TWI595055B - A green colored composition for a color filter - Google Patents

Description

Green coloring composition for color filter

The present invention relates to a green coloring composition for a color filter used for forming a color filter of a color display device having a white organic EL (Electroluminescence) element as a light source.

Recently, most display devices such as televisions, computers, and mobile phones have been gradually occupied by liquid crystal color display devices. A color filter for a liquid crystal color display device generally has a transparent substrate, a coloring layer formed on the transparent substrate and including three red color portions, a green pixel portion, and a blue pixel portion, and a coloring layer for dividing each coloring pattern. The light-shielding portion (black matrix) formed on the transparent substrate. The red pixel portion, the green pixel portion, and the blue pixel portion are formed by disposing a film of a synthetic resin having an organic pigment excellent in heat resistance and light resistance on a substrate, and red, green can be used as the organic pigment. And organic pigments of various colors.

As the backlight device in the liquid crystal color display device, there are a type using a cold cathode tube, a type of a light emitting diode using an inorganic material, a type using a white organic EL element, and the like. Further, a backlight device using a cold cathode tube or an inorganic material light-emitting diode has a large number of bright line spectra in terms of excellent display performance, matching with a color filter, and durability of a backlight device. In contrast, in the light-emitting spectrum of a backlight device using a white organic EL element, there is no peak near 420 to 430 nm depending on the characteristics of the material, and there are peaks near 460 nm and around 600 nm. Also, because compared to the previous light source It has a broad peak as a whole, so even on the wavelength side higher than 460 nm, the brightness becomes high up to around 500 nm.

On the other hand, in the case of using a backlight device using a white organic EL element, the color filter (x, y, Y) of the green filter segment of the liquid crystal color display device in the XYZ color system requires spectral separation. Photometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2° field of view; or manufactured by Otsuka Electronics Co., Ltd., LCF-100 type, microscopic spectrometry device), measured at x in the range of 0.180 ≦ x ≦ 0.250 ( Toyo Ink is in the range of 0.180≦x≦0.225), y is in the range of 0.650≦y≦0.715 (Toyo Ink is in the range of 0.650≦y≦0.715), and Y is higher.

In the relationship as described above, the color filter for forming a material of a green filter segment which is designed according to the wavelength characteristics of a backlight device using a cold cathode tube or a light-emitting diode of an inorganic material is a green pigment dispersion resist. The composition of the composition, specifically, CI Pigment Green 7, CI Pigment Green 36, etc., has a problem that the above-described color characteristic value cannot be obtained in the light-emitting spectrum of a backlight device using a white organic EL element, and it cannot be directly used.

In order to solve this problem, a green pigment-dispersed resist composition for a color filter containing a specific green pigment and a yellow pigment according to an emission spectrum of a backlight device using a white organic EL element has been proposed (for example, see Patent Document 1).

However, the industry is demanding further improvement in performance such as tinting strength and brightness, and countermeasures are urgently required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-089016

An object of the present invention is to provide a color filter which can be used for a color filter of a display device having a white organic EL light source and which has high coloring power and high brightness, and is colored with green color. combination.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that by using at least one green pigment selected from CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58, and a yellow pigment of CI Pigment Yellow 185 As a coloring pigment, and in combination with a pigment dispersing aid having an acid group as a pigment dispersing aid and a polymer pigment dispersing agent having a basic group as a pigment dispersing agent, a display device usable with a white organic EL light source can be obtained. The present invention has been completed by a green coloring composition for a color filter and a color filter having high coloring power and high luminance.

That is, the present invention is as follows.

(1) A green coloring composition for a color filter, which is mainly composed of a color pigment, a pigment dispersing aid having an acid group, a polymer pigment dispersing agent having a basic group, a transparent resin, and an organic solvent. In the composition, the coloring pigment includes at least one green pigment selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58, and a yellow pigment of CI Pigment Yellow 185, and the color filter is colored with green color. The object can be used for a color filter having a display device of a white organic EL light source.

(2) The green coloring composition for a color filter according to (1), wherein the green coloring composition for the color filter is mainly composed of a coloring pigment, a pigment dispersing aid having an acid group, and an alkalinity. The base polymer pigment dispersant, a transparent resin, and an organic solvent comprise an alkali-soluble resin and a photopolymerizable compound as the transparent resin.

(3) The green coloring composition for a color filter according to (1) or (2), wherein the mass ratio of the green pigment to the yellow pigment is 95:5 to 40:60.

(4) The green coloring composition for a color filter according to any one of (1) to (3) further comprising a barium sulfate having a primary particle diameter of 5 to 20 nm.

(5) The green coloring composition for a color filter according to any one of (1) to (4), wherein the coloring pigment is a micronized pigment.

(6) The green coloring composition for color filters according to any one of (1) to (5), wherein the yellow pigment of CI Pigment Yellow 185 as the coloring pigment is based on a pigment having an acid group At least one green pigment selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 as the coloring pigment, is subjected to a micronization treatment in the presence of a dispersing aid, and has an acid group. The micronized treatment of the salt milling treatment in the presence of the pigment dispersing aid.

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

(8) The green coloring composition for a color filter according to any one of (1) to (7), wherein the pigment dispersing aid having a sulfonic acid group used for the CI Pigment Green 7 has a sulfonate of a phthalocyanine skeleton and/or a sulfonate of CI Pigment Yellow 138, and a sulfonate-containing pigment dispersing aid used for the above CI Pigment Green 36 is a sulfonate having a phthalocyanine skeleton, and is used for the above CI Pigment Green 58 The pigment dispersing aid having a sulfonic acid group is a sulfonate having a phthalocyanine skeleton, and the pigment dispersing aid having a sulfonic acid group used for the above pigment yellow 185 is a sulfonate of the pigment yellow 185.

(9) A color filter comprising a display device for a white organic EL light source, comprising the coating formed by the green coloring composition for a color filter according to any one of the above (1) to (8) Floor.

Hereinafter, each component of the green coloring composition for a color filter of the present invention will be specifically described.

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

In either case, the green coloring composition for color filters of the present invention is a composition for a color filter having a display device of a white organic EL light source, thereby providing a high coloring power and high brightness. The color filter is a green coloring composition.

(green pigment)

As the coloring pigment used for the green coloring composition for a color filter of the present invention, at least one green pigment selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 and CI Pigment Yellow 185 may be used in combination. Use with yellow pigments. The preferred mass ratio of green pigment (CI Pigment Green 7+CI Pigment Green 36+CI Pigment Green 58) to Yellow Pigment (CI Pigment Yellow 185) is Green Pigment: Yellow Pigment = 95:5~30:70, more preferably Green pigment: yellow pigment = 95:5~40:60.

Furthermore, it is also possible to use a green pigment such as CI Pigment Green 10, 37 in a range that does not degrade the performance, CI 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, Yellow pigments such as 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193, 194, 198, 199, 213, 214 are used.

In the green coloring composition for a color filter of the present invention, the total amount of the coloring pigment used is based on the mass fraction of the total solid content of the green coloring composition for the color filter, and the amount of the coloring pigment used is It is preferably in the range of 5 to 80% by mass, more preferably in the range of 20 to 50% by mass.

