JP5644992B2 - Colored radiation-sensitive composition, color filter, and color liquid crystal display element - Google Patents

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 ELEMENT 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, green pixels formed using a pigment composition containing a polyhalogenated zinc phthalocyanine pigment have been used for C.I. I. Pigment Green 7 and C.I. I. Compared to Pigment Green 36, there was a problem that the solvent resistance was remarkably inferior.

From the background as described above, development of a radiation sensitive composition capable of forming a green pixel having high luminance and excellent solvent resistance is strongly demanded.

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 high luminance and excellent solvent resistance.
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. It has been found that the above-mentioned problems can be solved by including Pigment Green 58 together with an alkali-soluble resin and a polyfunctional monomer having a specific content ratio, and the present invention has been completed.

That is, the present invention is a colored radiation-sensitive composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator. (A) C.I. I. Pigment Green 58 is included, and the content of (C) the polyfunctional monomer is more than 100 parts by mass and less than or equal to 400 parts by mass with respect to 100 parts by mass of (B) alkali-soluble resin. A radiation-sensitive composition is provided.
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 provides a colored radiation-sensitive composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator. And (A) containing brominated chlorinated zinc phthalocyanine as a colorant, and (C) the content of polyfunctional monomer is more than 100 parts by mass with respect to 100 parts by mass of (B) alkali-soluble resin. The present invention provides a colored radiation-sensitive composition characterized by being no more than part by mass.
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.

By using the colored radiation-sensitive composition of the present invention, a green pixel having high luminance and excellent solvent resistance can be formed.
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 these, those containing a polymer having a carboxyl group are preferred, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing unsaturated monomer”). Copolymers (hereinafter referred to as “carboxyl group-containing copolymers”) with other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “copolymerizable unsaturated monomers”) are 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.

(C) in the present invention the polyfunctional monomer in order to enhance the good Ri solvent resistance, monomers having 7 or more polymerizable unsaturated bond (hereinafter, "multifunctional monomer ( C3) "hereinafter) it contains.
A monomer having 2 to 3 polymerizable unsaturated bonds (hereinafter referred to as “polyfunctional monomer (c1)”, which can be used together with such a polyfunctional monomer (C3). .), For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, monoesterified product of pentaerythritol tri (meth) acrylate and succinic acid, tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide modified triacrylate, etc. Raise Door can be.

  Examples of the monomer having 4 to 6 polymerizable unsaturated bonds (hereinafter referred to as “polyfunctional monomer (c2)”) include, for example, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, monoesterified product of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate ( And a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate).

Monomers having 7 or more polymerizable unsaturated bond, of the Application Benefits pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a compound represented by the following formula (2), dipenta It is a compound obtained by reacting erythritol penta (meth) acrylate with a polyfunctional isocyanate or a compound obtained by reacting dipentaerythritol penta (meth) acrylate with a polyfunctional epoxy compound.

(In Formula (2), R ¹ independently represents a hydrogen atom or a methyl group, and R ² represents a divalent organic group.)
Among the above-mentioned formula (2), compounds represented by For example, compounds obtained by reacting dipentaerythritol penta (meth) acrylate and tetracarboxylic acid dianhydride, polyfunctional monomer and (C3) It can be used in actual together.

Specific examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
Specific examples of the tetrabasic acid dianhydride include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride. , Cyclopentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene tetracarboxylic An acid dianhydride etc. can be mentioned.
Specific examples of the polyfunctional epoxy compound include tris (glycidylphenyl) methane, triglycidyl isocyanurate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl). ) Adipate, methylene bis (3,4-epoxycyclohexane), bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, novolac type epoxy resin and the like.

In the present invention, as a polyfunctional monomer, in particular, compounds obtained by reacting dipentaerythritol penta (meth) acrylate and a polyfunctional isocyanate are preferred.
In the present invention, the polyfunctional monomer, as possible out be used alone or in combination of two or more.

In this invention, content of (C) polyfunctional monomer is more than 100 mass parts with respect to 100 mass parts of (B) alkali-soluble resin, and is 400 mass parts or less, Preferably it is 110-300 mass parts. . In this case, if the content of the polyfunctional monomer is too low, the desired effect cannot be obtained. In particular, there is a tendency that dirt, film residue, etc. are likely to occur.
In addition, the content of the polyfunctional monomer (c3) is preferably 30% by mass or more, more preferably 50% by mass or more in the total polyfunctional monomer, from the viewpoint of enhancing a desired effect.
In general, it is expected that if the polyfunctional monomer is contained in the radiation-sensitive composition in a larger amount, the curability of the formed pixel is increased and the solvent resistance is improved. , C.I. I. When using CI Pigment Green 58, sufficient solvent resistance cannot be obtained simply by adding more polyfunctional monomer. In other words, it is important that the content of the polyfunctional monomer is adjusted by the ratio with respect to the alkali-soluble resin. This is because the radiation exposure area where the pixels are formed is also alkali-developed during development due to the presence of the alkali-soluble resin. This is thought to be due to liquid erosion.

