TWI459134B - Colored radiation sensitive composition, colorant dispersion, color filter and color liquid crystal display element - Google Patents

Description

Coloring sensitizing radiation composition, colorant dispersion, color filter, and color liquid crystal display element

The present invention relates to a color-sensitive radiation composition, a colorant dispersion, a color filter, and a color liquid crystal display element, and more particularly to a transmissive or reflective type color liquid crystal display device, a color image pickup device element, and an organic EL display element. a color sensitive filter for forming a colored layer suitable for use in a color filter used in electronic paper, a color filter having a coloring layer formed using the radiation-sensitive composition, and a color filter having the color filter Color liquid crystal display elements.

As a method of forming a color filter using a coloring-sensing radiation linear composition, it is known to form a color-sensitive radiation composition coating film on a substrate or a substrate on which a desired pattern-like light-shielding layer is formed in advance, by having a predetermined pattern The photomask irradiates rays (hereinafter referred to as "exposure"), and develops to dissolve and remove the unexposed portions, and then post-baking to obtain respective color pixels (refer to, for example, Patent Document 1 and Patent Document 2).

A liquid crystal display element having such a color filter requires high luminance and an expanded color reproduction range, and thus, in recent years, color filters have been increasingly required to have high light transmittance and high color purity.

For the green pixel, as a material capable of providing a color filter having a high luminance and a wide color reproduction range, a pigment composition containing a polyhalogenated zinc phthalocyanine pigment is known (refer to, for example, Patent Document 3). . However, in the case of a pigment composition containing a polyhalogenated zinc phthalocyanine pigment, if the contrast is to be increased, there is a problem that the contrast decreases with time.

Due to the above background, there is an urgent need to develop a radiation-sensitive linear composition capable of forming a green pixel having high luminance and contrast without a decrease in contrast with time.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-284589

An object of the present invention is to provide a radiation-sensitive linear composition capable of forming a green pixel having high luminance and contrast without a decrease in contrast with time.

Still another object of the present invention is to provide a color filter having a green pixel formed of the above-described radiation sensitive composition, and a color liquid crystal display element having the color filter.

In view of the above, the present inventors conducted intensive studies and unexpectedly found that the above problems can be solved by combining and dispersing a polyhalogenated zinc phthalocyanine pigment C.I. Pigment Green 58 with a specific solvent, thereby completing the present invention.

That is, the present invention provides a color-sensing radiation linear composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) The coloring sensitizing radiation composition of the solvent contains CI Pigment Green 58 as the (A) coloring agent, and contains a solvent having two ethoxylated groups as the (E) solvent.

The term "radiation" as used in the present invention means a ray containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.

Further, the present invention provides a color-sensing radiation linear composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) The coloring sensitizing radiation composition of the solvent is characterized in that (A) a coloring agent contains cerium zinc bromochloride and a solvent having two ethoxylated groups as the solvent (E).

Further, the present invention provides a coloring agent dispersion liquid comprising C.I. Pigment Green 58 and a solvent having two ethoxylated groups.

Further, the present invention provides a color filter having a green pixel formed using the coloring sensitizing radiation composition, and a color liquid crystal display element having the color filter.

The color-sensing radiation composition of the present invention is capable of forming a green pixel having high luminance and contrast, and the contrast does not decrease with time.

Therefore, a color filter having a green pixel formed by the colored radiation-sensitive composition of the present invention is very suitable for use in, for example, a transmissive or reflective type color liquid crystal display element, a color image pickup device element, a color sensor, and an organic EL. Display elements, electronic paper, etc.

In the colored radiation linear composition of the present invention (hereinafter also simply referred to as "sensing radiation composition"), the coloring agent (A) contains C.I. Pigment Green 58. C.I. Pigment Green 58 is bismuth brominated bismuth chloride, and is preferably a structure represented by the following formula (1).

(In the formula (1), X independently represents a hydrogen atom, a chlorine atom or a bromine atom, and in all X, 10 to 15 are bromine atoms, and 1 to 6 are chlorine atoms).

The radiation sensitive composition of the present invention may further contain a coloring agent other than C.I. Pigment Green 58. As the other coloring agent, there is no particular limitation, and any one of a pigment, a dye, and a natural coloring matter can be used, and since the color filter is required to have high purity and high light transmittance, color development and heat resistance, it is preferably an organic pigment. .

In the present invention, the content ratio of C.I. Pigment Green 58 is preferably from 20 to 100% by mass, particularly preferably from 35 to 75% by mass, based on the total amount of green pixels in which the luminance is high.

As the other coloring agent, for example, a compound classified into a pigment in the pigment index may be mentioned, and specifically, a pigment having the following color index (C.I.) name may be mentioned.

CI Pigment Green 7, CI Pigment Green 36; CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Yellow 219; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149 CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; these other colorants may be used alone or in combination of two or more.

Among these other colorants, in the formation of green pixels, CI pigment green 7, CI pigment green 36, CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 150, CI pigment yellow 180, CI pigment yellow 219, etc. are preferred. .