In order to obtain high definition or high contrast, the coloring pigment of the present invention preferably uses a micronized pigment. Coloring pigment can be obtained by performing micronization treatment The primary particle size is further fine and uniform.

As the above-mentioned fine particle treatment, for example, it is preferred to carry out a microparticulation treatment by salt grinding treatment: an inorganic salt containing an untreated coloring pigment and a water-soluble inorganic salt (preferably, an aqueous salt of a water-soluble inorganic salt used) has an average particle diameter of 50 μm or less of sodium chloride, barium chloride, potassium chloride or the like, preferably sodium chloride) and a water-soluble dispersion medium (alkoxy alcohols, glycols, and substantially insoluble of the above-mentioned water-soluble inorganic salt) A mixture of an ether or the like is a kneader, a roll mill, a ball mill, an attritor, a sand mill, and a well-prepared company as a planetary mixer described in JP-A-2006-192385. After mixing the manufactured TRI-MIX (trade name) and a mixing device such as Miracle KCK manufactured by Asada Iron Works Co., Ltd. as a continuous uniaxial kneading machine, the water-soluble inorganic salt and the water-soluble dispersion medium are removed.

Furthermore, in terms of suppressing the crystal growth of the coloring pigment and uniformly refining it, it is preferred to carry out the microparticulation treatment in the presence of a pigment dispersing aid which is a pigment derivative having an acid group as described below. The amount of the pigment dispersing aid having an acid group is from 0.5 to 30 parts by mass, preferably from 3 to 15 parts by mass, per 100 parts by mass of the coloring pigment.

(Pigment dispersing aid with acid group)

As the pigment dispersing aid having an acid group used in the green coloring composition for a color filter of the present invention, a pigment dispersing aid having a sulfonic acid group or the like can be used.

In the green coloring composition for a color filter of the present invention, the amount of the pigment dispersing aid used is 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, per 100 parts by mass of the coloring pigment. When the content of the pigment dispersing aid is less than 0.5 part by mass, the pigment dispersing effect is lowered. On the other hand, when it exceeds 30 parts by mass, the pigment dispersing effect is not further improved.

Regarding the above pigment dispersing aid having an acid group,

(1) In the case of a coloring pigment which is subjected to micronization treatment in the absence of a pigment dispersing aid having an acid group, when the coloring pigment is dispersed, relative to the colored pigment 100 parts by mass of the material is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, based on the pigment dispersing aid.

(2) In the case of a coloring pigment which is subjected to microparticulation treatment in the presence of a pigment dispersing aid having an acid group, a pigment dispersing aid is used in the microparticulation treatment of the coloring pigment with respect to 100 parts by mass of the coloring pigment. 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, and in the dispersion of the pigmented pigmented pigment, 0 to 29.5 parts by mass of the pigment dispersing aid is used, preferably 100 parts by mass of the coloring pigment. Use 0 to 12 parts by mass.

In addition, the total amount of the pigment dispersing aid used in the microparticulation treatment and the amount of the pigment dispersing aid used in dispersing the pigment of the microparticulated colored pigment are 100 parts by mass relative to the coloring pigment. The pigment dispersing aid is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass.

More specifically, a case where a pigment dispersing aid having a sulfonic acid group is used as a pigment dispersing aid having an acid group will be described.

When C.I. Pigment Yellow 185 is used as the yellow pigment, it is a sulfonate of C.I. Pigment Yellow 185 as a pigment dispersing aid having a sulfonic acid group. Further, when C.I. Pigment Green 7 is used as the green pigment, the pigment dispersing aid having a sulfonic acid group is a sulfonate of a pigment having a phthalocyanine skeleton and/or a sulfonate of C.I. Pigment Yellow 138. Further, when C.I. Pigment Green 36 is used as the green pigment, the pigment dispersing aid having a sulfonic acid group is preferably a sulfonate of a pigment having a phthalocyanine skeleton. Further, when C.I. Pigment Green 58 is used as the green pigment, the pigment dispersing aid having a sulfonic acid group is preferably a sulfonate of a pigment having a phthalocyanine skeleton.

Also, Solsperse 12000 or the like can be used.

(polymer pigment dispersant with basic base)

The polymer pigment dispersant having a basic group used as the green coloring composition for a color filter of the present invention can be used as previously used in the field of color filters. A polymer pigment dispersant having a basic group.

In the green coloring composition for a color filter of the present invention, the amount of the polymer pigment dispersant having a basic group is preferably from 1 to 200 parts by mass, more preferably from 1 to 60, per 100 parts by mass of the coloring pigment. Parts by mass. When the content of the polymer pigment dispersant having a basic group is less than 1 part by mass, the pigment dispersion effect may be lowered. On the other hand, when it exceeds 100 parts by mass, the developability may be lowered.

Examples of the polymer pigment dispersant having a basic group include the following.

(1) A polyamine compound (for example, poly(allylamine, polyvinylamine, polyethyleneimine, etc.), such as poly(lower alkylamine), and the like, and an amine group and/or an imine group are selected from a group having a free carboxyl group. A reaction product of at least one of a group consisting of an ester, a polyamidamine, and a polyester decylamine.

(2) having at least one carbon bismuth of at least one side chain and at least one basic nitrogen group selected from the group consisting of a polyester side chain, a polyether side chain, and a polypropylene fluorenyl side chain in the molecule. Imine compound.

(3) A reaction product of a poly(lower) alkyleneimine, a methylimidopropylamine, or the like, and a polyester having a free carboxyl group.

(4) A polyester having one hydroxyl group such as an isocyanate group of a polyisocyanate compound, an alcohol such as methoxypolyethylene glycol or a caprolactone polyester, or a compound having 2 to 3 isocyanate-reactive functional groups. And a reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having an isocyanate-reactive functional group and a tertiary amino group.

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

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

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

(9) A reaction product of a polycarbonate compound having a functional group reactive with an amine group at a single terminal and a polyamine compound.

(10) selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, At least one of methacrylate or acrylate such as propyl acrylate, butyl acrylate, stearyl acrylate or benzyl acrylate, acrylamide, methacrylamide, N-hydroxymethyl decylamine, vinyl At least one of a basic group-containing polymerizable monomer such as imidazole, vinyl pyridine, or a monomer having an amine group and a polycaprolactone skeleton, and styrene, a styrene derivative, or other polymerizable monomer At least one copolymer.

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

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

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

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

(15) A polyurethane-based compound having an amine group including an ethylene oxide chain and a propylene oxide chain and having an amine group which is quaternized by a quaternizing agent.

(16) a compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with an active hydrogen group of a compound having an active hydrogen group and having a carbazole ring and/or an azobenzene skeleton in the molecule, And in the molecule of the compound, the number of the carbazole ring and the azobenzene skeleton is relative to the isocyanate group derived from the isocyanate compound having an isocyanurate ring and the amine group formed by the reaction of the isocyanate group and the active hydrogen group. The total of the formate bond and the urea bond is 15 to 85%.

