that acts as a chain transfer agent. It can be produced by radical polymerization. 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, content of (B) alkali-soluble 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. In this case, if the content of the alkali-soluble resin is too small, for example, the alkali developability may be reduced, or a residue or background stain may occur on the unexposed portion of the substrate or on the light shielding layer. Since the colorant concentration is relatively lowered, it may be difficult to achieve the target color density as a thin film.

The (C) 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 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;
Examples include tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide-modified triacrylate, poly (meth) acrylate having a urethane structure, poly (meth) acrylate having a caprolactone structure, and the like.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products, poly (meth) acrylates having a urethane structure, and poly (meth) acrylates having a caprolactone structure (Meth) acrylate is 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 Preferred are monoesterified products of acrylate and succinic acid, monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, and particularly trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Monoesterified products of erythritol hexaacrylate, pentaerythritol triacrylate and succinic acid, and monoesterified products of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, excellent surface smoothness of the colored layer, and This is preferable in that ground stains, film residue, and the like are hardly generated on the substrate and the light shielding layer in the exposed portion.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  20-500 mass parts is preferable with respect to 100 mass parts of (B) alkali-soluble resin, and, as for content of (C) polyfunctional monomer in this invention, 100-300 mass parts is especially preferable. In this case, if the content of the polyfunctional monomer is too small, the strength and surface smoothness of the pixel, and the solvent resistance tend to decrease, while if too large, for example, alkali developability decreases, There is a tendency that background stains, film residue, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer.

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) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as mono [(meth) acryloyloxyalkyl] ester of acid, ω-carboxypolycaprolactone mono (meth) acrylate, and N- (meth) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
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% by mass or less, more preferably 50% by mass or less, with respect to the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the proportion of the monofunctional monomer used is too large, the pixel strength and surface smoothness tend to decrease.

The (D) radiation-sensitive polymerization initiator used in the present invention is used by the (C) polyfunctional monomer and optionally by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound that generates an active species capable of initiating polymerization of a monofunctional monomer.
Examples of such radiation-sensitive polymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, and benzophenone compounds. , Α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like.

In the present invention, the radiation-sensitive polymerization initiator can be used alone or in admixture of two or more kinds. Examples of the radiation-sensitive polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds. , At least one selected from the group of triazine compounds and O-acyloxime compounds is preferred. In addition, C.I. I. The radiation-sensitive composition containing CI Pigment Green 58 is preferable to contain a thioxanthone compound in the sense that it easily generates aggregated foreign substances of the pigment and reduces the aggregated foreign substances.
In the present invention, it is more preferable to use the thioxanthone compound in combination with another radiation-sensitive polymerization initiator. In this case, the content ratio of the thioxanthone compound is preferably 1 to 75% by mass, and particularly preferably 5 to 50% by mass in the total radiation-sensitive polymerization initiator. By using such a radiation sensitive polymerization initiator, a radiation sensitive composition having high sensitivity and excellent dispersion stability can be obtained.

Among preferred radiation-sensitive polymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-dodecylthioxanthone, and 2,4-dimethylthioxanthone. 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like.
Of these thioxanthone compounds, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-diethylthioxanthone are preferable.
The thioxanthone compounds can be used alone or in admixture of two or more.

Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpho And linophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.
Among these acetophenone compounds, 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 are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrafe 1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.
Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable.
The biimidazole compounds can be used alone or in admixture of two or more.

In addition, when using a biimidazole-type compound as a radiation sensitive polymerization initiator, 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, but it is preferable to use a mercaptan-based hydrogen donor.
In the present invention, when a hydrogen donor is used in combination with a biimidazole compound, the content of the hydrogen donor is preferably 1 to 300 parts by mass, particularly preferably 5 to 200 parts per 100 parts by mass of the biimidazole compound. Part by mass, more preferably 10 to 150 parts by mass. In this case, if the content of the hydrogen donor is too small, the effect of improving the sensitivity tends to be reduced. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

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.
The triazine compounds can be used alone or in admixture of two or more.