In the present invention, C.I. Pigment Green 58 and other colorants may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof, as needed, and then used. Further, C.I. Pigment Green 58 and other colorants may be modified with a polymer after use as needed. The polymer of the surface of the modified pigment particle is, for example, a polymer described in JP-A-H08-259876, or a commercially available polymer or oligomer for pigment dispersion.

In the present invention, the content ratio of the (A) colorant is preferably from 5 to 70% by mass, particularly preferably from 5 to 60, in terms of the total amount of the green pixels having high luminance and color purity. quality%. Here, the solid content means a component other than the solvent described below.

The (B) alkali-soluble resin contained in the radiation sensitive composition of the present invention is not particularly limited as long as it is soluble in the alkali developing solution used in the development treatment step at the time of formation of the colored layer, and is usually not particularly limited. It is a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, an alkali-soluble resin containing a polymer having a carboxyl group is preferable, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "carboxyl-containing unsaturated monomer") and other copolymerizable ethylenic groups are particularly preferable. A copolymer of an unsaturated monomer (hereinafter also referred to as "copolymerizable unsaturated monomer") (hereinafter also referred to as "carboxyl-containing copolymer").

Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. Unsaturated diacid or its anhydride such as itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; mono[2-(methyl)propenyloxyethyl] succinate, phthalic acid mono[ Mono[(meth)acryloxyalkylene] ester of a divalent or higher polycarboxylic acid such as 2-(meth)acryloxyethyl]ester; ω-carboxypolycaprolactone mono(methyl) A mono(meth)acrylate or the like of a polymer having a carboxyl group and a hydroxyl group at both terminals such as an acrylate.

The above carboxyl group-containing unsaturated monomers may be used singly or in combination of two or more.

In the present invention, as the carboxyl group-containing unsaturated monomer, (meth)acrylic acid, succinic acid mono [2-(methyl)propenyloxyethyl]ester, and ω-carboxypolycaprolactone mono(A) are preferred. Base) Acrylate, etc., especially (meth)acrylic acid.

These carboxyl group-containing unsaturated monomers may be used singly or in combination of two or more.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. In this case, when the copolymerization ratio is too small, the solubility of the obtained radiation sensitive composition to the alkali developer tends to be small. On the other hand, if the amount is too large, the solubility in the alkali developer is too large, and the alkali developer is used. When developing, it tends to cause the pixels to fall off from the substrate and the film surface to crack.

Further, examples of the copolymerizable unsaturated monomer include maleic imine: N-phenylmaleimide, N-o-hydroxyphenylmaleimide, and N-m-hydroxyphenyl malazone. Imine, N-p-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-ammonium imino-3-maleimide Benzoate, N-succinimide-4-maleimidobutyrate, N-succinimide-6-maleimidohexanoate, N-ammonium N-substituted maleimine such as imino-3-maleimidopropionate or N-(acridinyl)maleimide; styrene, α-methylstyrene, O-vinyltoluene, m-vinyltoluene, p-vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol , p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidol Ether, m-vinylbenzyl glycidyl ether, ethylene An aromatic vinyl compound such as benzyl glycidyl ether; an anthracene such as hydrazine or 1-methylhydrazine; methyl (meth) acrylate, ethyl (meth) acrylate or n-propyl (meth) acrylate; Isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-(meth)acrylate Hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, (A) Base) cyclohexyl acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxy (meth) acrylate Diethylene glycol ester, methoxy triethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, isobornyl (meth)acrylate Ester, tricyclo(meth)acrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid 4- Hydroxyphenyl ester, unsaturated carboxylic acid ester such as ethylene oxide modified (meth) acrylate of p-cumyl phenol; unsaturated carboxylic acid glycidyl ester such as glycidyl (meth) acrylate; acetic acid a vinyl carboxylate such as vinyl ester, vinyl propionate, vinyl butyrate or vinyl benzoate; an unsaturated ether such as vinyl methyl ether, vinyl ethyl ether or allyl glycidyl ether; a vinyl cyanide compound such as acrylonitrile, α-chloroacrylonitrile or divinyl cyanoethylene; (meth) acrylamide, α-chloropropenylamine, N-2-hydroxyethyl (meth) acrylamide, etc. Unsaturated guanamine; aliphatic conjugated diene such as 1,3-butadiene, isoprene, chloropentadiene; polystyrene, poly(methyl) methacrylate, poly(meth)acrylic acid A macromonomer having a mono(meth)acrylinyl group at the terminal of a polymer molecular chain such as n-butyl ester or polyoxyalkylene.

These copolymerizable unsaturated monomers may be used singly or in combination of two or more.

In the present invention, as the copolymerizable unsaturated monomer, it is preferred to contain a maleimide selected from an N-position, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a polymer molecular chain terminal having a single (A) a monomer of at least one of the group consisting of a macromonomer of a acrylonitrile group, more preferably containing N-phenylmaleimide, N-cyclohexylmaleimide, styrene, Α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) 2-hydroxyethyl acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, A monomer of at least one of the group consisting of ethylene oxide-modified (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer of phenol.