Further, among the polymer pigment dispersants, it is preferred to use, for example, Disprbyk 2001 and so on.

At present, a method for producing a color filter using a green coloring composition for a color filter is mainly a resist method, and is divided into a method other than a resist method and a resist method, and the following is for each of them. The components and the like contained therein will be described.

[A. For cases other than the resist method] (transparent resin)

The transparent resin used for the green coloring composition for a color filter of the present invention can be used for a resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. Examples of the transparent resin include a thermosetting resin, a thermoplastic resin, an alkali-soluble resin, and a photopolymerizable compound (photopolymerizable resin, a monomer having one or more photopolymerizable unsaturated bonds in the molecule, and an oligomer). and many more. These may be used alone or in combination of two or more.

The total amount of the transparent resin used in the green coloring composition is preferably in the range of 5 to 94% by mass, more preferably 20%, based on the total solid content of the green coloring composition for the color filter. Within the range of ~50% by mass.

Examples of the thermosetting resin or the thermoplastic resin include a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, and the like. Polyvinyl acetate, polyurethane 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, and the like.

The photopolymerizable resin which is a photopolymerizable compound can be introduced into a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group via an isocyanate group, an aldehyde group, an epoxy group or the like into a (meth)acrylic acid. A resin obtained by a photocrosslinkable group such as a compound or cinnamic acid. It is also possible to use a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer, and a hydroxyalkyl (meth)acrylate. A polymer obtained by semi-esterifying a (meth)acrylic compound having a hydroxyl group.

Examples of the monomer having one photopolymerizable unsaturated bond in the molecule of the photopolymerizable compound include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methyl acrylate. An alkyl methacrylate or an alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate; an aralkyl methacrylate or an aralkyl acrylate such as benzyl methacrylate or benzyl acrylate; Alkoxyalkyl methacrylate such as butoxyethyl acrylate or butoxyethyl acrylate or alkoxyalkyl acrylate; N,N-dimethylaminoethyl methacrylate, N, Aminoalkyl methacrylate or aminoalkyl acrylate such as N-dimethylaminoethyl ester; polyalkylene glycol alkane such as diethylene glycol diethyl ether, triethylene glycol butyl ether or dipropylene glycol methyl ether a methacrylate or acrylate of a vinyl ether; an methacrylate or an acrylate of a polyalkylene glycol aryl ether; Ester or acrylic Ester; glyceryl methacrylate or glyceryl acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule of the photopolymerizable compound include bisphenol A dimethacrylate and 1,4-butanediol dimethacrylate; , 3-butanediol dimethacrylate, diethylene glycol dimethacrylate, glyceryl dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, poly Propylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, Dipentaerythritol hexamethacrylate, dipentaerythritol pentamethyl acrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol II Acrylate, glyceryl diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate Ester, pentaerythritol IV Acrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.

The alkali-soluble resin will be described in detail in a green pigment-dispersed resist composition for a color filter to be described later.

(Barium sulfate)

In the green coloring composition for a color filter of the present invention, in order to improve heat resistance (brightness), barium sulfate having a primary particle diameter of 5 to 20 nm can be used.

The amount of barium sulfate used is in the range of 0 to 25% by mass, preferably 5 to 20% by mass based on the coloring pigment.

The above-mentioned barium sulfate is used in the case of dispersing and/or dispersing the coloring pigment which is subjected to the micronization treatment in the presence of the pigment dispersing aid having a sulfonic acid group.

(Organic solvents)

Specific examples of the organic solvent used in the green coloring composition for a color filter of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol. Monobutyl ether, diethylene glycol monomethyl 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, diethyl An ether-based organic solvent such as diol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, An ether ester such as propylene glycol monoethyl ether acetate; an organic solvent such as methyl isobutyl ketone, cyclohexanone, 2-heptanone or δ-butyrolactone; methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, butyl 3-methyl-3-methoxypropionate, methyl 3-methoxypropionate, 3-methoxypropane An ester-based organic solvent such as ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate or n-amyl formate; methanol, ethanol, Isopropanol, butanol Alcohol solvents; N-methyl pyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide and other nitrogen-containing organic solvent. These may be used alone or in combination of two or more.

The green coloring composition for a color filter of the present invention mainly comprises a color pigment, a pigment dispersing aid having an acid group, a polymer pigment dispersing agent having a basic group, a transparent resin, and It is composed of an organic solvent, and these components account for 90 to 100% by mass in the coloring composition.

(can be added as needed)

Various additives such as a photopolymerization initiator, a thermal polymerization inhibitor, a UV absorber, and an antioxidant can be suitably used in accordance with the method for producing a green coloring composition for a color filter. As the photopolymerization initiator, for example, the latter will be mentioned.

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

A method of producing a green coloring composition for a color filter which is not used in a resist method using the above materials will be described. The green coloring composition for a color filter can be obtained, for example, by the following production methods (1), (2), and the like.

(1) at least one green pigment dispersion composition selected from a pigment dispersion composition containing CI Pigment Green 7 , a pigment dispersion composition containing CI Pigment Green 36, and a pigment dispersion composition containing CI Pigment Green 58 in advance Method for producing green coloring composition for color filter of the present invention by mixing with yellow pigment dispersion composition containing pigment dispersion composition of CI Pigment Yellow 185

Pigment dispersion composition containing C.I. Pigment Green 7

A mixture comprising: a pigment dispersing aid having an acid group (preferably at least one selected from the group consisting of a sulfonate of a pigment having a phthalocyanine skeleton and a sulfonate of CI Pigment Yellow 138) is obtained. In the case of the CI pigment green 7 having a micronized treatment, a pigment dispersing aid having an acid group (preferably at least one selected from the group consisting of a sulfonate of a pigment having a phthalocyanine skeleton and a sulfonate of CI Pigment Yellow 138), A polymer pigment dispersant having a basic group, an organic solvent, barium sulfate as needed, a transparent resin, and other additives as needed. The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment green. A pigment dispersion composition of 7.

Pigment dispersion composition containing C.I. Pigment Green 36

Obtaining a mixture comprising the following components: in the presence or absence of a pigment having an acid group CI pigment green 36 which is micronized in the case of a dispersing aid (preferably a sulfonate of a pigment having a phthalocyanine skeleton), a pigment dispersing aid having an acid group (preferably a sulphur having a phthalocyanine skeleton) a compound, a polymer pigment dispersant having a basic group, an organic solvent, barium sulfate as needed, a transparent resin, and other additives as needed. The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment green. A pigment dispersion composition of 36.

Pigment dispersion composition containing C.I. Pigment Green 58

Obtaining a mixture comprising the following components: CI pigment green 58 having an acid group in the presence or absence of a pigment dispersing aid having an acid group (preferably a sulfonate of a pigment having a phthalocyanine skeleton) A pigment dispersing aid (preferably a sulfonate of a pigment having a phthalocyanine skeleton), a polymer pigment dispersing agent having a basic group, an organic solvent,, if necessary, barium sulfate, a transparent resin, and optionally other additives. The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment green. A pigment dispersion composition of 58.

