KR20130142931A - A green colored composition for a color filter - Google Patents

Abstract

An object of this invention is to provide the green coloring composition for color filters which has high coloring power and high brightness which can be used for the color filter of the display apparatus provided with a white organic EL light source.
In order to solve the said subject, the green coloring composition for color filters of this invention is a green coloring for color filters mainly comprised from a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, a transparent resin, and the organic solvent. As the composition, the colored pigment comprises one or more green pigments selected from CI Pigment Green 7, CI Pigment Green 36 and CI Pigment Green 58, and a yellow pigment of CI Pigment Yellow 185, and also a white organic EL. It is used for the color filter of the display apparatus provided with a light source.

Description

A green colored composition for a color filter

This invention relates to the green coloring composition for color filters used for formation of the color filter of the color display apparatus which has a white organic EL (electroluminescence) element as a light source.

In recent years, a liquid crystal color display device occupies most of display devices, such as a television, a computer, and a mobile telephone. The color filter used for the liquid crystal color display device generally includes a transparent substrate, a colored layer formed on the transparent substrate, the colored layer comprising three primary colors of the red pixel portion, the green pixel portion, and the blue pixel portion, and partitioning each color pattern. And a light shielding portion (black matrix) formed on the transparent substrate. These red pixel part, green pixel part, and blue pixel part have the structure which provided the film | membrane of the synthetic resin which disperse | distributed the organic pigment with favorable heat resistance and light resistance on a board | substrate, As organic pigment, organic pigment of each color of red, green, and blue Is being used.

As the backlight in this liquid crystal color display device, there are a type using a cold cathode tube, a type using a light emitting diode of an inorganic material, a type using a white organic EL element, and the like. The backlight using a cold cathode tube or a light emitting diode made of an inorganic material has a bright line spectrum set in terms of excellent display performance, color filter matching, and durability of the backlight. In the case of the light emission spectrum, the peak has no peak in the vicinity of 420 to 430 nm, and the peak in the vicinity of 460 nm and 600 nm from the characteristics of the material. Moreover, since it has a broad peak as a whole compared with the conventional light source, luminance is high up to 500 nm vicinity also in wavelength side higher than 460 nm.

On the other hand, in the case of using a backlight using a white organic EL device, as a color characteristic (x, y, Y) in the XYZ display system of the green filter segment of the liquid crystal color display device, a spectrophotometer (manufactured by Shimadzu Corporation, UV- When measured with 2500PC, C light source 2 ° field, or manufactured by Otsuka Electronics Co., Ltd., LCF-100 type, brown rice spectrophotometer, x is in the range of 0.180≤x≤0.250 (Toyo ink is in the range of 0.180≤x≤0.225) and y is required to be higher in the range of 0.650 ≦ y ≦ 0.715 (in the case of the coating ink, the range of 0.650 ≦ y ≦ 0.715).

In the above relationship, the green pigment dispersion resist composition for color filters which is the formation material of the green filter segment designed according to the wavelength characteristic of the backlight using the conventional cold cathode tube or the light emitting diode of an inorganic material, Specifically, C.I. Pigment Green 7, C.I. Pigment Green 36 and the like have a problem in that the color characteristic value cannot be obtained from the emission spectrum of a backlight using a white organic EL element and cannot be used as it is.

In order to solve this problem, the green pigment dispersion resist composition for color filters which consists of a specific green pigment and a yellow pigment is proposed according to the emission spectrum of the backlight using a white organic electroluminescent element (for example, refer patent document 1). ).

However, further improvement in performance such as coloring power, brightness, and the like has been demanded, and its response has been urged.

Japanese Patent Publication No. 2001-089016

The subject of this invention is providing the green coloring composition for color filters which has high coloring power and high brightness which can be used for the color filter of the display apparatus provided with a white organic EL light source.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors found C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. By using a yellow pigment of Pigment Yellow 185, and using a pigment dispersing assistant having an acid group as a pigment dispersing aid, and a polymer pigment dispersing agent having a basic group as a pigment dispersing agent, to a color filter of a display device having a white organic EL light source. The present inventors have found that a green coloring composition for color filters having high coloring power and high luminance that can be used can be obtained, and has completed the present invention.

That is, the present invention is as follows.

(1) The green coloring composition for color filters mainly comprised from a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, a transparent resin, and the organic solvent, The said coloring pigment is C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. It is used for the color filter of the display apparatus containing the yellow pigment of pigment yellow 185, and having a white organic electroluminescent light source, The green coloring composition for color filters characterized by the above-mentioned.

(2) The said green coloring composition for color filters consists mainly of a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, a transparent resin, and the organic solvent, Alkali-soluble resin and photopolymerizable as said transparent resin A green coloring composition for color filters as described in (1) characterized by including a compound.

(3) The mass ratio of the said green pigment and the said yellow pigment is 95: 5-40: 60, The green coloring composition for color filters as described in (1) or (2) characterized by the above-mentioned.

(4) Furthermore, the green coloring composition for color filters in any one of (1)-(3) containing barium sulfate whose primary particle diameter is 5-20 nm.

(5) The colored pigment for color filters according to any one of (1) to (4), wherein the colored pigment is a colored pigment subjected to micronization treatment.

(6) C.I., which is the colored pigment. The yellow pigment of Pigment Yellow 185 was subjected to salt milling and micronized treatment in the presence of a pigment dispersion aid having an acid group, and the colored pigment was C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. The color according to any one of (1) to (5), wherein the at least one green pigment selected from Pigment Green 58 is subjected to salt milling treatment in the presence of a pigment dispersion aid having an acid group. Green coloring composition for the filter.

(7) The green coloring composition for color filters according to any one of (1) to (6), wherein the acid group is a sulfonic acid group.

(8) Said C.I. Pigment dispersion aids having sulfonic acid groups used for Pigment Green 7 are sulfonates having a phthalocyanine skeleton and / or C.I. Pigment Yellow 138 is a sulfonate, and C.I. Pigment dispersion adjuvant which has the sulfonic acid group used for pigment green 36 is sulfonate which has a phthalocyanine skeleton, The said C.I. The pigment dispersion adjuvant having a sulfonic acid group used for Pigment Green 58 is a sulfonate having a phthalocyanine skeleton, and the pigment dispersion adjuvant having a sulfonic acid group used for the pigment Yellow 185 is a sulfonate of Pigment Yellow 185. The green coloring composition for color filters in any one of (1)-(7) characterized by the above-mentioned.

(9) The color filter of the display apparatus provided with the white organic electroluminescent light source which has an application layer formed with the green coloring composition for color filters of said (1)-(8).

Hereinafter, the green coloring composition for color filters of this invention is demonstrated concretely for every component.

The present invention relates to a green coloring composition for a color filter. The green coloring composition for a color filter may be a composition other than a resist or a resist composition.

In any case, the green coloring composition for color filters of this invention is a composition used for the color filter of the display apparatus provided with a white organic EL light source, thereby providing the green coloring composition for color filters which has high coloring power and high brightness. can do.