In the present invention, the side chain disclosed in, for example, JP-A No. 5-19467, JP-A-H06-230212, and JP-A-2008-181095, etc., may have a (meth) propylene group. A carboxyl group-containing copolymer having a polymerizable unsaturated bond such as a mercapto group is used as an alkali-soluble resin.

The alkali-soluble resin in the present invention is a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran), and is usually 1,000 to 45,000, preferably 3,000. ~20000. When the Mw is too small, the residual film ratio of the obtained film is lowered, the pattern shape and heat resistance are impaired, and the electrical properties are deteriorated. On the other hand, if the Mw is too large, the resolution is lowered to impair the pattern shape, and When coated by a slit nozzle method, there is a risk of drying foreign matter.

In addition, the ratio of the 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) (Mw/Mn) Preferably, it is 1.0 to 5.0, more preferably 1.0 to 3.0.

The alkali-soluble resin in the present invention may be, for example, an unsaturated monomer such as (meth)acrylic acid in a suitable solvent in 2,2'-azobisisobutyronitrile, 2,2'-azobis (2) It is prepared by carrying out polymerization in the presence of a radical polymerization initiator such as 4-dimethylpentanenitrile or 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).

The alkali-soluble resin in the present invention can be produced by subjecting an unsaturated monomer to radical polymerization as described above and then purifying it by a reprecipitation method using two or more organic solvents having different polarities. In other words, the solution in the good solvent after the polymerization is removed by filtration or centrifugation as necessary, and then a large amount of a precipitant (usually 5 to 10 times the volume of the polymer solution) is introduced (poor solvent). In the case, the copolymer is reprecipitated and refined. At this time, among 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.

As a combination of a good solvent/precipitant used in the reprecipitation method, for example, diethylene glycol monomethyl ether acetate/n-hexane, methyl ethyl ketone/n-hexane, diethylene glycol monomethyl ether acetate may be mentioned. / n-heptane, methyl ethyl ketone / n-heptane, and the like.

In addition, the alkali-soluble resin in the present invention may also be obtained by copolymerizing components of each unsaturated monomer in 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethyl Radical polymerization initiators such as valeronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and pyrazole-1-dithiocarboxylic acid cyano ( Dimethyl)methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethyl thiuram disulfide, bis(pyrazole-1-ylthiocarbonyl) disulfide, double ( 3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis(4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis(5-methyl-pyrazole- 1-ylthiocarbonyl)disulfide, bis(3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis(pyrrol-1-ylthiocarbonyl) disulfide In the presence of a molecular weight modifier such as a dithiobenzimidyl disulfide or the like which initiates an action of an intermerator, the reaction temperature is usually from 0 to 150 ° C, preferably from 50 to 120, in an inert solvent. °C, prepared by living radical polymerization.

Further, the alkali-soluble resin in the present invention can also be carried out in a suitable solvent by using a copolymerizable component of each unsaturated monomer in the presence of the above-mentioned radical polymerization initiator and a polythiol compound which functions as a chain transfer agent. Prepared by free radical polymerization. Here, the polythiol compound refers to a compound having two or more mercapto groups in one molecule, and examples thereof include trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate). Tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), 1,4-bis(3-mercaptobutyloxy) Butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three -2,4,6-(1H,3H,5H)trione and the like.

In the present invention, the content of the (B) alkali-soluble resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. In this case, if the content of the alkali-soluble resin is too small, for example, the alkali developability may be lowered, and the residue or the scum may be generated on the unexposed portion of the substrate or the light-shielding layer. On the other hand, if it is excessive, there is a coloring agent. The concentration is relatively low, making it difficult for the film to reach the target color density.

The (C) polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.

Examples of such a polyfunctional monomer include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and di(methyl) polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Acrylate; polymethacrylate or a dicarboxylic acid modified product of a trihydric or higher polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol; polyester, epoxy resin, urethane Oligomer (meth) acrylate such as resin, alkyd resin, fluorenone resin, spiro resin; hydroxy poly-1,3-butadiene at both ends, hydroxypolyisoprene at both ends, hydroxyl group at both ends Di(meth)acrylate of a two-terminal hydroxyl polymer such as caprolactone; tris[2-(methyl)propenyloxyethyl]phosphate, isocyanuric acid ethylene oxide-modified triacrylate A polymethacrylate having a urethane structure, a polymethacrylate having a caprolactone structure, or the like.

Among these polyfunctional monomers, polymethacrylates of a trihydric or higher polyhydric alcohol and modified dicarboxylic acids thereof, polymethacrylates having a urethane structure, and having Polyester methacrylate of ester structure. As the polymethacrylate of the trihydric or higher polyhydric alcohol and the dicarboxylic acid modified product thereof, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, or the like is preferable. Pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, pentaerythritol triacrylate Monoester of ester and succinic acid, monoester of pentaerythritol trimethacrylate and succinic acid, monoester of dipentaerythritol pentaacrylate and succinic acid, monoester of dipentaerythritol pentamethyl acrylate and succinic acid For example, it is excellent in the strength of the colored layer, the surface smoothness of the colored layer is excellent, and it is difficult to generate scum, residual film, etc. on the unexposed portion of the substrate and the light-shielding layer, and the trimethylolpropane triacrylate and pentaerythritol are particularly preferable. Triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tripropyl Ester with succinic acid monoester and dipentaerythritol pentaacrylate succinic acid monoester with.