Pigment dispersion composition containing C.I. Pigment Yellow 185

Obtaining a mixture comprising the following components: CI Pigment Yellow 185, having an acid group in the presence or absence of a pigment dispersing aid having an acid group (preferably a sulfonate of CI Pigment Yellow 185) A dispersing aid (preferably a sulfonate of CI Pigment Yellow 185), a polymeric pigment dispersing agent having a basic group, an organic solvent, barium sulfate as needed, a transparent resin, and, if necessary, other additives. The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment yellow. A pigment dispersion composition of 185.

Pigment dispersion composition containing complementary color pigment

The complementary color pigment is also used as a complementary color pigment which is micronized in the presence or absence of a pigment dispersing aid having an acid group, and a pigment dispersion composition containing a complementary color pigment is obtained in the same manner.

Each of the above pigment dispersion compositions is at a specific ratio of at least one green pigment selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58, a yellow pigment of CI Pigment Yellow 185, and optionally a complementary pigment. In the manner of mixing, a transparent resin, barium sulfate, an organic solvent, and other additives are added as needed to obtain a green coloring composition for a color filter of the present invention.

(2) A green coloring composition for color filters selected from CI pigment green 7 and a green coloring composition for color filters containing CI pigment green 36 and CI pigment green, respectively, which are separately manufactured in advance The color filter of 58 is used to produce a green coloring composition for a color filter of the present invention by mixing at least one of the green coloring composition with the coloring filter containing the CI pigment yellow 185 and the yellow coloring composition. Methods

A coloring composition for each color filter is prepared by adding a transparent resin, barium sulfate, an organic solvent, and other additives to each of the pigment dispersion compositions obtained by the above method. Then, each color filter prepared by using the coloring composition is selected from at least one green pigment 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 The required complementary color pigments are mixed in a specific ratio to obtain a green coloring composition for a color filter of the present invention.

In the production method of the above (1) and (2), when the finely divided pigment is subjected to the microparticulation treatment in the presence of the acid dispersing aid having an acid group, even when the finely divided pigment is dispersed, even if it is not contained A pigment dispersing aid having an acid group can also be produced.

Further, in the production methods of the above (1) and (2), the transparent resin or barium sulfate may be added after the production of the pigment dispersion composition and/or after the production of the pigment dispersion composition.

Further, in the production methods of the above (1) and (2), in terms of obtaining high coloring power and high brightness, it is preferred to carry out the use of the particles in the presence of a pigment dispersing aid having an acid group. Sub-treated pigment.

[B. Case for resist method]

Next, the green coloring composition for a color filter of the green pigment dispersion resist composition for color filters used in the photographic method of the present invention will be described.

The green pigment dispersion resist composition for a color filter of the present invention has active energy ray hardenability and is an alkali developable resist composition mainly composed of a color pigment, a pigment dispersing aid, a pigment dispersing agent, and a transparent resin. The organic solvent is composed of an alkali-soluble resin and a photopolymerizable compound as the transparent resin.

(coloring pigment)

As the coloring pigment, those described in the green coloring composition for a color filter described above are used. The amount of the coloring pigment used is preferably 5 to 80% by mass, more preferably 5 to 80% by mass, based on the total solid content of the green pigment-dispersed resist composition of the color filter. 20 to 50% by mass.

(Pigment dispersing aid with acid group)

As the pigment dispersing aid having an acid group, the same as those described in the green coloring composition for a color filter described above is used. In the green pigment-dispersed resist composition for a color filter of the present invention, the amount of the pigment dispersing aid having an acid group is from 0.5 to 30 parts by mass based on 100 parts by mass of the coloring pigment. When the content of the above-mentioned pigment dispersing aid having an acid group is less than 0.5 part by mass, the pigment dispersing effect is lowered, and on the other hand, when it exceeds 30 parts by mass, the pigment dispersing effect is not further improved.

Regarding the above pigment dispersing aid having an acid group,

(1) When a coloring pigment which is micronized in the absence of a pigment dispersing aid having an acid group is used, when the coloring pigment is dispersed, a pigment dispersing aid 0.5 is used with respect to 100 parts by mass of the coloring pigment. ~30 parts by mass, preferably 3 to 15 parts by mass.

(2) performing micronization in the presence of a pigment dispersing aid having an acid group In the case of a coloring pigment, in the case of the fine particle treatment of the coloring pigment, the pigment dispersing aid is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, based on 100 parts by mass of the coloring pigment. In the case of dispersing the pigment, the pigment dispersing aid is used in an amount of 0 to 29.5 parts by mass, preferably 0 to 12 parts by mass, based on 100 parts by mass of the coloring pigment.

In addition, the total amount of the pigment dispersing aid used in the microparticulation treatment and the amount of the pigment dispersing aid used in dispersing the pigment of the microparticulated colored pigment are 100 parts by mass relative to the coloring pigment. The pigment dispersing aid is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass.

(pigment dispersant)

As the pigment dispersant, a polymer pigment dispersant having a basic group similar to those described in the green coloring composition for a color filter described above is used.

In the green pigment-dispersed resist composition for a color filter of the present invention, the amount of the polymer pigment dispersant having a basic group is preferably from 1 to 200 parts by mass, based on 100 parts by mass of the coloring pigment. Good 1~60 parts by mass. When the content of the polymer pigment dispersant having a basic group is less than 1 part by mass, the pigment dispersion effect may be lowered. On the other hand, when it exceeds 200 parts by mass, the developability may be lowered.

(as an alkali-soluble resin of transparent resin)

The alkali-soluble resin which is a transparent resin used for the green pigment-dispersed resist composition for a color filter of the present invention functions as a binder for a green pigment and is used as a binder when manufacturing a color filter. The developer to be used in the development treatment step, particularly preferably soluble in the alkali developer, is not particularly limited, and the prior user can be used. Among them, an alkali-soluble resin having a carboxyl group is preferred, and a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer is particularly preferred.

Specific examples thereof include an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid or methacrylic acid, and a copolymerizable with an ethylenically unsaturated monomer having a carboxyl group, which is selected from the group consisting of styrene and C. 2-hydroxyethyl enoate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , glyceryl monoacrylate, glyceryl methacrylate, N-phenyl maleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, phenolphthalein epoxy diacrylate, etc. a copolymer of at least one ethylenically unsaturated monomer in the group of the bulk or oligomer.

The acid value of the alkali-soluble resin in the present invention is preferably from 50 to 300 mg KOH/g in terms of development characteristics. Further, in the present invention, the acid value is a theoretical acid value, which is a value obtained by calculation based on an ethylenically unsaturated monomer having a carboxyl group and a content thereof.

Further, the weight average molecular weight of the alkali-soluble resin in the present invention is preferably from 1,000 to 100,000 in terms of development characteristics and solubility in an organic solvent. Furthermore, in the present invention, the weight average molecular weight of the alkali-soluble resin is a weight average molecular weight in terms of polystyrene obtained by GPC (Gel Permeation Chromatography). In the present invention, as a device, Water 2690 (manufactured by Waters Co., Ltd.) was used, and as a column, PLgel 5 μ MIXED-D (manufactured by Polymer Laboratories) was used.