  Specific examples of the O-acyloxime compound include 1,2-heptanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (benzoyl) phenyl]-, 2- (O-benzoyloxime), ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (3- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl)-, 1- O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl- 6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5) -Tetrahydropyranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4 (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl) -4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- 3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxy) Cibenzoyl) -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.

Among these O-acyloxime compounds, 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-tetrahydrofuranylmethoxybenzoyl)- 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) is preferred.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In this invention, content of a radiation sensitive polymerization initiator is 0.01-120 mass parts normally with respect to 100 mass parts of (C) polyfunctional monomers, Preferably it is 1-100 mass parts, More preferably Is 1 to 70 parts by mass. In this case, if the content of the radiation sensitive polymerization initiator is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which a pixel pattern is arranged according to a predetermined arrangement. If it is too high, the formed pixel pattern tends to drop off from the substrate during development.

The (E) solvent used in the present invention contains a solvent having two acetoxy groups. Specific examples of the solvent having two acetoxy groups include propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and the like.
The solvent having two acetoxy groups can be used alone or in admixture of two or more.

In the present invention, other solvents can be used together with a solvent having two acetoxy groups. Examples of such other solvents include:
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, such as tripropylene glycol monoethyl ether (poly) alkylene glycol monoalkyl 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, 3-methyl-3-methoxybutylpropionate;

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, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, Other esters such as n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Mention may be made of amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone.

Among these other solvents, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-methoxypropionate, 3-ethoxy from the viewpoints of pigment dispersibility, solubility of components other than pigment, and coating properties. Methyl propionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate are preferred.
The other solvents can be used alone or in admixture of two or more.

  The solvent used in the present invention is preferably a mixture of a solvent having two acetoxy groups and another solvent, and the content ratio of the solvent having two acetoxy groups is 1 to 60% by mass in the total solvent. It is preferable that it is 1 to 45% by mass. In this case, if the content ratio of the solvent having two acetoxy groups is too small, the desired effect may not be obtained. On the other hand, if the content is too large, the solvent component is difficult to evaporate and it is difficult to form a coating film. There is.

  The content of the solvent is not particularly limited, but from the viewpoint of applicability, stability and the like of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is 5 to 5%. An amount of 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly preferable.

In the present invention, the radiation-sensitive composition can be prepared by an appropriate method. For example, the radiation-sensitive composition can be prepared by mixing the components (A) to (E) together with the additives described later. Preferred methods for preparing the radiation sensitive composition include C.I. I. In the presence of (F) a dispersant and, if necessary, a dispersion aid, a colorant comprising CI Pigment Green 58 is optionally added in a solvent comprising a solvent having two acetoxy groups. (B) Along with a part of the component, for example, a bead mill, a roll mill or the like is used to mix and disperse while pulverizing to obtain a colorant dispersion. In this colorant dispersion, the components (B) to (D) are necessary. Depending on the method, an additional solvent or additive may be further added and mixed for mixing.
In this case, the content ratio of the solvent having two acetoxy groups in the total solvent used for the preparation of the colorant dispersion is preferably 2% by mass or more, and particularly preferably 5% by mass or more.

  As the dispersant (F) used in the preparation of the colorant dispersion, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable, A block copolymer comprising a block having a pigment adsorbing group in the side chain and a block having no pigment adsorbing group in the side chain (hereinafter sometimes referred to as “block copolymer type dispersant”) is preferred.

Examples of the pigment adsorption group in the block copolymer type dispersant include basic groups such as amino groups, carboxyl groups, phosphono groups, quaternary ammonium bases, carboxylate groups, and phosphate groups. The block having a pigment adsorbing group in the side chain is composed of, for example, a repeating unit derived from a (meth) acrylic acid ester having such a pigment adsorbing group.
On the other hand, a block having no pigment adsorbing group in the side chain preferably has a chain or cyclic alkyl group, aryl group, aralkyl group, polycaprolactone structure, polyether structure or the like in the side chain. The block having no pigment adsorbing group in the side chain is constituted by, for example, a repeating unit derived from a (meth) acrylic acid ester having these functional groups and structures.

Such a block copolymer type dispersing agent can be obtained commercially, and examples thereof include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (BIC Chemie (BYK)).
The block copolymer dispersants can be used alone or in admixture of two or more.