These polyfunctional compounds may be used singly or in combination of two or more kinds.

The content of the (C) polyfunctional monomer in the present invention is preferably 20 to 500 parts by mass, particularly preferably 100 to 300 parts by mass, per 100 parts by mass of the (B) alkali-soluble resin. In this case, when the content of the polyfunctional monomer is too small, the strength of the pixel, the surface smoothness, and the solvent resistance tend to be lowered. On the other hand, if the content is too large, for example, the alkali developability is lowered, and the unexposed portion of the substrate is present. There is a tendency that scum, residual film, and the like are likely to occur on the upper surface or the light shielding layer.

Further, in the present invention, a part of the polyfunctional monomer may be replaced with a monofunctional monomer having one polymerizable unsaturated bond.

The monofunctional monomer may, for example, be mono[2-(methyl)propenyloxyethyl] succinate or mono[2-(methyl)propenyloxyethyl] phthalate. Mono[(meth)acryloxyalkylalkyl]ester of a dibasic or higher polycarboxylic acid; single crystal of a polymer having a carboxyl group and a hydroxyl group at both ends of the ω-carboxypolycaprolactone mono(meth)acrylate (M) acrylate; N-(methyl) propylene decyl morpholine, N-vinyl pyrrolidone, N-vinyl-ε-caprolactam, and other commercially available products, M- 5600 (trade name, East Asian synthetic (share) production).

These monofunctional monomers may be used singly or in combination of two or more.

The content of the monofunctional monomer in the present invention is preferably 90% by mass or less, and more preferably 50% by mass or less based on the total amount of the polyfunctional monomer and the monofunctional monomer. At this time, if the use ratio of the monofunctional monomer is too large, the strength of the pixel and the surface smoothness tend to be lowered.

The (D) radiation-sensitive polymerization initiator used in the present invention is formed by exposure using rays containing visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, or the like, and can generate the above-mentioned (C) polyfunctional single. A compound of the polymerized active species of the monofunctional monomer used as needed.

Examples of such a radiation-sensitive polymerization initiator include a thioxanthone compound, an acetophenone compound, a diimidazole compound, and the like. Compounds, O-mercaptopurines, phosphonium salts, benzoin compounds, benzophenones, α-diketones, polynuclear terpenoids, diazo compounds, sulfhydrazine sulfonic acid An ester (imide sulfonate) compound or the like.

In the present invention, the radiation-sensitive polymerization initiator may be used singly or in combination of two or more, and as a radiation-sensitive polymerization initiator, preferably selected from the group consisting of thioxanthone compounds, acetophenone compounds, diimidazole compounds, and three At least one of the group consisting of a compound or an O-mercaptoquinone compound. Further, the radiation-sensitive linear composition containing CI Pigment Green 58 tends to cause agglomerated foreign matter of the pigment, and preferably contains a thioxanthone compound in the sense of reducing aggregation of foreign matter.

In the present invention, it is more preferred to use the above thioxanthone compound in combination with other radiation-sensitive polymerization initiators. In this case, the content ratio of the thioxanthone compound is preferably from 1 to 75% by mass, particularly preferably from 5 to 50% by mass, based on the total radiation polymerization initiator. By using such a radiation-sensitive polymerization initiator, a radiation-sensitive composition having high sensitivity and excellent dispersion stability can be obtained.

In a preferred radiation-sensitive polymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isomeric. Propyl thioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like.

Among these thioxanthone compounds, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-diethylthioxanthone are preferred.

The above thioxanthone compounds may be used singly or in combination of two or more.

Further, specific examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1-[4-(methylthio)benzene. 2-ylmorpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(4- Methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 1-hydroxycyclohexyl ‧ phenyl ketone, 2, 2-dimethoxy Base-1,2-diphenylethane-1-one and the like.

Among these acetophenone compounds, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and 2-benzyl-2-dimethyl group are preferred. Amino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylbenzene Butane-1-one.

The above acetophenone compounds may be used singly or in combination of two or more.

Further, specific examples of the above diimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1. , 2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dichlorobenzene -4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-di Imidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2, 4,6-Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole.

Among these diimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'- is preferred. Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorobenzene Base 4,4',5,5'-tetraphenyl-1,2'-diimidazole and the like.

The above diimidazole compounds may be used singly or in combination of two or more.

Further, when a diimidazole compound is used as the radiation-sensitive linear polymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated by a diimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis(dimethylamino)benzophenone, and 4,4. An amine hydrogen donor such as '-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more kinds, and a thiol-based hydrogen donor is preferably used.