(Green pigment)

As a coloring pigment used for the green coloring composition for color filters of this invention, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. Pigment Yellow 185 is used in combination with a yellow pigment. The preferable mass ratio of the green pigment (CI pigment green 7 + CI pigment green 36 + CI pigment green 58) and yellow pigment (CI pigment yellow 185) is green pigment: Yellow pigment = 95: 5-30: 70 It is more preferable that it is green pigment: yellow pigment = 95: 5-40: 60.

In addition, C.I. Green pigments such as Pigment Green 10 and 37, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1 , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193 It is also possible to use together yellow pigments, such as 194, 198, 199, 213, and 214.

In the green coloring composition for color filters of this invention, the total usage-amount of a coloring pigment is the mass fraction with respect to the total solid of the green coloring composition for color filters in the quantity of the coloring pigment to be used, Preferably it is 5-80 mass% More preferably, it is the range of 20-50 mass%.

It is preferable to use the colored pigment processed into microparticles | fine-particles in order to obtain high brightness and high contrast as the colored pigment of this invention. By performing micronization process, the primary particle diameter of a coloring pigment can be made more fine and uniform.

As the micronization treatment, for example, an untreated color pigment and a water-soluble inorganic salt (sodium chloride, barium chloride, potassium chloride, etc.), preferably sodium chloride, and an average particle diameter of the water-soluble inorganic salt to be used is preferably 50 μm or less. And a mixture containing a water-soluble dispersion medium (alkoxyalcohols, glycols, ethers, etc.) that do not substantially dissolve the water-soluble inorganic salts, kneader, roll mill, ball mill, attritor, sand mill, Japanese Patent Publication Kneaded with a kneading apparatus such as Trimix (trade name) manufactured by Inoue Co., Ltd., a planetary mixer described in No. 2006-192385, and Miracle KCK, manufactured by Asada Iron Works Co., Ltd., a continuous single-axis kneader. Thereafter, it is preferable to perform salt milling to remove the water-soluble inorganic salt and the water-soluble dispersion medium, and to perform the fine particle treatment.

Moreover, since the crystal growth of a colored pigment can be suppressed and it can refine | miniaturize uniformly, it is preferable to perform micronization process in the presence of the dispersion | distribution adjuvant which is a pigment derivative which has an acidic radical mentioned later. The usage-amount of the pigment dispersion adjuvant which has an acidic radical is 0.5-30 mass parts with respect to 100 mass parts of colored pigments, Preferably it is 3-15 mass parts.

(Pigment Dispersion Aid Having Acidic Group)

As a pigment dispersion adjuvant which has an acidic radical used for the green coloring composition for color filters of this invention, the pigment dispersion adjuvant which has a sulfonic acid group, etc. can be used.

In the green coloring composition for color filters of this invention, the usage-amount of a pigment dispersion adjuvant is 0.5-30 mass parts with respect to 100 mass parts of colored pigments, Preferably it is 3-15 mass parts. When content of the said pigment dispersion adjuvant is less than 0.5 mass part, a pigment dispersion effect will fall, and when it exceeds 30 mass parts, a pigment dispersion effect will not improve anymore.

The pigment dispersion adjuvant having the acid group,

(1) In the case of using a colored pigment which has been micronized in the absence of a pigment dispersing assistant having an acid group, 0.5 to 30 parts by mass of the pigment dispersing assistant is preferably added to 100 parts by mass of the colored pigment at the time of dispersing the colored pigment. Use 3-15 parts by mass.

(2) In the case of using the colored pigment subjected to the micronization treatment in the presence of the pigment dispersion auxiliary having an acid group, 0.5 to 30 parts by mass of the pigment dispersion aid is 100 parts by mass based on 100 parts by mass of the colored pigment during the micronization treatment of the colored pigment, Preferably it is 3-15 mass parts, 0-29.5 mass parts of pigment dispersion adjuvant, Preferably 0-12 mass parts is used with respect to 100 mass parts of colored pigments at the time of dispersing the colored pigment processed into microparticles | fine-particles.

In addition, the sum of the usage-amount of the pigment dispersion adjuvant used at the time of micronization process, and the usage-amount of the pigment dispersion adjuvant used at the time of pigment dispersion of the color pigment which processed microparticles | fine-particles is 0.5- about a pigment dispersion adjuvant with respect to 100 mass parts of colored pigments. 30 mass parts, Preferably 3-15 mass parts is used.

More specifically, the case where the pigment dispersion adjuvant which has a sulfonic acid group is used as a pigment dispersion adjuvant which has an acidic radical is demonstrated.

As a yellow pigment, C.I. When pigment yellow 185 is used, as a pigment dispersion adjuvant which has a sulfonic acid group, it is C.I. Pigment Yellow 185 is a sulfone cargo. In addition, C.I. When pigment green 7 is used, as a pigment dispersion adjuvant which has a sulfonic acid group, sulfonate and / or C.I. Pigment Yellow 138 is a sulfonate. In addition, C.I. When pigment green 36 is used, it is preferable that it is sulfonate of the pigment which has a phthalocyanine skeleton as a pigment dispersion adjuvant which has a sulfonic acid group. In addition, C.I. When pigment green 58 is used, it is preferable that it is sulfonate of the pigment which has a phthalocyanine skeleton as a pigment dispersion adjuvant which has a sulfonic acid group.

It is also possible to use Solsperth 12000 or the like.

(Polymer Pigment Dispersant Having a Basic Group)

As a polymeric pigment dispersant which has a basic group used for the green coloring composition for color filters of this invention, the polymeric pigment dispersant which has a basic group conventionally used in the field of a color filter can be used.

In the green coloring composition for color filters of this invention, it is preferable that the usage-amount of the polymeric pigment dispersant which has a basic group is 1-200 mass parts with respect to 100 mass parts of colored pigments, More preferably, it is 1-60 mass parts. When content of the polymeric pigment dispersant which has the said basic group is smaller than 1 mass part, pigment dispersion effect may fall, and when it exceeds 100 mass parts, there exists a possibility that developability may fall.

As a polymeric pigment dispersing agent which has a basic group, the following are mentioned, for example.

(1) a polyester having an amino group and / or an imino group and a free carboxyl group of a polyamine compound (for example, poly (lower alkyleneamine such as polyallylamine, polyvinylamine, polyethylene polyimine, etc.)), At least one reaction product selected from the group consisting of polyamides and polyesteramides.

(2) A carbodiimide compound having at least one side chain selected from the group consisting of polyester side chains, polyether side chains, and polyacrylic side chains and at least one basic nitrogen-containing group in the molecule.

(3) A reaction product of low molecular amino compounds such as poly (lower) alkyleneimine and methyliminobispropylamine and polyester having a free carboxyl group.

(4) The isocyanate group of a polyisocyanate compound has alcohols, such as methoxy polyethyleneglycol, polyester which has one hydroxyl group, such as caprolactone polyester, the compound which has 2-3 isocyanate group reactive functional groups, an isocyanate group reactive functional group A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a tertiary amino group.

(5) A reaction product obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group.