The radiation-sensitive polymerization initiator (D) used in the present invention initiates polymerization of the polyfunctional monomer (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates a possible active species.
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 this invention, a radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types. The radiation sensitive polymerization initiator is preferably at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds. 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 is preferred.
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, Furthermore, Preferably it is 1-70 mass parts. 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.

Although the radiation sensitive composition of this invention contains the said (A)-(D) component, it can also contain another additive as needed.
Examples of other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, and anionic surfactants. Surfactants such as surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyl Adhesion promoters such as methoxysilane, 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-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Anticoagulation agents such as sodium polyacrylate; development residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method, and for example, it can be prepared by mixing the components (A) to (D) together with a solvent and additives. Preferred methods for preparing the radiation sensitive composition include C.I. I. In a solvent, in the presence of a dispersing agent and a dispersing aid to be added as necessary, a coloring agent containing CI Pigment Green 58 is optionally used together with a part of the component (B), for example, using a bead mill, a roll mill or the like. Mix and disperse while pulverizing to obtain a colorant dispersion, and add (B) to (D) components and, if necessary, additional solvents and additives to the colorant dispersion and mix. The method of preparing by can be mentioned.

Examples of the solvent used for the preparation of the colorant dispersion include the solvents described later.
Moreover, as a dispersing agent used for preparation of the said colorant dispersion liquid, suitable dispersing agents, such as a cation type | system | group, anionic type | system | group, nonionic type | system | group, and amphoteric, can be used, for example, but a polymer dispersing agent is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, an alkyl ammonium salt or a phosphate ester salt of a polymer copolymer, a cationic graft polymer, and the like can be given. Here, the cationic graft polymer refers to a polymer having a structure in which two or more branch polymers are grafted to one molecule of a backbone polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer having a part of polyethyleneimine and a branch polymer part of ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethanes, and cationic 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 Corp.), Solsperse 24000 as a cationic graft polymer (Manufactured by Lubrizol Co., Ltd.), Ajisper PB821, Azisper PB822, Azisper PB823, Azisper PB824, Azisper PB827 (Ajinomoto Fine Techno Co., Ltd.), and the like.

  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, when the content of the dispersant exceeds 100 parts by mass, developability and the like may be impaired.

The radiation-sensitive composition of the present invention comprises the components (A) to (D) as essential components and, if necessary, the additive component, but can also be prepared as a liquid composition by blending a solvent. .
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive 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, 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;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
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.

Of these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol from the viewpoints of pigment dispersibility, solubility of components other than pigment, and coating properties. Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl Cetate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n-Butyl and ethyl pyruvate are preferred.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can 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 from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually An amount of 5 to 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly preferable.

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 high luminance and a wide color reproduction region, 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. In Examples, Examples 1 to 10, 13, 14, and 18 are reference 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 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).

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 Pigment Yellow 150, 22 parts by mass of Solsperse 76500 (manufactured by Lubrizol Co., Ltd., solid content concentration 50%) as a dispersant, and propylene glycol methyl ether acetate 138 as a solvent A mixed liquid consisting of parts by mass was mixed and dispersed by a bead mill for 12 hours 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 40/60 (mass ratio) mixture with Pigment Yellow 138, 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 136 parts by mass of ether acetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-3).

Preparation Example 4
(A) C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of 55/45 (mass ratio) mixture with 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-4).

(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 liquid composition 500 parts by mass of pigment dispersion (A-1), (B) 50 parts by mass (solid content conversion) of resin solution (B-1) as alkali-soluble resin, (C) polyfunctionality 100 parts by mass of dipentaerythritol hexaacrylate as a monomer, (D) 10 parts by mass of 2,4-diethylthioxanthone as a radiation sensitive polymerization initiator, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE OX02) and solid using propylene glycol monomethyl ether acetate as a solvent A liquid composition (G-1) was prepared by mixing so that the partial concentration was 20%.
The liquid composition (G-1) was evaluated according to the following procedure. The evaluation results are shown in Table 2.