In the present invention, when a hydrogen donor is used in combination with a diimidazole compound, the content of the hydrogen donor is preferably from 1 to 300 parts by mass, particularly preferably from 5 to 200, per 100 parts by mass of the diimidazole compound. The mass part is more preferably 10 to 150 parts by mass. At this time, if the content of the hydrogen donor is too small, the effect of improving the sensitivity tends to be lowered. On the other hand, if the amount is too large, the formed coloring layer tends to fall off from the substrate during development.

In addition, as the above three Specific examples of the compound can be exemplified by 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three with a halogenated methyl group Class of compounds.

Above three The compounds may be used singly or in combination of two or more. Further, as specific examples of the above O-indenyl quinone compound, 1,2-heptanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidene fluorene) can be cited. ), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzhydrylhydrazine), 1,2-octanedione, 1-[4- (benzylidene)phenyl]-,2-(O-benzhydrylhydrazine), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole Zyrid-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-(3-methylbenzylidene)-9H-carbazole-3- Base]-, 1-(O-acetamidoxime), ethyl ketone, 1-(9-ethyl-6-benzylidene-9H-carbazol-3-yl)-, 1-(O-B醯 肟), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-, 1-(O- Ethyl hydrazide), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9H-indazol-3-yl]-,1 -(O-acetylhydrazine), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-, 1-(O-acetamidoxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzylidene)-9H-indazole-3- Base]-, 1-(O-acetylhydrazine), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1 ,3-dioxolanyl)benzimidyl}-9H-indazol-3-yl]-,1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-B -6-(2-methyl-4-tetrahydropyranylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone ,1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-,1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzylidene)-9H-indazol-3-yl]-, 1- (O-acetyl hydrazine), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) A Oxylbenzylidene}-9H-indazol-3-yl]-, 1-(O-ethylindenyl) and the like.

Among these O-mercaptopurine compounds, preferred are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidenehydrazine), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9 -ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-carbazole 3-yl]-, 1-(O-ethylindenyl).

The above O-indenyl quinone compounds may be used singly or in combination of two or more.

In the present invention, the content of the radiation-sensitive polymerization initiator is usually 0.01 to 120 parts by mass, preferably 1 to 100 parts by mass, more preferably 1 to 1 part by mass per 100 parts by mass of the (C) polyfunctional monomer. 70 parts by mass. At this time, if the content of the radiation-sensitive polymerization initiator is too small, exposure curing is insufficient, and it is difficult to obtain a color filter in which the pixel pattern is arranged in a predetermined layout. On the other hand, if it is too large, it is formed. The pixel pattern tends to fall off from the substrate during development.

The (E) solvent used in the present invention contains a solvent having two ethoxylated groups. Specific examples of the solvent having two ethoxylated groups include propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate.

The above solvent having two ethoxylated groups may be used singly or in combination of two or more.

In the present invention, other solvents may be used together with a solvent having 2 ethoxylated 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, and diethylene glycol monoethyl ether. , diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether; 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 Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc. Glycol monoalkyl ether acetate; diglyme, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-glycol Ketone, 3 a ketone such as heptanone; an alkyl lactate such as methyl lactate or ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate or 3-methoxypropionic acid Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, ethyl acetate Ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyl Other esters such as isopropyl acid ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate An aromatic hydrocarbon such as toluene or xylene; a decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone or an indoleamine.

Among these other solvents, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl 3-methoxypropionate are preferred from the viewpoints of pigment dispersibility, solubility of components other than pigments, and coating properties. Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate.

The above other solvents may be used singly or in combination of two or more.

The solvent used in the present invention is preferably a mixture of a solvent having two ethoxylated groups and another solvent, and a content ratio of a solvent having two ethoxylated groups, preferably from 1 to 60% by mass based on the total solvent. It is particularly preferably from 1 to 45% by mass. In this case, when the content ratio of the solvent having two ethoxylated groups is too small, there is a risk that the desired effect cannot be obtained. On the other hand, if the content is too large, the solvent component is less likely to evaporate, and formation of the coating film is difficult. Danger.

The content of the solvent is not particularly limited, and the total concentration of each component other than the solvent of the composition is preferably from 5 to 50% by mass from the viewpoint of coatability and stability of the obtained radiation sensitive composition. It is particularly preferably in an amount of 10 to 40% by mass.

In the present invention, the radiation sensitive composition can be prepared by an appropriate method, and can be prepared, for example, by mixing the components (A) to (E) with the additives described below. As a preparation method of a preferred radiation-sensitive composition, a coloring agent containing CI Pigment Green 58 can be exemplified in a solvent containing a solvent having two ethoxylated groups, (F) a dispersing agent, and if necessary. In the presence of the dispersing aid, depending on the case, a part of the component (B) is pulverized by a ball mill, a roller mill or the like while being mixed and dispersed to prepare a colorant dispersion, which is then added to the colorant dispersion ( A method of preparing a mixture of B) to (D) and a solvent and an additive which are further added as needed.