(6) A reaction product obtained by adding a polyether chain to a low molecular amino compound.

(7) A reaction product obtained by reacting a compound having an amino group with a compound having an isocyanate group.

(8) A reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group.

(9) A reaction product of a polycarbonate compound and a polyamine compound having a functional group capable of reacting with an amino group at one end.

(10) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 1 or more types selected from methacrylic esters or acrylic esters such as stearyl acrylate and benzyl acrylate, acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, amino group and polycapro At least one copolymer of basic group-containing polymerizable monomers such as monomers having a lactone skeleton, and at least one copolymer of styrene, styrene derivatives, and other polymerizable monomers.

(11) An acrylic block copolymer comprising a block having a basic group such as a tertiary amino group and a quaternary ammonium base group and a block having no basic functional group.

(12) A pigment dispersant obtained by Michael addition reaction of a polycarbonate compound to polyallylamine.

(13) A carbodiimide compound having at least one polybutadiene chain and at least one basic nitrogen-containing group.

(14) A carbodiimide compound having a side chain having an amide group in the molecule and at least one basic nitrogen-containing group.

(15) A polyurethane compound having a structural unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized with a quaternizing agent.

(16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule with an active hydrogen group in a molecule having an active hydrogen group and having a carbazole ring and / or an azobenzene skeleton. The number of carbazole rings and azobenzene skeletons relative to the sum of the isocyanate group derived from an isocyanate compound having an isocyanurate ring having an isocyanurate ring and the urethane bond and the urea bond produced by the reaction of the isocyanate group and the active hydrogen group is 15 to 85 % Compound. Etc.

And among these polymeric pigment dispersants, Preferably, it is also possible to use Disprbyk2001 etc., for example.

Currently, as a method of manufacturing a color filter using the green coloring composition for color filters, the resist method is mostly used, but after that it is divided into methods other than the resist method and the resist method, and the component contained in each is demonstrated below. do.

[A. When used other than resist method]

(Transparent resin)

As transparent resin used for the green coloring composition for color filters of this invention, the transmittance | permeability is 80% or more in the all wavelength range of 400-700 nm of a visible light region, Preferably 95% or more resin can be used. Examples of these transparent resins include thermosetting resins, thermoplastic resins, alkali-soluble resins, and photopolymerizable compounds (photopolymerizable resins, monomers having one or more photopolymerizable unsaturated bonds in a molecule, oligomers, and the like). These can be used individually or in mixture of 2 or more types.

Such a transparent resin is a mass fraction with respect to the total solid of the green coloring composition for color filters, Preferably it is 5-94 mass%, More preferably, it is the range of 20-50 mass% in the total amount of the transparent resin to be used.

As the thermosetting resin or the thermoplastic resin, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane-based resin, phenol Resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, etc. Can be mentioned.

As a photopolymerizable resin as a photopolymerizable compound, photocrosslinkable groups, such as a (meth) acryl compound and cinnamic acid, are introduced into the linear polymer which has reactive substituents, such as a hydroxyl group, a carboxyl group, and an amino group, via an isocyanate group, an aldehyde group, an epoxy group, etc. One resin is used. Half-esterification of linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers with (meth) acryl compounds having hydroxyl groups such as hydroxyalkyl (meth) acrylates One polymer is also used.

As a monomer which has one photopolymerizable unsaturated bond as a photopolymerizable compound in a molecule | numerator, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Alkyl methacrylates or acrylates; aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate Aminoalkyl methacrylates or acrylates such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethyl acrylate; diethylene glycol ethyl ether, triethylene glycol butyl ether, dipropylene glycol methyl ether and the like; Methacrylic acid ester of polyalkylene glycol alkyl ether Methacrylate esters; methacrylate esters or acrylate esters of polyalkylene glycol aryl ethers such as hexaethylene glycol phenyl ether; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate Elate or an acrylate can be illustrated.

As a monomer which has two or more photopolymerizable unsaturated bonds as a photopolymerizable compound in a molecule | numerator, bisphenol A dimethacrylate, 1, 4- butanediol dimethacrylate, 1, 3- butylene glycol dimethacrylate, diethylene glycol Dimethacrylate, glycerol dimethacrylate, neopentylglycol dimethacrylate, polyethyleneglycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethyleneglycol dimethacrylate, trimethylolpropane trimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate Acrylate, 1,3-butylene glycol diacrylate, diethyl Lenglycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate And pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.

About alkali-soluble resin, it describes in detail in the green pigment dispersion resist composition part for color filters mentioned later.

(Barium sulfate)

In the green coloring composition for color filters of this invention, in order to improve heat resistance (luminance), barium sulfate with a primary particle diameter of 5-20 nm can be used.

The usage-amount of barium sulfate is used in 0-25 mass% with respect to a coloring pigment, Preferably it is 5-20 mass%.

The said barium sulfate is used at the time of dispersion | distribution and / or after disperse | distributing the coloring pigment fine-processed in presence of the pigment dispersion adjuvant which has a sulfonic acid group.

(Organic solvent)

Specifically as an organic solvent used for the green coloring composition for color filters of this invention, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ethers such as ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether Organic solvents; ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Organic solvents; ketone-based organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2- Ethyl methyl propionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, Ester organic solvents such as hydroxyethyl acetate and n-amyl formate; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol; N-methylpyrrolidone, N, N-dimethylformamide, N, N- Nitrogen-containing organic solvents, such as dimethylacetamide, etc. can be illustrated. These may be used alone or in combination of two or more.

The green coloring composition for color filters of this invention consists mainly of a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, a transparent resin, and the organic solvent, These components are 90-100 mass% in a coloring composition. Occupy.

(Additive that can be added as needed)

According to the manufacturing method of the green coloring composition for color filters, various additives, such as a photoinitiator, a thermal polymerization inhibitor, a ultraviolet absorber, antioxidant, can be used suitably. As said photoinitiator, what is mentioned later is mentioned, for example.

(Method for Producing Green Coloring Composition for Color Filters of the Present Invention)

The method of manufacturing the green coloring composition for color filters which is not used by the resist method using the above material is demonstrated. The green coloring composition for color filters can be obtained by the method (1), the method (2), etc., for example.

(1) In advance, C.I. Pigment Green 7-containing pigment dispersion composition, C.I. Pigment Green 36-containing pigment dispersion composition and C.I. Pigment green 58-containing pigment dispersion composition and at least one green pigment dispersion composition, and C.I. Pigment Yellow 185 A method of producing the green coloring composition for a color filter of the present invention after the step of mixing the yellow pigment dispersion composition of the pigment dispersion composition

C.I. Pigment Green 7-containing pigment dispersion composition

C.I. micronized in the presence or absence of pigment dispersion aid having an acid group (preferably at least one selected from sulfonates of pigments having a phthalocyanine skeleton and sulfonates of C. I. pigment yellow 138). Pigment green 7, pigment dispersing aid having an acid group (preferably at least one selected from sulfonates of pigments having a phthalocyanine skeleton and sulfonates of CI pigment yellow 138), polymeric pigment dispersants having a basic group, organic solvents If necessary, a mixture of barium sulfate, a transparent resin, and, if necessary, other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Green 7-containing pigment dispersion composition is obtained.