The amount of the alkali-soluble resin used in the present invention is from 1 to 300% by mass, preferably from 10 to 200% by mass, based on the mass fraction of the total coloring pigment used. In this case, if the amount of the alkali-soluble resin used is less than 1% by mass, the development characteristics may be lowered. On the other hand, when the amount exceeds 300 parts by mass, the concentration of the colorant is relatively lowered, so that it is difficult to achieve the target color density as a film.

(Photopolymerizable compound forming a transparent resin)

The photopolymerizable compound which is a transparent resin which can be used for the green pigment dispersion resist composition for color filters of the present invention is used as a monomer having one or more photopolymerizable unsaturated bonds in the molecule, and oligomerization. Things, etc., and with the above color filter with green The same as those described in the color composition. The photopolymerizable unsaturated bond is an unsaturated bond which can be polymerized by the action of a radical or a cation which is generated when a photopolymerization initiator is decomposed by an active energy ray such as an ultraviolet ray or an electron beam.

These photopolymerizable compounds which are transparent resins can be used singly or in combination of two or more. In the present invention, the amount of the photopolymerizable compound to be used is preferably in the range of 3 to 50% by mass based on the total solid content of the green pigment-dispersed resist composition for a color filter.

(photopolymerization initiator)

The photopolymerization initiator used in the green pigment dispersion resist composition for a color filter of the present invention is not particularly limited as long as it can generate radicals and cations by irradiation of active energy rays such as ultraviolet rays or electron beams. For example, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone can be cited. , benzoin, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, α-hydroxyisobutyl benzophenone, 9-oxosulfur 2-chloro 9-oxosulfur , 1-hydroxycyclohexyl phenyl ketone, tert-butyl hydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole, 2-ethyl hydrazine, 1,4-naphthoquinone, 1,2-benzopyrene, 1,4-dimethylindole, 2-phenylindole, 2-methyl-1[4-(methylthio)phenyl] -2- Lolinylpropan-1-one, three A photopolymerization initiator or the like. These photopolymerization initiators may be used singly or in combination of two or more.

In the present invention, the content of the photopolymerization initiator is preferably in the range of 1 to 20% by mass based on the total solid content of the green pigment-dispersed resist composition for a color filter.

(Barium sulfate)

In the green pigment-dispersed resist composition for a color filter of the present invention, in order to improve heat resistance (brightness), barium sulfate having a primary particle diameter of 5 to 20 nm can be used.

The amount of barium sulfate used is in the range of 0 to 25% by mass relative to the coloring pigment, It is preferably used in the range of 5 to 20% by mass.

The above-mentioned barium sulfate is used in the case of dispersing and/or dispersing the coloring pigment which is subjected to the micronization treatment in the presence of the pigment dispersing aid having a sulfonic acid group.

(Organic solvents)

As the organic solvent used for the green coloring composition for a color filter of the present invention, an organic solvent which has been used in the field of the liquid crystal color filter resist has been preferably used. Specifically, it is an ester-based organic solvent having a boiling point of 100 to 220 ° C at normal pressure (1.013 × 10 ² kPa), an ether-based organic solvent, an ether ester-based organic solvent, a ketone-based organic solvent, an aromatic hydrocarbon-based organic solvent, A nitrogen-containing organic solvent or the like. When a large amount of the organic solvent having a boiling point of more than 220 ° C is used, when the coating film formed by coating is pre-baked, the organic solvent is not sufficiently evaporated and remains in the dried coating film, so that the heat resistance of the dried coating film is lowered. . Further, when a large amount of an organic solvent having a boiling point of less than 100 ° C is contained, it is difficult to apply uniformly without unevenness, and a coating film having excellent surface smoothness cannot be obtained.

Preferred examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether. Ether-based organic solvents such as 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 methyl ethyl ether Ether ester organic solvent such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate a ketone-based organic solvent such as methyl isobutyl ketone, cyclohexanone, 2-heptanone or δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2- Ethyl methacrylate, butyl 3-methyl-3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Esters, organic solvents such as ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate; N-methylpyrrolidone, N,N-dimethyl Nitrogen-containing organic solvents such as guanamine and N,N-dimethylacetamide Wait. 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 B are preferable in terms of solubility, dispersibility, coatability and the like. Acid ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, butyl 3-methyl-3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc., more preferably propylene glycol monomethyl ether acetate.

The organic solvent is preferably 50 mass in the green pigment dispersion resist composition for a color filter of the present invention in terms of solubility of the alkali-soluble resin, dispersibility of a coloring pigment, coating property, and the like. More than %, more preferably 70% by mass or more.

The green pigment dispersion resist composition for a color filter of the present invention mainly comprises a color pigment, a pigment dispersion assistant having an acid group, a polymer pigment dispersant having a basic group, an alkali-soluble resin, a photopolymerizable compound, The photopolymerization initiator and the organic solvent are contained, and these components are 90 to 100% by mass in the green pigment dispersion resist composition for a color filter.

(can be added as needed)

In the green pigment-dispersed resist composition for a color filter of the present invention, various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant may be suitably used as needed.

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

A method of producing a green pigment-dispersed resist composition for a color filter using the above materials will be described. The green pigment dispersion resist composition for a color filter can be obtained by the following production methods (1) and (2).

(1) at least one green pigment dispersion composition selected from a pigment dispersion composition containing CI Pigment Green 7 , a pigment dispersion composition containing CI Pigment Green 36, and a pigment dispersion composition containing CI Pigment Green 58 in advance Method for producing green pigment dispersion resist composition for color filter of the present invention by mixing with yellow pigment dispersion composition containing pigment dispersion composition of CI Pigment Yellow 185

Pigment dispersion composition containing C.I. Pigment Green 7

A mixture comprising: a pigment dispersing aid having an acid group (preferably at least one selected from the group consisting of a sulfonate of a pigment having a phthalocyanine skeleton and a sulfonate of CI Pigment Yellow 138) is obtained. In the case of the CI pigment green 7 having a micronized treatment, a pigment dispersing aid having an acid group (preferably at least one selected from the group consisting of a sulfonate of a pigment having a phthalocyanine skeleton and a sulfonate of CI Pigment Yellow 138), A polymer pigment dispersant having a basic group, an organic solvent, barium sulfate as needed, an alkali-soluble resin, and other additives as needed. The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment green. A pigment dispersion composition of 7.

Pigment dispersion composition containing C.I. Pigment Green 36

Obtaining a mixture comprising the following components: CI pigment green 36 having an acid group in the presence or absence of a pigment dispersing aid having an acid group (preferably a sulfonate of a pigment having a phthalocyanine skeleton) a pigment dispersing aid (preferably a sulfonate of a pigment having a phthalocyanine skeleton), a polymer pigment dispersing agent having a basic group, an organic solvent, a barium sulfate as needed, an alkali-soluble resin, and optionally other additives . The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment green. A pigment dispersion composition of 36.