In this case, the content ratio of the solvent having two ethoxylated groups in all the solvents used for preparation of the colorant dispersion is preferably 2% by mass or more, and particularly preferably 5% by mass or more.

As the (F) dispersing agent used for preparation of the above-mentioned colorant dispersion liquid, a suitable dispersing agent such as a cationic type, an anionic type, a nonionic type or an amphoteric type can be used, and a polymer dispersing agent is preferable. A block copolymer (hereinafter also referred to as "block copolymer type dispersant") composed of a block having a pigment adsorbing group on the side chain and a block having no pigment adsorbing group on the side chain is particularly preferable.

The pigment adsorption group in the block copolymer type dispersant may, for example, be a basic group such as an amine group, a carboxyl group, a phosphinium group, a quaternary ammonium group, a carbonate group, a phosphate group or the like. The block having a pigment adsorbing group on the side chain is composed of, for example, a repeating unit derived from a (meth) acrylate having these pigment adsorbing groups.

Further, the block having no pigment adsorbing group on the side chain preferably has a chain or cyclic alkyl group, an aryl group, an aralkyl group, a polycaprolactone structure, a polyether structure or the like in its side chain. The block having no pigment adsorbing group on the side chain is composed of, for example, a repeating unit derived from a (meth) acrylate having these functional groups or structures.

Such a block copolymer type dispersant is commercially available, and examples thereof include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (manufactured by BYK-Chemie (BYK)), and the like.

The above block copolymer dispersants may be used singly or in combination of two or more.

In the present invention, other dispersants may be used together with the block copolymer type dispersant. Specific examples of such other dispersing agents include polyurethanes, polyesters, cationic graft polymers, and the like. Here, the cationic comb-type graft polymer refers to a polymer having a structure in which a branched polymer of two or more molecules is branched on a main chain polymer having a plurality of basic groups (cationic functional groups). For example, a polymer comprising a polyethyleneimine in a main chain polymer portion and a ring-opening polymer in which a branched polymer portion is ε-caprolactone may be mentioned.

Such dispersants are commercially available, for example, as polyurethanes, such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above BYK-Chemie ( BYK), Soluspass 76500 (manufactured by Rubrizol Co., Ltd.), as a cationic graft polymer, Soluspass 24000 (manufactured by Rubrizol), Ajisper PB821, Ajisper PB822, Ajisper PB823, Ajisper PB824, Ajisper PB827 (manufactured by AJINOMOTO Finechemical) and the like.

These dispersing agents may be used alone or in combination of two or more.

The content of the dispersant is usually 100 parts by mass or less, preferably 0.5 to 100 parts by mass, more preferably 1 to 70 parts by mass, even more preferably 10 to 50 parts by mass, per 100 parts by mass of the (A) coloring agent. At this time, when the content of the dispersant exceeds 100 parts by mass, there is a risk of impairing developability.

The radiation sensitive composition of the present invention contains the above components (A) to (E), and may further contain an additive as needed.

Here, examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a nonionic surfactant, a cationic surfactant, and an anionic surface. Surfactant such as active agent; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxy Propoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropane Adhesion promoters such as methyl-dimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; , an antioxidant such as 2-sulfobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; 2-(3-tert-butyl-5-methyl-2 -hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. Line absorber; anti-coagulant such as sodium polyacrylate; development residue improver such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

The color filter of the present invention has a green pixel formed of the radiation sensitive composition of the present invention.

Hereinafter, a method of forming the color filter of the present invention will be described.

First, on the surface of the substrate, a light-shielding layer for dividing a pixel to be formed is formed as needed, and then a liquid composition of the radiation-sensitive linear composition of the present invention in which the green pigment is dispersed is applied onto the substrate, and then pre-prepared. Baking causes the solvent to evaporate to form a coating film. Next, the coating film is exposed by means of a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film, followed by post-baking to form a pixel array in which the green pixel pattern is arranged in a predetermined layout.

Then, the liquid composition of each of the radiation-sensitive linear compositions in which the red or blue pigment is dispersed is applied, and the respective liquid compositions are applied in the same manner as described above, pre-baked, exposed, developed, and post-baked, and sequentially formed on the same substrate. A red pixel array and a blue pixel array are used to produce a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on a substrate. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above order.

Examples of the substrate used for forming the pixel include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, on these substrates, if necessary, chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition, or the like may be performed in advance.

When the liquid composition of the radiation sensitive composition is applied onto a substrate, a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet method, or the like may be employed. Coating method, special spin coating method, slit die coating method.

The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, and particularly preferably 0.2 to 6.0 μm, as the film thickness after drying.

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

The exposure amount of the rays is usually preferably from 10 to 10,000 J/m ² .

Further, as the above alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo[5.4.0]-7-ten An aqueous solution of monocarbene, 1,5-diazabicyclo[4.3.0]-5-nonene or the like.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkali developer. Further, after alkali development, it is usually washed with water.

As the development treatment method, a rinsing development method, a spray development method, a immersion (immersion) development method, a poddle (liquid pool method) development method, or the like can be employed. The developing conditions are preferably developed at room temperature for 5 to 300 seconds.