C.I. Pigment Green 36-Containing Pigment Dispersion Composition

C.I. micronized in the presence or absence of a pigment dispersion aid having an acid group (preferably sulfonated of a pigment having a phthalocyanine skeleton). Pigment Green 36, pigment dispersing aid having an acid group (preferably sulfonate of a pigment having a phthalocyanine skeleton), polymeric pigment dispersant having a basic group, an organic solvent, barium sulfate, transparent resin, if necessary further A mixture consisting of other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Green 36 containing pigment dispersion composition is obtained.

C.I. Pigment Green 58 Containing Pigment Dispersion Composition

C.I. micronized in the presence or absence of a pigment dispersion aid having an acid group (preferably sulfonated of a pigment having a phthalocyanine skeleton). Pigment Green 58, pigment dispersing aid having an acid group (preferably sulfonate of a pigment having a phthalocyanine skeleton), polymeric pigment dispersant having a basic group, an organic solvent, barium sulfate, transparent resin, if necessary further A mixture consisting of other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Green 58 containing pigment dispersion composition is obtained.

C.I. Pigment Yellow 185-containing pigment dispersion composition

C.I. micronized with or without an acidic pigment dispersing aid (preferably C.I. Pigment Yellow 185 sulfonates) or in the absence. Pigment Yellow 185, a pigment dispersing aid having an acid group (preferably a sulfonate of CI Pigment Yellow 185), a polymeric pigment dispersant having a basic group, an organic solvent, barium sulfate, transparent resin, if necessary, further A mixture consisting of other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Yellow 185-containing pigment dispersion composition is obtained.

Complementary Pigment-containing Pigment Dispersion Compositions

Complementary pigments containing pigment dispersion compositions are similarly obtained using complementary pigments which have been micronized in the presence or absence of a pigment dispersion aid having an acid group, if necessary.

Each pigment dispersion composition described above is obtained by C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. The yellow pigment of Pigment Yellow 185 and the complementary pigment as needed are mixed in a predetermined ratio, and further, a transparent resin, barium sulfate, an organic solvent, and other additives are added as necessary to add the green coloring composition for color filters of the present invention. Get

(2) C.I. which is obtained by manufacturing each separately beforehand. Pigment Green 7-containing green coloring composition for color filters, C.I. Green coloring composition for pigment green 36 containing pigment green, and C.I. Pigment Green 58 or more selected from green coloring compositions for color filters, and C.I. Pigment Yellow 185 A method of producing the green coloring composition for color filters of the present invention after the step of mixing the yellow coloring composition for color filters

To each pigment dispersion composition obtained by the above method, a transparent resin, barium sulfate, an organic solvent, and other additives are added as necessary to prepare a color composition for each color filter. Subsequently, the coloring composition for each color filter prepared was made into C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. The yellow pigment of pigment yellow 185 and a complementary pigment are mixed as needed in a predetermined ratio, and the green coloring composition for color filters of this invention is obtained.

In the production methods of (1) and (2) above, in the case of using the micronized pigment which is micronized in the presence of a pigment dispersion auxiliary having an acid group, a pigment dispersion auxiliary having an acid group at the time of dispersing the micronized pigment is used. Even if it does not contain, it is possible to manufacture.

In addition, in the manufacturing method of said (1), (2), transparent resin and barium sulfate can be added at the time of preparation of a pigment dispersion composition, and / or after preparation of a pigment dispersion composition.

In addition, in the manufacturing method of said (1), (2), since high coloring power and high brightness are obtained, it is preferable to use the pigment processed into microparticles | fine-particles in presence of the pigment dispersion adjuvant which has an acidic radical.

[B. When used by resist method]

Next, the green coloring composition for color filters used as a green pigment dispersion resist composition for color filters of the photography method of this invention is demonstrated.

The green pigment dispersion resist composition for color filters of this invention is a resist composition which has active energy ray curability, and is alkali developable, Comprising mainly of a coloring pigment, a pigment dispersion adjuvant, a pigment dispersant, a transparent resin, and the organic solvent, The said transparent It is what contains alkali-soluble resin and a photopolymerizable compound as resin.

(Colored pigment)

As a coloring pigment, the thing described by the said green coloring composition for color filters is used. The usage-amount of a coloring pigment is 5 to 80 mass%, More preferably, it is 20 to 50 mass% by mass amount with respect to the total solid of the green pigment dispersion resist composition for color filters in total amount.

(Pigment Dispersion Aid Having Acidic Group)

As a pigment dispersion adjuvant which has an acidic radical, the thing similar to what was described by the said green coloring composition for color filters is used. The usage-amount of the pigment dispersion adjuvant which has an acidic radical in the green pigment dispersion resist composition for color filters of this invention is 0.5-30 mass parts with respect to 100 mass parts of colored pigments. When content of the pigment dispersion adjuvant which has the said acidic radical is less than 0.5 mass part, a pigment dispersion effect will fall, and when it exceeds 30 mass parts, a pigment dispersion effect will not improve any more.

The pigment dispersion adjuvant having the acid group,

(1) In the case of using the colored pigment finely divided in the absence of the pigment dispersion aid having an acid group, 0.5-30 parts by mass of the pigment dispersion aid, preferably 3, relative to 100 parts by mass of the colored pigment at the time of dispersing the colored pigment. Use ˜15 parts by mass.

(2) In the case of using the colored pigment granulated in the presence of a pigment dispersing assistant having an acid group, 0.5 to 30 parts by mass of the pigment dispersing assistant is preferably based on 100 parts by mass of the colored pigment at the time of the granulation treatment of the colored pigment. Is 3-15 mass parts, 0-29.5 mass parts of pigment dispersion adjuvant, Preferably 0-12 mass parts is used with respect to 100 mass parts of colored pigments at the time of dispersion of the colored pigment microparticles | fine-particles.

In addition, the sum of the usage-amount of the pigment dispersion adjuvant used at the time of micronization process, and the usage-amount of the pigment dispersion adjuvant used at the time of pigment dispersion of the color pigment which processed microparticles | fine-particles is 0.5- about a pigment dispersion adjuvant with respect to 100 mass parts of colored pigments. 30 mass parts, Preferably 3-15 mass parts is used.

(Pigment dispersant)

As the pigment dispersant, a polymer pigment dispersant having the same basic group as described in the green coloring composition for color filters is used.

In the green pigment dispersion resist composition for color filters of this invention, it is preferable that the usage-amount of the polymeric pigment dispersant which has a basic group is 1-200 mass parts with respect to 100 mass parts of colored pigments, More preferably, it is 1-60 mass parts. . When content of the polymeric pigment dispersant which has the said basic group is smaller than 1 mass part, pigment dispersion effect may fall, and when it exceeds 200 mass parts, there exists a possibility that developability may fall.