Pigment dispersion composition containing C.I. Pigment Green 58

Obtaining a mixture comprising the following components: CI pigment green 58 having an acid group in the presence or absence of a pigment dispersing aid having an acid group (preferably a sulfonate of a pigment having a phthalocyanine skeleton) a pigment dispersing aid (preferably a sulfonate of a pigment having a phthalocyanine skeleton), a polymer pigment dispersing agent having a basic group, an organic solvent, a barium sulfate as needed, an alkali-soluble resin, and optionally other additives . The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser. A pigment dispersion composition containing C.I. Pigment Green 58 was obtained.

Pigment dispersion composition containing C.I. Pigment Yellow 185

Obtaining a mixture comprising the following components: CI Pigment Yellow 185, having an acid group in the presence or absence of a pigment dispersing aid having an acid group (preferably a sulfonate of CI Pigment Yellow 185) A dispersing aid (preferably a sulfonate of CI Pigment Yellow 185), a polymeric pigment dispersing agent having a basic group, an organic solvent, an optional barium sulfate, an alkali-soluble resin, and, if necessary, other additives. The obtained mixture is kneaded and dispersed by using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a CI-containing pigment yellow. A pigment dispersion composition of 185.

Pigment dispersion composition containing complementary color pigment

The complementary color pigment is also used as a complementary color pigment which is micronized in the presence or absence of a pigment dispersing aid having an acid group, and a pigment dispersion composition containing a complementary color pigment is obtained in the same manner.

Each of the above pigment dispersion compositions is selected from at least one green pigment selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58, a yellow pigment of CI Pigment Yellow 185, and optionally a complementary pigment. Mixing in a ratio, further adding a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin as needed, barium sulfate, an organic solvent, and other additives to obtain a green pigment dispersion resist for a color filter of the present invention Composition.

(2) Dispersing a resist composition with a green pigment by using a green pigment-dispersed resist composition selected from the group consisting of a color pigment containing green pigment 7 and a green pigment-containing color filter containing CI pigment green 36, and a CI-containing pigment The color filter of green color 58 is prepared by mixing at least one of the green pigment dispersion resist composition and the color filter containing CI pigment yellow 185 with a yellow pigment dispersion resist composition. Method for dispersing resist composition with green pigment for color filter

Further, each of the pigment dispersion compositions obtained by the above method is further prepared by adding a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin as needed, barium sulfate, an organic solvent, and other additives to prepare each color filter. Green pigment dispersion resist composition. Then, each color filter prepared is a green pigment dispersion resist composition selected from at least one green pigment selected from CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58, and yellow of CI Pigment Yellow 185. The pigment and the complementary color pigments are mixed in a specific ratio to obtain a green pigment dispersion resist composition for a color filter of the present invention.

In the production method of the above (1) and (2), in the case of using a microparticulated pigment which is subjected to microparticulation treatment in the presence of a pigment dispersing aid having an acid group, even when the finely divided pigment is dispersed, A pigment dispersing aid containing an acid group can also be produced.

Further, in the production methods of the above (1) and (2), the alkali-soluble resin or barium sulfate may be added after the production of the pigment dispersion composition and/or after the production of the pigment dispersion composition.

Further, in the production methods of the above (1) and (2), in terms of obtaining high coloring power and high brightness, it is preferably used for the micronization treatment in the presence of a pigment dispersing aid having an acid group. pigment.

Further, as a method of producing a color filter including a display device of a white organic EL light source using the green coloring composition for a color filter of the present invention, a known mechanism can be employed as a device including the necessary one. It is manufactured by the structure other than a coloring composition.

[Examples]

The invention is further illustrated by the following examples, but the invention is not limited to the examples. In addition, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.

Here, Solsperse 125000 (manufactured by Lubrizol Co., Ltd.), which is a pigment dispersing aid having a sulfonic acid group, is a sulfonate of copper phthalocyanine. Disprbyk 2001 (manufactured by BYK-Chemie Co., Ltd.) is a modified acrylic block copolymer having an amine value of 29 and an acid value of 13 and having a basic group. A polymer pigment dispersant.

As the barium sulfate, a primary particle diameter of 16 nm is used.

The benzyl methacrylate-methacrylic acid copolymer (benzyl methacrylate-methacrylic acid copolymer) is an alkali-soluble resin having a theoretical acid value of 120 mg KOH/g and a mass average molecular weight of 25,000.

DPEHA (dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate) is a photopolymerizable compound.

IRGACURE 369(2-benzyl-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone) is a photopolymerization initiator.

<organic solvent>

PGMEA (propylene glycol monomethyl ether acetate): propylene glycol monomethyl ether acetate

<Pigment Dispersing Aid> (C.I. Pigment Yellow 185 sulfonate)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, and 10 g of C.I. Pigment Yellow 185 was added while stirring with a magnetic stirrer, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was placed in a 1 L beaker, and the above reactant was poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered under reduced pressure, washed with water, and the obtained solid was dried to obtain 12 g of sulfonate of C.I. Pigment Yellow 185.

(C.I. Pigment Yellow 138 sulfonate)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, and 10 g of C.I. Pigment Yellow 138 was placed while stirring with a magnetic stirrer, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was placed in a 1 L beaker, and the above reactant was poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered under reduced pressure, washed with water, and the obtained solid was dried to obtain 12 g of the sulfonate of C.I.

<Microparticle treatment pigment No. 1 to 19> <Coloring pigment which is subjected to micronization treatment using a pigment dispersing aid having a sulfonic acid group>

(Microparticle-treated pigment No. 1: C.I. Pigment Yellow 185) which was subjected to a kneader treatment in the presence of a sulfonate of C.I. Pigment Yellow 185.

100 parts by mass of CI Pigment Yellow 185, 7 parts by mass of a sulfonate of CI Pigment Yellow 185 as a pigment dispersing aid, and 1000 parts by mass of a particle size of 20 μm were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). The sodium chloride and 240 parts by mass of diethylene glycol were kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 98 parts by mass of the fine particle-treated pigment 1.

(Microparticle-treated Pigment No. 2: C.I. Pigment Yellow 185) which was subjected to a kneader treatment in the presence of a sulfonate of C.I. Pigment Yellow 185.

100 parts by mass of CI Pigment Yellow 185, 3.5 parts by mass of a sulfonate of CI Pigment Yellow 185 as a pigment dispersing aid, and 1000 parts by mass of a particle size of 20 μm were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). The sodium chloride and 240 parts by mass of diethylene glycol were kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 95 parts by mass of the fine particle-treated pigment 2.

(Microparticle-treated pigment No. 3: C.I. Pigment Yellow 185 which was subjected to continuous uniaxial kneading in the presence of a sulfonate of C.I. Pigment Yellow 185)

800 parts by mass of C.I. Pigment Yellow 185, 56 parts by mass as a pigment dispersing aid, C.I. Pigment Yellow 185 sulfonate, 8000 parts by mass of 20 μm sodium chloride, and 1000 parts by mass of diethylene glycol were premixed. The mixture was quantitatively supplied to a continuous uniaxial kneading machine (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), and kneaded at 75 ° C to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded material is put into 3 liters of warm water. In the middle, the mixture was stirred while heating to 70 ° C for 1 hour to form a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 98 parts by mass of the fine particle-treated pigment 3.