The color filter of the present invention thus obtained is highly suitable for use in a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, or the like because of high brightness and contrast.

[Examples]

Hereinafter, embodiments of the present invention will be more specifically described by way of examples. However, the invention is not limited to the following embodiments.

Modulation of colorant dispersion

Modulation example 1

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass, and 116 parts by mass of propylene glycol methyl ether acetate as a solvent and 20 parts by mass of 1,3-butylene glycol diacetate. The ball mill was mixed and dispersed for 12 hours to prepare a pigment dispersion liquid (A-1).

Modulation example 2

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent The company produced a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass, and 116 parts by mass of propylene glycol methyl ether acetate as a solvent and 20 parts by mass of propylene glycol diacetate, which were mixed and dispersed in a ball mill for 12 hours. The pigment dispersion (A-2) was prepared.

Modulation example 3

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass, and 96 parts by mass of propylene glycol methyl ether acetate as a solvent and 40 parts by mass of 1,3-butanediol diacetate. The ball mill was mixed and dispersed for 12 hours to prepare a pigment dispersion liquid (A-3).

Modulation example 4

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent ) The company produces a solid content concentration of 45.1% by mass, 24 parts by mass, and a mixture of 76 parts by mass of ethyl 3-ethoxypropionate as a solvent and 60 parts by mass of 1,3-butylene glycol diacetate. The liquid was mixed and dispersed in a ball mill for 12 hours to prepare a pigment dispersion liquid (A-4).

Modulation example 5

40 parts by mass of a mixture of 60% by weight (mass ratio) of CI Pigment Green 58 (produced by Di Aisheng Co., Ltd.) as a coloring agent (A), Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent ) produced by the company, having a solid content concentration of 45.1% by mass, 24 parts by mass, and 76 parts by mass of 3-methoxybutyl acetate as a solvent, and 60 parts by mass of 1,3-butanediol diacetate. The mixed solution was mixed and dispersed in a ball mill for 12 hours to prepare a pigment dispersion liquid (A-5).

Modulation example 6

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent The company produced a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass and 136 parts by mass of 1,3-butanediol diacetate as a solvent, which was mixed and dispersed in a ball mill for 12 hours to prepare a pigment. Dispersion (A-6).

Comparative modulation example 1

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent The company produced a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass and 136 parts by mass of propylene glycol methyl ether acetate as a solvent, which was mixed and dispersed in a ball mill for 12 hours to prepare a pigment dispersion (a- 1).

Comparative modulation example 2

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent ) The company produced a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass and 136 parts by mass of triacetin (a solvent having three ethoxylated groups) as a solvent, which was mixed and dispersed by a ball mill. The pigment dispersion (a-2) was prepared in an hour.

Comparative modulation example 3

40 parts by mass of a mixture of 60/40 (mass ratio) of CI Pigment Green 58 (produced by Di Aisen Co., Ltd.) as a coloring agent (A) and Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent The company produced a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass, and 116 parts by mass of propylene glycol methyl ether acetate as a solvent and 20 parts by mass of cyclohexanone, which were mixed and dispersed in a ball mill for 12 hours to prepare a mixture. The pigment dispersion (a-3) was taken out.

Comparative modulation example 4

40 parts by mass of a mixture of CI Pigment Green 58 (manufactured by DIC Corporation) as a coloring agent (A) and 60/40 (mass ratio) of CI Pigment Yellow 150, Disperbyk-2001 (BYK-Chemie (BYK) as a dispersing agent) The company produced a mixture of 24 parts by mass of a solid content concentration of 45.1% by mass, and 116 parts by mass of propylene glycol methyl ether acetate as a solvent and 20 parts by mass of propylene glycol monomethyl ether, which were mixed and dispersed in a ball mill for 12 hours to prepare a mixture. The pigment dispersion (a-4) was taken out.

Comparative modulation example 5

40 parts by mass of a mixture of CI Pigment Green 36 as a coloring agent (A) and 53/47 (mass ratio) of CI Pigment Yellow 150, Disperbyk-2001 (by BYK-Chemie (BYK) Co., Ltd. as a dispersing agent, solid content A mixed liquid having a concentration of 45.1% by mass and 24 parts by mass, and 116 parts by mass of propylene glycol methyl ether acetate as a solvent and 20 parts by mass of cyclohexanone was mixed and dispersed in a ball mill for 12 hours to prepare a pigment dispersion liquid (a). -5).

(B) Synthesis of alkali soluble resin

Synthesis Example 1

To a flask equipped with a condenser and a stirrer, 2.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of ethylene glycol monomethyl ether acetate were added. 15 parts by mass of methacrylic acid, 10 parts by mass of ω-carboxydicaprolactone monoacrylate, 15 parts by mass of N-phenylmaleimide, 33 parts by mass of 2-ethylhexyl methacrylate, and styrene 12 parts by mass, 15 parts by mass of glycerin monomethacrylate, and 5.0 parts by mass of α-methylstyrene dimer (chain transfer agent), after replacing with nitrogen, the reaction solution was heated to 80 ° C with slow stirring. The polymerization was carried out while maintaining this temperature for 3 hours. Then, the reaction solution was heated to 100 ° C, and 0.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added thereto, and polymerization was further continued for 1 hour to obtain a resin solution (solid content concentration = 30 mass). %). The obtained resin Mw = 14000 and Mn = 5,700. This resin solution was referred to as "resin solution (B-1)".