(Alkali-soluble resin as transparent resin)

As alkali-soluble resin as a transparent resin used for the green pigment dispersion resist composition for color filters of this invention, it acts as a binder with respect to a green pigment, and when developing a color filter, the developing solution used in the developing process, especially Preferably, if it has solubility with respect to alkaline developing solution, it will not specifically limit, What is conventionally used can be used. Especially, alkali-soluble resin which has a carboxyl group is preferable, and the copolymer of the ethylenically unsaturated monomer which has one or more carboxyl groups, and the other copolymerizable ethylenically unsaturated monomer especially is preferable.

Specifically, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl copolymerizable with an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid, and an ethylenically unsaturated monomer having a carboxyl group Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethyl And copolymers of at least one ethylenically unsaturated monomer selected from the group of monomers such as methacrylate macromonomers and cardoepoxy diacrylates and oligomers.

As an acid value of alkali-soluble resin in this invention, 50-300 mgKOH / g is preferable from a developing characteristic viewpoint. In addition, in this invention, the said acid value is a theoretical acid value, and is a value calculated arithmetically based on the ethylenically unsaturated monomer which has a carboxyl group, and its content.

In addition, as for the weight average molecular weight of alkali-soluble resin in this invention, 1,000-100,000 are preferable from a developing characteristic or the solubility with respect to the organic solvent normally. In addition, in this invention, the weight average molecular weight of the said alkali-soluble resin is the weight average molecular weight of polystyrene conversion obtained based on GPC. In the present invention, Water 2690 (manufactured by Waters) is used as the apparatus, and PLgel 5 mu MIXED-D (manufactured by Polymer Laboratories) is used as the column.

The usage-amount of alkali-soluble resin in this invention is 1-300 mass% in mass fraction with respect to all the coloring pigments used, Preferably it is 10-200 mass%. In this case, when the usage-amount of alkali-soluble resin is less than 1 mass%, there exists a possibility that developability may fall. On the other hand, when it exceeds 300 mass parts, since the coloring agent density | concentration falls relatively, there exists a possibility that it may become difficult to achieve the target color density as a thin film.

(Photopolymerizable Compound Forming Transparent Resin)

As a photopolymerizable compound which can form the transparent resin used for the green pigment dispersion resist composition for color filters of this invention, it is a monomer, oligomer, etc. which have one or more photopolymerizable unsaturated bonds in a molecule | numerator, The said green coloring composition for color filters Use the same one as described in. A photopolymerizable unsaturated bond is an unsaturated bond which can superpose | polymerize by the action of the radical and cation which generate | occur | produce when the photoinitiator mentioned later is decomposed | disassembled by active energy rays, such as an ultraviolet-ray and an electron beam.

The photopolymerizable compounds as these transparent resins can be used individually or in combination of 2 or more types. In this invention, the usage-amount of a photopolymerizable compound is a mass fraction with respect to the total solid in the green pigment dispersion resist composition for color filters, Preferably it is the range of 3-50 mass%.

(Photoinitiator)

As a photoinitiator used for the green pigment dispersion resist composition for color filters of this invention, if radical energy and a cation can be generated by irradiating active energy rays, such as an ultraviolet-ray or an electron beam, it will not specifically limit, For example, benzo Phenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoinmethyl Ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenyl ketone, t-butyl anthraquinone, 1-chloroanthra Quinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, tri Triazine may include a photopolymerization initiator and the like. These photoinitiators are used individually or in combination of 2 or more types.

In this invention, content of the said photoinitiator becomes like this. Preferably it is the range of 1-20 mass% with respect to the total solid in the said green pigment dispersion resist composition for color filters.

(Barium sulfate)

In the green pigment dispersion resist composition for color filters of this invention, in order to improve heat resistance (luminance), barium sulfate with a primary particle diameter of 5-20 nm can be used.

The usage-amount of barium sulfate is used in 0-25 mass% with respect to a coloring pigment, Preferably it is 5-20 mass%.

The said barium sulfate is used at the time of dispersion | distribution and / or after disperse | distributing the coloring pigment fine-processed in presence of the pigment dispersion adjuvant which has a sulfonic acid group.

(Organic solvent)

As an organic solvent used for the green coloring composition for color filters of this invention, the organic solvent conventionally used in the field of a liquid crystal color filter resist can be used preferably. Specifically, an ester organic solvent, an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an aromatic hydrocarbon organic solvent, containing a boiling point at atmospheric pressure (1.013 × 10 ² kPa) is 100 to 220 ° C. Nitrogen-based organic solvents; If the boiling point contains a large amount of an organic solvent exceeding 220 ° C., the organic solvent may remain in the dry coating film without sufficiently evaporating when the applied coating film is prebaked, and the heat resistance of the dry coating film may be lowered. Moreover, when it contains a large amount of the organic solvent below boiling point 100 degreeC, it becomes difficult to apply | coat uniformly and there exists a possibility that the coating film excellent in surface smoothness may not be obtained.

Specifically as a preferable solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol mono Ether organic solvents such as methyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Ether ester organic solvents such as monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; methyl isobutyl ketone, cyclohexanone, Ketone organic solvents such as 2-heptanone and δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxy Esters such as butyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, n-amyl formate Organic solvents; nitrogen-containing organic solvents such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. These may be used alone or in combination of two or more.

Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate from the viewpoint of solubility, dispersibility, coating properties, and the like. , Cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc. Preferably, it is propylene glycol monomethyl ether acetate.

It is preferable that these organic solvents are 50 mass% or more in the green pigment dispersion resist composition for color filters of this invention from a viewpoint of the solubility of the said alkali-soluble resin, the dispersibility of a coloring pigment, applicability | paintability, etc., and are 70 mass% or more It is more preferable to make it contain.

The green pigment dispersion resist composition for color filters of this invention consists mainly of a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and the organic solvent, These components Silver occupies 90-100 mass% in the green pigment dispersion resist composition for color filters.

(Additive that can be added as needed)

The green pigment dispersion resist composition for color filters of this invention can use various additives, such as a thermal polymerization inhibitor, a ultraviolet absorber, and antioxidant, suitably as needed.

(Method for Producing Green Pigment Dispersion Resist Composition for Color Filter of the Present Invention)

The method of manufacturing the green pigment dispersion resist composition for color filters using the above material is demonstrated. The green pigment dispersion resist composition for color filters can be obtained by the following manufacturing methods (1) and (2).

(1) In advance, C.I. Pigment Green 7-containing pigment dispersion composition, C.I. Pigment Green 36-containing pigment dispersion composition and C.I. Pigment green 58-containing pigment dispersion composition and at least one green pigment dispersion composition, and C.I. Pigment Yellow 185 A method for producing a green pigment dispersion resist composition for a color filter of the present invention after the step of mixing the yellow pigment dispersion composition of the pigment dispersion composition

C.I. Pigment Green 7-containing pigment dispersion composition

C.I. micronized in the presence or absence of pigment dispersion aid having an acid group (preferably at least one selected from sulfonates of pigments having a phthalocyanine skeleton and sulfonates of C. I. pigment yellow 138). Pigment green 7, pigment dispersing aid having an acid group (preferably at least one selected from sulfonates of pigments having a phthalocyanine skeleton and sulfonates of CI pigment yellow 138), polymeric pigment dispersants having a basic group, organic solvents A mixture of barium sulfate, an alkali-soluble resin, and further other additives, if necessary, is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Green 7-containing pigment dispersion composition is obtained.