In the present invention, other dispersants can be used together with the block copolymer type dispersant. Specific examples of such other dispersants include polyurethane, polyester, and cationic graft polymer. 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.

Such dispersants are commercially available, for example, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK) (BYK) as polyurethane Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), as a cationic graft polymer, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Azisper PB821, Azisper PB822, Azisper PB823, Azisper PB824, Ajisper PB827 (Ajinomoto) Fine Techno Co., Ltd.).
These dispersants can be used alone or in admixture of two or more.

  Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 0.5-100 mass parts, More preferably, it is 1-70 mass parts, Most preferably, it is 10-10 mass parts. 50 parts by mass. In this case, if the content of the dispersant exceeds 100 parts by mass, the developability may be impaired.

Although the radiation sensitive composition of this invention contains the said (A)-(E) component, it can further contain an additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic surfactants Surfactant such as an agent; 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-epoxycyclohexyl) ethyltri Methoxysilane, 3-chloropropylmethyldimethyl Adhesion promoters such as xysilane, 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; development residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

The color filter of the present invention includes a green pixel formed from the radiation-sensitive composition of the present invention.
The method for forming the color filter of the present invention will be described below.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming a pixel, and a liquid of the radiation sensitive composition in which the green pigment of the present invention is dispersed on the substrate. After applying the composition, pre-baking is performed to evaporate the solvent and form a coating film. Next, this 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, whereby a green pixel pattern is formed in a predetermined pattern. A pixel array arranged in an array is formed.
Then, using the liquid composition of each radiation-sensitive composition in which a red or blue pigment is dispersed, each liquid composition is coated, pre-baked, exposed, developed and post-baked in the same manner as described above, and then red. By sequentially forming the pixel 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 a liquid composition of a radiation sensitive composition to a substrate, an appropriate application 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, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly 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.
In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
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.

  Since the color filter of the present invention thus obtained has a high luminance and contrast ratio, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

  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.

Preparation of colorant dispersion Preparation Example 1
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid composed of 116 parts by mass of ether acetate and 20 parts by mass of 1,3-butylene glycol diacetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-1).

Preparation Example 2
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid consisting of 116 parts by mass of ether acetate and 20 parts by mass of propylene glycol diacetate was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-2).

Preparation Example 3
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid consisting of 96 parts by mass of ether acetate and 40 parts by mass of 1,3-butylene glycol diacetate was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-3).

Preparation Example 4
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration: 45.1% by mass) as a dispersant, and 3-ethoxy as a solvent A mixed liquid consisting of 76 parts by mass of ethyl propionate and 60 parts by mass of 1,3-butylene glycol diacetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-4).

Preparation Example 5
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and 3-methoxy as a solvent A mixed liquid composed of 76 parts by mass of butyl acetate and 60 parts by mass of 1,3-butylene glycol diacetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-5).

Preparation Example 6
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and 1,3 as a solvent -A liquid mixture consisting of 136 parts by mass of butylene glycol diacetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-6).

Comparative Preparation Example 1
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid composed of 136 parts by mass of ether acetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (a-1).

Comparative Preparation Example 2
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and triacetin (3 A solvent dispersion having 136 acetoxy groups) was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (a-2).

Comparative Preparation Example 3
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid composed of 116 parts by mass of ether acetate and 20 parts by mass of cyclohexanone was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (a-3).

Comparative Preparation Example 4
(A) C.I. I. Pigment Green 58 (manufactured by DIC) and C.I. I. 40 parts by mass of a 60/40 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid composed of 116 parts by mass of ether acetate and 20 parts by mass of propylene glycol monomethyl ether was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (a-4).

Comparative Preparation Example 5
(A) C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 53/47 (mass ratio) mixture with CI Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (BYK) (solid content concentration 45.1% by mass) as a dispersant, and propylene glycol methyl as a solvent A mixed liquid composed of 116 parts by mass of ether acetate and 20 parts by mass of cyclohexanone was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (a-5).