Example 1

Modulation of radioactive linear composition

400 parts by mass of the pigment dispersion liquid (A-1), 200 parts by mass of the resin solution (B-1) as the (B) alkali-soluble resin, and 60 parts by mass of dipentaerythritol hexaacrylate as the (C) polyfunctional monomer. 6 parts by mass of 2,4-diethylthioxanthone as (D) radiation-sensitive polymerization initiator, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)- 9H-carbazol-3-yl J-, 1-(O-ethenylhydrazine) (produced by Ciba Specialty Chemicals, trade name IRGACURE OX02) 5 parts by mass, 2,2'-bis(2-chlorophenyl) 2 parts by mass of 4,4',5,5'-tetraphenyl-1,2'-diimidazole and 2 parts by mass of 2-mercaptobenzothiazole, and propylene glycol monomethyl ether acetate as a solvent are mixed The solid content concentration was 20.0%, and the liquid composition (G1) was prepared.

The liquid composition (G1) was evaluated in the following order. The evaluation results are shown in Table 1.

Evaluation of chromaticity characteristics and contrast

On the day of the preparation, a spin coater was used to apply a liquid composition (G1) to the soda lime glass substrate on which the liquid composition (G1) was formed on the three surfaces to form a SiO ₂ film for preventing sodium ion elution. The baking was performed on a hot plate of ° C for 4 minutes to form three coating films having different film thicknesses.

Then, after the substrates were cooled to room temperature, exposure of the coating film containing rays of respective wavelengths of 365 nm, 405 nm, and 436 nm was performed on the coating film at a exposure amount of 400 J/m ² using a high pressure mercury lamp. Then, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) on these substrates, and rinsing and developing were performed for 1 minute. Then, the substrate was washed with ultrapure water, air-dried, and then baked in a clean oven at 220 ° C for 30 minutes to form a cured film for evaluation.

For the obtained three cured films, a color analyzer (MCPD 2000 manufactured by Otsuka Electronics Co., Ltd.) was used, and the chromaticity coordinate value (x, y) in the CIE color system was measured by a C light source in a 2 degree field of view. Stimulus value (Y). From the measurement results, the chromaticity coordinate value x and the stimulation value (Y) at the chromaticity coordinate value y=0.600 were obtained.

Further, the obtained three cured films were subjected to measurement of contrast using a contrast meter (C T-1, blank 5000 manufactured by Hosei Electric Co., Ltd.), and the contrast at the chromaticity coordinate value y = 0.600 was obtained.

The liquid composition (G1) was stored at room temperature for one month, and the chromaticity performance and contrast were measured in the same manner, and the chromaticity coordinate value x, the stimulus value (Y), and the contrast at the chromaticity coordinate value y=0.600 were obtained. . The evaluation results are shown in Table 1.

Examples 2 to 6 and Comparative Examples 1 to 5

In the first embodiment, the liquid compositions (G2) to (G11) were prepared in the same manner as in Example 1 except that the types of the pigment dispersion liquid were replaced with those shown in Table 1.

Then, 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, the radioactive linear composition containing C.I. Pigment Green 58 and a solvent having two ethoxylated groups can form a green pixel having high luminance and contrast, and the contrast does not decrease with time. In contrast, when a solvent having one acetoxy group was used (Comparative Example 1), and when a solvent having three ethoxylated groups was used (Comparative Example 2), a solvent having two ethoxylated groups was used. When compared, the contrast is low.

Claims (7)

A color-sensing radiation linear composition characterized by containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent A radiation sensitive composition containing CI Pigment Green 58 as the (A) colorant and a solvent having two ethoxylated groups as the (E) solvent. A color-sensing radiation linear composition characterized by containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent The radiation sensitive composition contains cyanium bromide bromine as the (A) colorant, and contains a solvent having two ethoxylated groups as the solvent (E). The color-sensitive radiation linear composition according to claim 1 or 2, wherein the solvent (E) is a mixture of a solvent having two ethoxylated groups and another solvent, and a solvent having two ethoxylated groups. The ratio is 1 to 60% by mass in all the solvents. The colored radiation linear composition of claim 3, further comprising (F) a dispersing agent. The color-sensing radioactive composition of claim 4, wherein the (F) dispersant comprises a block having a pigment-adsorbing group on a side chain and a block having no pigment-adsorbing group on the side chain. Block copolymer. A color filter having a green pixel formed using a color-sensitive radiation composition as in the first or second aspect of the patent application. A color liquid crystal display element having a color filter as in claim 6 of the patent application.