C.I. Pigment Green 36-Containing Pigment Dispersion Composition

C.I. micronized in the presence or absence of a pigment dispersion aid having an acid group (preferably sulfonated of a pigment having a phthalocyanine skeleton). Pigment Green 36, pigment dispersing aid having an acid group (preferably sulfonate of a pigment having a phthalocyanine skeleton), polymeric pigment dispersant having a basic group, an organic solvent, barium sulfate, alkali-soluble resin, if necessary, further Accordingly a mixture consisting of other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Green 36 containing pigment dispersion composition is obtained.

C.I. Pigment Green 58 Containing Pigment Dispersion Composition

C.I. micronized in the presence or absence of a pigment dispersion aid having an acid group (preferably sulfonated of a pigment having a phthalocyanine skeleton). Pigment Green 58, pigment dispersing aid having an acid group (preferably sulfonate of a pigment having a phthalocyanine skeleton), polymeric pigment dispersant having a basic group, an organic solvent, barium sulfate, alkali-soluble resin, if necessary, further Accordingly a mixture consisting of other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Green 58 containing pigment dispersion composition is obtained.

C.I. Pigment Yellow 185-containing pigment dispersion composition

C.I. micronized with or without an acidic pigment dispersing aid (preferably C.I. Pigment Yellow 185 sulfonates) or in the absence. Pigment Yellow 185, a pigment dispersion aid having an acid group (preferably a sulfonate of CI Pigment Yellow 185), a polymeric pigment dispersant having a basic group, an organic solvent, barium sulfate, alkali-soluble resin, if necessary, further Accordingly a mixture consisting of other additives is obtained. The resulting mixture was kneaded and dispersed by using various dispersers such as roll mill, kneader, high speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high pressure disperser and the like. Pigment Yellow 185-containing pigment dispersion composition is obtained.

Complementary Pigment-containing Pigment Dispersion Compositions

Complementary pigments containing pigment dispersion compositions are similarly obtained using complementary pigments which have been micronized in the presence or absence of a pigment dispersion aid having an acid group, if necessary.

Each pigment dispersion composition described above is obtained by C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. The yellow pigment of Pigment Yellow 185 and the complementary pigment as needed are mixed in a predetermined ratio, and further, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, barium sulfate, an organic solvent, and other additives are added as necessary. The green pigment dispersion resist composition for color filters of this invention is obtained.

(2) C.I. Pigment Green 7-containing green pigment dispersion resist composition for color filters, C.I. Pigment Green 36 Green pigment dispersion resist composition for color filter containing C.I. Pigment Green 58 or more selected from green pigment dispersion resist compositions for color filters, and C.I. Pigment Yellow 185 A method for producing the green pigment dispersion resist composition for color filters of the present invention after the step of mixing the yellow pigment dispersion resist composition for color filters

To each pigment dispersion composition obtained by the above method, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, barium sulfate, an organic solvent, and other additives are added as necessary to prepare a green pigment dispersion resist composition for each color filter. Next, the prepared green pigment dispersion resist composition for each color filter was prepared using C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. The yellow pigment of pigment yellow 185 and the complementary pigment as needed are mixed so that a predetermined ratio may be obtained, and the green pigment dispersion resist composition for color filters of this invention is obtained.

In the production methods of (1) and (2) above, in the case of using the micronized pigment which is micronized in the presence of a pigment dispersion auxiliary having an acid group, a pigment dispersion auxiliary having an acid group at the time of dispersing the micronized pigment is used. Even if it does not contain, it is possible to manufacture.

In addition, in the manufacturing method of said (1), (2), alkali-soluble resin and barium sulfate can be added at the time of preparation of a pigment dispersion composition, and / or after preparation of a pigment dispersion composition.

In addition, in the manufacturing method of said (1), (2), since high coloring power and high brightness are obtained, it is preferable to use the pigment processed into microparticles | fine-particles in presence of the pigment dispersion adjuvant which has an acidic radical.

Moreover, as a method of manufacturing the color filter of the display apparatus provided with a white organic EL light source using the green coloring composition for color filters of this invention, including the apparatus required for it, well-known means as a structure other than this coloring composition It can manufacture by employing.

Example

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples. In addition, unless otherwise indicated, "%" means "mass%", and "part" shall mean "mass part."

Here, Solsperth 125000 (manufactured by Lubrizol Japan), which is a pigment dispersion aid having a sulfonic acid group, is a sulfonated product of copper phthalocyanine. Disprbyk2001 (manufactured by Vicchemy Co., Ltd.) is a polymer pigment dispersant having a basic group of a modified acrylic block copolymer having an amine value of 29 and an acid value of 13.

As barium sulfate, the thing with a primary particle diameter of 16 nm was used.

BMA / MAA copolymer (benzyl methacrylate / methacrylic acid copolymer) is alkali-soluble resin whose theoretical acid value is 120 mgKOH / g and the mass mean molecular weight is 25,000.

DPEHA (Dipentaerythritol hexaacrylate) is a photopolymerizable compound.

Irgacure 369 (2-benzyl- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone) is a photopolymerization initiator.

<Organic solvent>

PGMEA: Propylene glycol monomethyl ether acetate

<Pigment dispersion aid>

(Sulfonated cargo of C.I. Pigment Yellow 185)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, followed by stirring with a magnetic stirrer. 10 g of Pigment Yellow 185 was added and stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was added to a 1 L beaker, and the reaction was poured into this ice water and stirred for 30 minutes with a magnetic stirrer. This was filtered and washed under reduced pressure, and the obtained solid was dried to give C.I. 12 g of sulfonates of Pigment Yellow 185 were obtained.

(Sulfone cargo of C.I. Pigment Yellow 138)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, followed by stirring with a magnetic stirrer. 10 g of Pigment Yellow 138 was added and stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was added to a 1 L beaker, and the reaction was poured into this ice water and stirred for 30 minutes with a magnetic stirrer. This was filtered and washed under reduced pressure, and the obtained solid was dried to give C.I. 12 g of sulfonates of Pigment Yellow 138 were obtained.

<Particulate treatment pigment No.1-19>

<Colored Pigment Treated with Particles Using Pigment Dispersion Aid Having Sulfonate Group>

(C.I. Pigment Yellow 185 treated by kneading in the presence of a sulfonated particle of No. 1: C.I. Pigment Yellow 185)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. Pigment Yellow 185, 100 parts by mass, C.I. 7 mass parts of pigment yellow 185 sulfonates, 1000 mass parts of sodium chloride of 20 micrometers of particle diameters, and 240 mass parts of diethylene glycol were thrown in, and it kneaded at 75 degreeC for 10 hours, and performed salt milling. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 98 mass parts of particulate-form pigment 1.