The development residue and the solvent resistance evaluation liquid composition (G-1) were 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 90 ° C. Was baked for 4 minutes on the hot plate, and four coating films having a film thickness of 2.5 μm after pre-baking were formed.
Next, after these substrates were cooled to room temperature, the coating film was exposed with a radiation dose of 2,000 J / m ² including wavelengths of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp. . After that, after developing a developer consisting of a 0.04 wt% aqueous potassium hydroxide solution at 23 ° C. for 1 minute at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm), these substrates were subjected to shower development. Further, post-baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm green dot pattern on the substrate.

The obtained dot pattern was observed with an optical microscope. When no development residue was observed on the unexposed portion of the glass substrate, ○, when a slight development residue was observed, Δ, severe development residue was observed. The case was evaluated as x.
The substrate on which the dot pattern was formed was immersed in N-methylpyrrolidone at 60 ° C. for 10, 20, 30, and 40 minutes. As a result, the case where the dot pattern was retained after immersion and the N-methylpyrrolidone after immersion was not colored at all; the dot pattern was retained after immersion, but the N-methylpyrrolidone after immersion was slightly colored The case was evaluated as Δ, and the case where the dot pattern peeled off from the substrate after immersion was observed and the N-methylpyrrolidone after immersion was colored as x.

Evaluation of Chromaticity Characteristics After applying the liquid composition (G-1) on a soda glass substrate on which a SiO ₂ film that prevents elution of sodium ions is formed on the surface using a spin coater, a hot 90 ° C. The plate was pre-baked for 4 minutes to form three coating films having different film thicknesses.
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured. From the measurement results, a chromaticity coordinate value x and a stimulus value (Y) at a constant chromaticity coordinate value y were obtained. The evaluation results are shown in Table 2. The larger the Y value, the higher the light transmittance (brightness).

Examples 2-18 and Comparative Examples 1-10
In Example 1, the liquid composition (G-2)-(G-28) was prepared like Example 1 except having changed the kind and quantity of the containing component as shown in Table 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (G-2) to (G-28) were used instead of the liquid composition (G-1). The results are shown in Table 2.

In Table 1, each component is as follows.
C-1: Dipentaerythritol hexaacrylate C-2: Pentaerythritol tetraacrylate C-3: Pentaerythritol triacrylate hexamethylene diisocyanate C-4: Dipentaerythritol pentaacrylate hexamethylene diisocyanate (dipentaerythritol pentaacrylate and hexamethylene diisocyanate Reaction product)
C-5: Biscote # 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate)
D-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
D-2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-3: 2,4-diethylthioxanthone

  As is clear from Tables 1 and 2, C.I. I. By including CI Pigment Green 58 together with an alkali-soluble resin and a polyfunctional monomer having a specific content ratio, a green pixel having high luminance and excellent solvent resistance can be formed, and a development residue is generated. It can be seen that no radiation sensitive composition is obtained. As is clear from Comparative Examples 1 and 3, sufficient solvent resistance cannot be achieved simply by adding more polyfunctional monomer.

Claims (7)

A colored radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator, wherein (A) coloring C. as an agent I. Pigment Green 58 and (C) polyfunctional monomer reacts with tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, dipentaerythritol penta (meth) acrylate and polyfunctional isocyanate And a compound obtained by reacting dipentaerythritol penta (meth) acrylate with a polyfunctional epoxy compound , and (C) a polyfunctional monomer. A colored radiation-sensitive composition, wherein the content is more than 100 parts by mass and not more than 400 parts by mass with respect to 100 parts by mass of (B) alkali-soluble resin. A colored radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator, wherein (A) coloring Containing brominated chlorinated zinc phthalocyanine as an agent, and (C) a polyfunctional monomer is tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, dipentaerythritol penta (meth) acrylate A compound obtained by reacting a polyfunctional isocyanate, and at least one selected from the group consisting of a compound obtained by reacting dipentaerythritol penta (meth) acrylate and a polyfunctional epoxy compound , and (C) polyfunctional The content of the functional monomer is more than 100 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin. Colored radiation-sensitive composition being not more than 0 parts by mass. (D) sensitive colored radiation-sensitive composition according to claim 1, the radiation polymerization initiator comprises the thioxanthone compound. (D) sensitive colored radiation-sensitive composition according to claim 2, radiation polymerization initiator contains a thioxanthone compound. (D) The colored radiation-sensitive composition according to claim 3 or 4, wherein the radiation-sensitive polymerization initiator further contains an O-acyloxime compound. The color filter provided with the green pixel formed using the colored radiation-sensitive composition as described in any one of Claims 1-5.   A color liquid crystal display device comprising the color filter according to claim 6.