(Microparticle-treated pigment No. 4: C.I. Pigment Green 7 which was subjected to kneading treatment in the presence of Solsperse 12000)

100 parts by mass of CI Pigment Green, 7 parts by mass of Solsperse 12000 as a pigment dispersing aid, and 1000 parts by mass of sodium chloride having a particle diameter of 20 μm were placed in a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). 240 parts by mass of diethylene glycol was kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 97 parts by mass of the fine particle-treated pigment 4.

(Microparticle-treated pigment No. 5: C.I. Pigment Green 7 which was subjected to a kneader treatment in the presence of Solsperse 12000)

100 parts by mass of CI Pigment Green 7 and 3.5 parts by mass of Solsperse 12000 as a pigment dispersing aid, and 1000 parts by mass of sodium chloride having a particle diameter of 20 μm were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). 240 parts by mass of diethylene glycol was kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 94 parts by mass of the fine particle-treated pigment 5.

(Microparticle-treated pigment No. 6: C.I. Pigment Green 7 which was subjected to continuous uniaxial kneading machine treatment in the presence of Solsperse 12000)

800 parts by mass of C.I. Pigment Green 7, and 56 parts by mass of Solsperse 12000 as a pigment dispersing aid, 8000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 1000 parts by mass of diethylene glycol were premixed. The mixture is metered into a continuous single-axis kneading machine (Miracle) KCK-42, manufactured by Asada Iron Works Co., Ltd., was kneaded at 75 ° C for salt grinding. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 98 parts by mass of the fine particle-treated pigment 6.

(Microparticle-treated Pigment No. 7: C.I. Pigment Green 7 in a kneader treatment in the presence of a sulfonate of C.I. Pigment Yellow 138)

100 parts by mass of CI Pigment Green 7 and 7 parts by mass of a sulfonate of CI Pigment Yellow 138 as a pigment dispersing aid, and 1000 parts by mass of a particle size of 20 μm were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). The sodium chloride and 240 parts by mass of diethylene glycol were kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 98 parts by mass of the finely divided pigment 7 .

(Microparticle-treated pigment No. 8: C.I. Pigment Green 58 which was subjected to a kneader treatment in the presence of Solsperse 12000)

100 parts by mass of CI Pigment Green 58 and 7 parts by mass of Solsperse 12000 as a pigment dispersing aid, and 1000 parts by mass of sodium chloride having a particle diameter of 20 μm were placed in a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). 240 parts by mass of diethylene glycol was kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 97 parts by mass of the finely divided pigment 8 .

(Microparticle-treated pigment No. 9: C.I. Pigment Green 58 which was subjected to continuous uniaxial kneading in the presence of Solsperse 12000)

800 parts by mass of C.I. Pigment Green 58 and 56 parts by mass as a pigment dispersing aid Solsperse 12000, 8000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 1000 parts by mass of diethylene glycol were premixed. The mixture was quantitatively supplied to a continuous uniaxial kneading machine (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), and kneaded at 75 ° C to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 98 parts by mass of the fine particle-treated pigment 9.

<Coloring pigment which is micronized without using a pigment dispersing aid having a sulfonic acid group>

(Microparticle-treated pigment No. 10: C.I. Pigment Yellow 185 which was subjected to a kneader treatment in the absence of a pigment dispersing aid having a sulfonic acid group)

100 parts by mass of CI 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 placed in a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.) at 75 ° C. The salt milling treatment was carried out by kneading for 10 hours. Then, 1350 parts by mass of the obtained kneaded product was placed in 3 liters of warm water, and the mixture was stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the microparticulated pigment 10.

(Microparticle-treated pigment No. 11: C.I. Pigment Yellow 150 which was subjected to a kneader treatment in the absence of a pigment dispersing aid having a sulfonic acid group)

100 parts by mass of CI Pigment Yellow 150, 1000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 240 parts by mass of diethylene glycol were placed in a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.) at 75 ° C. The salt milling treatment was carried out by kneading for 10 hours. Then, 1350 parts by mass of the obtained kneaded product was placed in 3 liters of warm water, and the mixture was stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the microparticulated pigment 11.

(Microparticle-treated Pigment No. 12: C.I. Pigment Yellow 138 which was subjected to a kneader treatment in the absence of a pigment dispersing aid having a sulfonic acid group)

100 parts by mass of CI Pigment Yellow 138, 1000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 240 parts by mass of diethylene glycol were placed in a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.) at 75 ° C. The salt milling treatment was carried out by kneading for 10 hours. Then, 1350 parts by mass of the obtained kneaded product was placed in 3 liters of warm water, and the mixture was stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the microparticulated pigment 12 .

(Microparticle-treated Pigment No. 13: C.I. Pigment Green 7 which was subjected to a kneader treatment in the absence of a pigment dispersing aid having a sulfonic acid group)

100 parts by mass of CI Pigment Green 7, 1000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 240 parts by mass of diethylene glycol were placed in a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.) at 75 ° C. The salt milling treatment was carried out by kneading for 10 hours. Then, 1350 parts by mass of the obtained kneaded product was placed in 3 liters of warm water, and the mixture was stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the finely divided pigment 13 .

(Microparticle-treated Pigment No. 14: C.I. Pigment Green 58 which was subjected to a kneader treatment in the absence of a pigment dispersing aid having a sulfonic acid group)

100 parts by mass of CI Pigment Green 58 and 1000 parts by mass of sodium chloride having a particle diameter of 20 μm and 240 parts by mass of diethylene glycol were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.) at 75 ° C. The salt milling treatment was carried out by kneading for 10 hours. Then, 1350 parts by mass of the obtained kneaded product was placed in 3 liters of warm water, and the mixture was stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the fine particle-treated pigment 14.

(Microparticle-treated pigment No. 15: C.I. Pigment Green 36 which was subjected to kneading treatment in the presence of Solsperse 12000)

100 parts by mass of C.I. Pigment Green 36 and 7 parts by mass of Solsperse 12000 as a pigment dispersing aid were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). 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 carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the microparticulated pigment 15 .

(Microparticle-treated Pigment No. 16: C.I. Pigment Green 36 which was subjected to a kneader treatment in the presence of Solsperse 12000)

100 parts by mass of CI Pigment Green 36, 3.5 parts by mass of Solsperse 12000 as a pigment dispersing aid, and 1000 parts by mass of sodium chloride having a particle diameter of 20 μm were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.). 240 parts by mass of diethylene glycol was kneaded at 75 ° C for 10 hours to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 94 parts by mass of the finely divided pigment 16 .

(Microparticle-treated pigment No. 17: C.I. Pigment Green 36 which was subjected to continuous uniaxial kneading machine treatment in the presence of Solsperse 12000)

800 parts by mass of C.I. Pigment Green 36, 56 parts by mass of Solsperse 12000 as a pigment dispersing aid, 8000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 1000 parts by mass of diethylene glycol were premixed. The mixture was quantitatively supplied to a continuous uniaxial kneading machine (Miracle KCK-42, manufactured by Asada Iron Works Co., Ltd.), and kneaded at 75 ° C to carry out salt milling treatment. Then, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating to 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 97 parts by mass of the finely divided pigment 17 .