(C.I. Pigment Yellow 185 treated by kneading in the presence of sulfonated particles of micronized pigment No. 2: C.I. Pigment Yellow 185)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. Pigment Yellow 185, 100 parts by mass, C.I. Pigment Yellow 185 sulfonate was charged with 3.5 parts by mass, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol, and kneaded at 75 ° C for 10 hours to perform salt milling. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 95 mass parts of particulate-formation pigment 2.

(C.I. Pigment Yellow 185 treated with a continuous uniaxial kneader in the presence of a sulfonate of micronized pigment No. 3: C.I. Pigment Yellow 185)

C.I. Pigment Yellow 185, 800 parts by mass, C.I. The sulfonate of Pigment Yellow 185 was premixed with 56 parts by mass, 8000 parts by mass of sodium chloride having a particle diameter of 20 µm, and 1000 parts by mass of diethylene glycol. This mixture was quantitatively supplied to a continuous single screw kneader (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), kneaded at 75 ° C, and salt milling was performed. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 98 mass parts microparticles | fine-particles treatment pigment 3.

(Micronized Pigment No. 4: C.I. Pigment Green 7 kneaded in the presence of Solsperth 12000)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Green 7, 7 parts by mass of Solsperth 12000 as a pigment dispersion aid, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol were kneaded at 75 ° C for 10 hours to perform salt milling. It was. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 97 mass parts of fine-grained pigment 4.

(Micronized Pigment No. 5: C.I. Pigment Green 7 kneaded in the presence of Solsperth 12000)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Green 7, 3.5 parts by mass of Solsperth 12000 as a pigment dispersion aid, 1000 parts by mass of sodium chloride having a particle diameter of 20 µm, and 240 parts by mass of diethylene glycol were kneaded at 75 ° C. for 10 hours to perform salt milling. It was. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 94 mass parts of fine-grained pigment 5.

(Micronized Pigment No. 6: C.I. Pigment Green 7 treated with a continuous monoaxial kneader in the presence of Solsperth 12000)

C.I. Pigment Green 7 was premixed with 800 parts by mass, 56 parts by mass of Solsperth 12000 as a pigment dispersion aid, 8000 parts by mass of sodium chloride having a particle size of 20 µm, and 1000 parts by mass of diethylene glycol. This mixture was quantitatively supplied to a continuous single screw kneader (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), kneaded at 75 ° C, and salt milling was performed. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 98 mass parts of particulate-form pigment 6.

(C.I. Pigment Green 7 treated by kneading in the presence of a sulfonated product of particulate matter No. 7: C.I. pigment yellow 138)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. Pigment Green 7 in 100 parts by mass, C.I. 7 mass parts of pigment yellow 138 sulfonates, 1000 mass parts of sodium chloride of 20 micrometers of particle diameters, and 240 mass parts of diethylene glycol were thrown in, and it kneaded at 75 degreeC for 10 hours, and performed salt milling. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 98 mass parts of particulate-form pigment 7.

(Micronized Pigment No. 8: C.I. Pigment Green 58 kneading in the presence of Solsperth 12000)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Green 58, 7 parts by mass of Solsperth 12000 as a pigment dispersion aid, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol were kneaded at 75 ° C for 10 hours to perform salt milling. It was. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 97 mass parts of particulate-form pigment 8.

(Micronized Pigment No. 9: C.I. Pigment Green 58 treated with a continuous monoaxial kneader in the presence of Solsperth 12000)

C.I. The pigment green 58 was premixed with 800 parts by mass, 56 parts by mass of Solsperth 12000 as a pigment dispersion aid, 8000 parts by mass of sodium chloride having a particle size of 20 µm, and 1000 parts by mass of diethylene glycol. This mixture was quantitatively supplied to a continuous single screw kneader (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), kneaded at 75 ° C, and salt milling was performed. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 98 mass parts microparticles | fine-particles treatment pigment 9.

<Colored Pigment Treated with Particles Without Using Pigment Dispersion Aid Having Sulfonate Group>

(Micronized Pigment No. 10: C.I. Pigment Yellow 185 treated by kneading in the absence of pigment dispersion aid having sulfonic acid group)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Yellow 185, 1000 parts by mass of sodium chloride having a particle diameter of 20 µm, and 240 parts by mass of diethylene glycol were added, and kneaded at 75 ° C for 10 hours to perform salt milling. Next, 1350 mass parts of kneaded material obtained were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of particulate-form pigment 10.

(Micronized Pigment No. 11: C.I. Pigment Yellow 150 treated by kneading in the absence of pigment dispersion aid having sulfonic acid group)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Yellow 150, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol were charged, and kneaded at 75 ° C for 10 hours to perform salt milling. Next, 1350 mass parts of kneaded material obtained were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of particulate-form pigment 11.

(Micronized Pigment No. 12: C.I. Pigment Yellow 138 kneader-treated in the absence of pigment dispersion aid having sulfonic acid group)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Yellow 138, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol were charged, and kneaded at 75 ° C for 10 hours to perform salt milling. Next, 1350 mass parts of kneaded material obtained were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of granulation pigment 12.

(Micronized Pigment No. 13: C.I. Pigment Green 7 treated by kneading in the absence of pigment dispersion aid having sulfonic acid group)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. Pigment Green 7 was charged with 100 parts by mass, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol, and kneaded at 75 ° C for 10 hours to perform salt milling. Next, 1350 mass parts of kneaded material obtained were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of particulate-form pigment 13.

(C.I. Pigment Green 58 treated by kneading in the absence of pigment dispersing adjuvant having a micronized pigment No. 14: sulfonic acid group)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of pigment green 58, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol were added, and kneaded at 75 ° C for 10 hours to perform salt milling. Next, 1350 mass parts of kneaded material obtained were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of particulate-form pigment 14.

(Micronized Pigment No. 15: C.I. Pigment Green 36 kneaded in the presence of Solsperth 12000)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Green 36, 7 parts by mass of Solsperth 12000 as a pigment dispersion aid, 1000 parts by mass of sodium chloride having a particle diameter of 20 µm, and 240 parts by mass of diethylene glycol were kneaded at 75 ° C for 10 hours to perform salt milling. It was. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of particulate-form pigment 15.

(Micronized Pigment No. 16: C.I. Pigment Green 36 kneaded in the presence of Solsperth 12000)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. 100 parts by mass of Pigment Green 36, 3.5 parts by mass of Solsperth 12000 as a pigment dispersion aid, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol were kneaded at 75 ° C. for 10 hours to perform salt milling. It was. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 94 mass parts of granulated pigment 16.

(Micronized Pigment No. 17: C.I. Pigment Green 36 treated with a continuous monoaxial kneader in the presence of Solsperth 12000)

C.I. The pigment green 36 was premixed with 800 parts by mass, 56 parts by mass of Solsperth 12000 as a pigment dispersion aid, 8000 parts by mass of sodium chloride having a particle size of 20 µm, and 1000 parts by mass of diethylene glycol. This mixture was quantitatively supplied to a continuous single screw kneader (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), kneaded at 75 ° C, and salt milling was performed. Next, 1300 mass parts of obtained kneaded material were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 97 mass parts of microparticles | fine-particles-treated pigment 17.