(B) Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2.5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of ethylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid, ω -10 parts by weight of carboxydicaprolactone monoacrylate, 15 parts by weight of N-phenylmaleimide, 33 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of styrene, 15 parts by weight of glycerol monomethacrylate and α-methylstyrene dimer (chain transfer agent) After charging 0 parts by mass and substituting with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring and polymerized for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 30% by mass) was obtained. The obtained resin was Mw = 14,000 and Mn = 5,700. This resin solution is referred to as “resin solution (B-1)”.

Example 1
Preparation of radiation-sensitive composition Pigment dispersion (A-1) 400 parts by mass, (B) 200 parts by mass of resin solution (B-1) as alkali-soluble resin, (C) Dipentaerythritol as polyfunctional monomer 60 parts by mass of hexaacrylate, (D) 6 parts by mass of 2,4-diethylthioxanthone as a radiation-sensitive polymerization initiator, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (O-acetyloxime) (Ciba Specialty Chemicals, trade name IRGACURE OX02) 5 parts by mass, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 2 parts by mass of 5′-tetraphenyl-1,2′-biimidazole and 2 parts by mass of 2-mercaptobenzothiazole, and propylene glycol monomethyl as a solvent It was mixed so that the solid content concentration of 20.0% with over ether acetate, liquid composition (G1) was prepared.
The liquid composition (G1) was evaluated according to the following procedure. The evaluation results are shown in Table 1.

On the day of evaluation and preparation of chromaticity characteristics and contrast , the liquid composition (G1) was rotated using a spin coater on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface. After coating three sheets with variable numbers, pre-baking was performed for 4 minutes on a hot plate at 90 ° C. 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, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged onto these substrates at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 1 minute. Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a cured film for evaluation.

Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement results, a chromaticity coordinate value x and a stimulus value (Y) at a chromaticity coordinate value y = 0.600 were obtained.
Further, for the three cured films obtained, the contrast ratio was measured using a contrast meter (CT-1, made by Aisaka Electric Co., Ltd., blank 5000), and the contrast ratio at the chromaticity coordinate value y = 0.600 was determined. Asked.
Similarly, the liquid composition (G1) is stored at room temperature for one month, and the chromaticity characteristics and the contrast ratio are measured. The chromaticity coordinate value x and the stimulation value (Y ) And the contrast ratio. The evaluation results are shown in Table 1.

Examples 2-6 and Comparative Examples 1-5
Liquid compositions (G2) to (G11) were prepared in the same manner as in Example 1, except that the type of pigment dispersion was changed as shown in Table 1 in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (G2) to (G11) were used instead of the liquid composition (G1). The evaluation results are shown in Table 1.

  As is apparent from Table 1, C.I. I. It can be seen that the radiation-sensitive composition containing Pigment Green 58 and a solvent having two acetoxy groups can form a green pixel having a high luminance and contrast ratio, and the contrast ratio does not decrease with time. In contrast, when a solvent having one acetoxy group is used (Comparative Example 1), when a solvent having three acetoxy groups is used (Comparative Example 2), a solvent having two acetoxy groups is used. The contrast ratio is lower than when used.

Claims (8)

  A colored radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent, (A) C.I. I. A colored radiation-sensitive composition containing Pigment Green 58 and (E) a solvent having two acetoxy groups as a solvent.   A colored radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent, A colored radiation-sensitive composition comprising (A) brominated chlorinated zinc phthalocyanine as a colorant and (E) a solvent having two acetoxy groups as a solvent.   (E) The solvent is a mixture of a solvent having two acetoxy groups and another solvent, and the content ratio of the solvent having two acetoxy groups is 1 to 60% by mass in the total solvent. The colored radiation-sensitive composition according to 2. The colored radiation-sensitive composition according to claim 1, further comprising (F) a dispersant. The colored radiation-sensitive composition according to claim 4, comprising (F) a block copolymer comprising a block having a pigment adsorbing group in the side chain and a block having no pigment adsorbing group in the side chain as the dispersant.   C. I. A colorant dispersion comprising Pigment Green 58 and a solvent having two acetoxy groups.   A color filter comprising a green pixel formed using the colored radiation-sensitive composition according to claim 1.   A color liquid crystal display device comprising the color filter according to claim 7.