(Microparticle-treated Pigment No. 18: C.I. Pigment Green 36 which was subjected to a kneader treatment in the absence of a pigment dispersing aid having a sulfonic acid group)

100 parts by mass of CI Pigment Green 36, 1000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 240 parts by mass of diethylene glycol were placed in a tank of a kneading machine (trade name: KHD-2, manufactured by Inoue Seisakusho Co., Ltd.) at 75 ° C. The salt milling treatment was carried out by kneading for 10 hours. Then, 1350 parts by mass of the obtained kneaded product was placed in 3 liters of warm water, and the mixture was stirred while heating to 70 ° C for 1 hour to obtain a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 40 ° C to obtain 96 parts by mass of the microparticulated pigment 18 .

(Microparticle-treated Pigment No. 19: C.I. Pigment Yellow 185 which was not subjected to dispersion treatment in the absence of a pigment dispersing aid)

Prepare C.I. Pigment Yellow 185.

<Pigment dispersion composition for color filter>

Mixing the above-mentioned fine particle-treated pigments No. 1 to 18 or the microparticle-treated pigment No. 19 as C.I. Pigment Yellow 185, which is not subjected to microparticulation, as a composition of Table 2, A polymer pigment dispersant having a basic group, a pigment dispersing aid having a sulfonic acid group, an alkali-soluble resin (BMA/MAA copolymer), a photopolymerizable compound, an organic solvent (PGMEA), and a zirconia bead of 0.2 mmΦ is used. The mixture was kneaded by a paint adjuster for 6 hours to obtain a pigment dispersion composition for color filters 1 to 26.

<Pigment Dispersion Resist Composition for Color Filter>

Then, use a high-speed mixer to uniformly mix colors in a manner that becomes a component of Table 3. After the pigment dispersion compositions 1 to 26, BMA/MAA copolymer, DPEHA, Irgacure 369, and PGMEA are used for the filter, the membrane filter is filtered through a membrane having a pore size of 3 μm to obtain a pigment dispersion resist composition for a color filter. 1~26.

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

The composition selected from the pigment-dispersed resist compositions 1 to 26 for color filters was uniformly mixed so as to have a pigment ratio of Table 4, and color filters of Examples 1 to 11 and Comparative Examples 1 to 6 were obtained. The resist composition is dispersed with a green pigment.

(Evaluation) <Dispersion stability>

The green pigment-dispersed resist compositions for the color filters of Examples 1 to 11 and Comparative Examples 1 to 6 were collected into glass bottles, sealed, and stored at room temperature for 7 days, and then evaluated according to the following evaluation. Standards are evaluated. The results are shown in Table 1.

A: Viscosity and sediment were not confirmed.

B: It is confirmed that the viscosity or the precipitate is restored to the extent that it is gently oscillated.

C: It is confirmed that the viscosity or the precipitate is not restored even if it is strongly shaken.

<Evaluation of Color Characteristics of Green Pigment Dispersed Resist Composition for Color Filters>

The green color filter dispersion resist compositions of Examples 1 to 11 and Comparative Examples 1, 2, 4, and 5 were applied onto a glass substrate using a spin coater. Then, after prebaking at 100 ° C for 3 minutes, it was exposed by a high pressure mercury lamp, and then post-baked at 230 ° C for 30 minutes. Then, the colors of the resists of Examples 1 to 11 and Comparative Examples 1, 2, 4, and 5 were specifically The properties (x, y, Y) were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2° field of view). In Examples 1 to 11 and Comparative Examples 1, 2, 4, and 5, the film thickness and the lightness Y under the chromaticity x = 0.224 and y = 0.669 were determined.

According to the examples 1 to 11 which are examples of the present invention, it is understood that the pigment of the color filter for a color filter has good dispersibility of the pigment and a low value of Y, so that it is provided as a white organic EL light source. The appropriate optical properties of the color filter.

On the other hand, according to Comparative Examples 2, 3, 5, and 6 in which other pigments were used without using Pigment Yellow 185, since the values of x and y were the same as in the examples, the value of Y was also high, so that it could not be used as a white organic EL. A color filter for a light source is used as appropriate.

Further, according to Comparative Examples 1 and 4 in which the dispersing aid was not used, the dispersion stability of the pigment-colored resist composition for a color filter obtained was insufficient, and it was confirmed that the viscosity was not restored even if it was strongly shaken. Or sediment.

Claims (9)

A green coloring composition for a color filter, which is mainly composed of a color pigment, a pigment dispersing aid having an acid group, a polymer pigment dispersing agent having a basic group, a transparent resin, and an organic solvent. The coloring pigment includes a yellow pigment containing CI Pigment Green 7 and containing a green pigment of CI Pigment Green 36 and/or CI Pigment Green 58 and a CI Pigment Yellow 185, and the green coloring composition for the color filter can be used for A color filter for a display device of a white organic EL light source. The green coloring composition for a color filter according to claim 1, wherein the green coloring composition for the color filter is mainly composed of a color pigment, a pigment dispersing aid having an acid group, and a polymer pigment dispersing agent having a basic group. The transparent resin and the organic solvent are contained, and an alkali-soluble resin and a photopolymerizable compound are contained as the transparent resin. The color filter of claim 1 or 2, wherein the mass ratio of the green pigment to the yellow pigment is 95:5 to 40:60. The color filter of claim 1 or 2 is a green coloring composition which further contains barium sulfate having a primary particle diameter of 5 to 20 nm. The color filter of claim 1 or 2 is a green coloring composition, wherein the coloring pigment is a micronized pigment. A green coloring composition for a color filter according to claim 1 or 2, wherein the yellow pigment of CI Pigment Yellow 185 as the coloring pigment is subjected to salt milling treatment in the presence of a pigment-dispersing assistant having an acid group As a chemical treatment, CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 which are the above-mentioned coloring pigments are subjected to a salting treatment in the presence of a pigment dispersion aid having an acid group. The color filter of claim 1 or 2, wherein the acid group is a sulfonic acid group, using a green coloring composition. The color filter of claim 1 or 2, wherein the pigment dispersing aid having a sulfonic acid group for the above CI Pigment Green 7 is a sulfonate having a phthalocyanine skeleton and/or CI Pigment Yellow 138. The sulfonate, the sulfonate-containing pigment dispersing aid used for the above CI Pigment Green 36 is a sulfonate having a phthalocyanine skeleton, and the sulfonic acid group-containing pigment dispersing aid used for the above CI Pigment Green 58 has a hydrazine. A sulfonate of a cyanine skeleton, and a sulfonate-containing pigment dispersing aid used for the above pigment yellow 185 is a sulfonate of Pigment Yellow 185. A color filter comprising a display device of a white organic EL light source, comprising a coating layer formed by a green coloring composition for a color filter according to any one of claims 1 to 8.