(Micronized Pigment No. 18: C.I. Pigment Green 36 treated by kneading in the absence of pigment dispersion aid having sulfonic acid group)

To tank of kneader (brand name: KHD-2, Inoue Co., Ltd.), C.I. Pigment Green 36 was charged with 100 parts by mass, 1000 parts by mass of sodium chloride having a particle size of 20 µm, and 240 parts by mass of diethylene glycol, and kneaded at 75 ° C for 10 hours to conduct salt milling. Next, 1350 mass parts of kneaded material obtained were thrown into 3 liters of warm water, it stirred for 1 hour, heating at 70 degreeC, and it was set as the slurry form. Filtration and water washing were repeated, and sodium chloride and diethylene glycol were removed, and it dried at 40 degreeC, and obtained 96 mass parts of particulate-form pigment 18.

(Micronized Pigment No. 19: C.I. Pigment Yellow 185 without dispersion treatment in the absence of pigment dispersion aid)

C.I. Pigment Yellow 185 was prepared.

<Pigment Dispersion Composition for Color Filters>

The micronized pigment Nos. 1 to 18 or C.I. The pigmentation treatment pigment No. 19 which is Pigment Yellow 185, the polymeric pigment dispersant which has a basic group, the pigment dispersion adjuvant which has a sulfonic acid group, alkali-soluble resin (BMA / MAA copolymer), a photopolymerizable compound, and the organic solvent (PGMEA) It mixed so that it might become a composition of 2, and knead | mixed for 6 hours with the paint conditioner using 0.2 mm zirconia beads, and obtained the pigment dispersion compositions 1-26 for color filters.

<Pigment Dispersion Resist Composition for Color Filter>

Subsequently, after mixing the pigment dispersion compositions 1-26 for color filters, BMA / MAA copolymer, DPEHA, Irgacure 369, and PGMEA uniformly using a high speed stirrer so that the composition of Table 3 may be obtained, Filtration was carried out with a membrane filter to obtain pigment dispersion resist compositions 1 to 26 for color filters.

<Green pigment dispersion resist composition for color filters of Examples 1-11 and Comparative Examples 1-6>

The composition selected from the pigment dispersion resist compositions 1-26 for color filters so that it may become the pigment ratio of Table 4 was mixed uniformly, and the green pigment dispersion resist compositions for color filters of Examples 1-11 and Comparative Examples 1-6 were obtained.

(evaluation)

<Dispersion Stability>

About the green pigment dispersion resist composition for color filters of Examples 1-11 and Comparative Examples 1-6, each was taken in a glass bottle, the stopper was sealed, and the state after storing for 7 days at room temperature was evaluated according to the following evaluation criteria. The results are shown in Table 1.

A: No thickening or sediment was found.

B: Shake lightly to find the thickening or sediment that returns to its original level.

C: A thickening or sediment is identified that does not return to normal shaking.

<Evaluation of the color characteristic of the green pigment dispersion resist composition for color filters>

The green pigment dispersion resist compositions for color filters of Examples 1 to 11 and Comparative Examples 1, 2, 4 and 5 were applied onto a glass substrate using a spin coater. Subsequently, after prebaking at 100 degreeC for 3 minutes, it exposed with high pressure mercury lamp, and post-baked at 230 degreeC for 30 minutes. Subsequently, the color characteristics (x, y, Y) of each of the resists of Examples 1 to 11 and Comparative Examples 1, 2, 4, and 5 were measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view). Measured. In Examples 1-11 and Comparative Examples 1, 2, 4, and 5, the film thickness and brightness Y in chromaticity x = 0.224 and y = 0.669 were calculated | required.

According to Examples 1 to 11, which are examples according to the present invention, the pigment-colored resist composition for color filters has good optical properties as a color filter of a white organic EL light source because the pigment dispersibility is good and the value of Y is lowered. I can see that.

On the other hand, according to Comparative Examples 2, 3, 5, and 6 in which pigment yellow 185 is used and other pigments are used, even though the values of x and y are common to the examples, the values of Y are high, so that white organic It cannot be used suitably as a color filter for EL light sources.

Moreover, according to the comparative examples 1 and 4 which do not use a dispersion aid, the dispersion stability of the obtained pigment coloring resist composition for color filters is inadequate, and the thickening and sediment of the grade which do not return to an original even if it shakes vigorously is confirmed.

Claims (9)

As a green coloring composition for color filters mainly comprised from a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, a transparent resin, and the organic solvent, The said coloring pigment is C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. At least one green pigment selected from Pigment Green 58 and C.I. It is used for the color filter of the display apparatus containing the yellow pigment of pigment yellow 185, and having a white organic electroluminescent light source, The green coloring composition for color filters characterized by the above-mentioned. The method of claim 1,
The said green coloring composition for color filters consists mainly of a coloring pigment, the pigment dispersion adjuvant which has an acidic radical, the polymeric pigment dispersant which has a basic group, a transparent resin, and the organic solvent, and contains alkali-soluble resin and a photopolymerizable compound as said transparent resin. The green coloring composition for color filters characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The mass ratio of the said green pigment and the said yellow pigment is 95: 5-40: 60, The green coloring composition for color filters characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
Furthermore, the green coloring composition for color filters containing barium sulfate whose primary particle diameter is 5-20 nm. 5. The method according to any one of claims 1 to 4,
The colored pigment is a green coloring composition for a color filter, characterized in that the colored pigment subjected to the micronization treatment. The method according to any one of claims 1 to 5,
The yellow pigment of CI pigment yellow 185 which is the said pigment is salt-milled and micronized by the presence of the pigment dispersion adjuvant which has an acidic radical, CI pigment green 7, CI pigment green 36 and CI which are the said pigments The green coloring composition for color filters, wherein the at least one green pigment selected from Pigment Green 58 is subjected to salt milling treatment in the presence of a pigment dispersion aid having an acid group. 7. The method according to any one of claims 1 to 6,
The acid group is a sulfonic acid group, characterized in that the green coloring composition for color filters. 8. The method according to any one of claims 1 to 7,
The pigment dispersion adjuvant having a sulfonic acid group used for the CI Pigment Green 7 is at least one selected from sulfonates having a phthalocyanine skeleton and sulfonates of CI Pigment Yellow 138, and sulfones used for the CI Pigment Green 36. The pigment dispersion adjuvant having an acid group is a sulfonate having a phthalocyanine skeleton, and the pigment dispersion adjuvant having a sulfonic acid group used for the CI pigment green 58 is a sulfonate having a phthalocyanine skeleton, and used for the pigment yellow 185. The pigment coloring adjuvant which has a sulfonic acid group is the sulfonate of pigment yellow 185, The green coloring composition for color filters characterized by the above-mentioned. The color filter of the display apparatus provided with the white organic electroluminescent light source which has an application layer formed with the green coloring composition for color filters in any one of Claims 1-8.