TWI872016B - Pigment dispersion composition for color filter and resist composition for color filter - Google Patents

Abstract

The subject of the present invention is to improve the viscosity stability, PGMEA resolubility and developer solubility of the anti-corrosion agent composition for color filters when the anti-corrosion agent composition for color filters is prepared based on the color filter pigment dispersion composition. Specifically, the present invention provides a color filter pigment dispersion composition, which contains a coloring pigment, a pigment dispersing aid, an alkali-soluble resin and an organic solvent, wherein the alkali-soluble resin contains a block polymer.

Description

Pigment dispersion composition for color filter and anti-corrosion agent composition for color filter

The present invention relates to a pigment dispersion composition for a color filter and an anti-corrosion agent composition for a color filter.

In recent years, the development of color filters for high color reproduction has become more advanced, and the required performance of color filter pigment dispersion compositions and color filter anti-etching agent compositions has become more stringent. In pursuit of the quality of the color filter as the final product, the pigment dispersion composition contained in the anti-etching agent has also become more difficult to meet the process requirements. In particular, it has become difficult to achieve the coexistence of the opposite performance of improved solubility in propylene glycol monomethyl ether acetate (PGMEA) and improved solubility in alkaline developer. [Prior art literature] [Patent literature]

Patent document 1: Japanese Patent Application Publication No. 2017-142475

[Problem to be solved by the invention] The problem to be solved by the present invention is to improve the viscosity stability, PGMEA solubility and developer solubility of the anti-corrosion agent composition for color filters when the anti-corrosion agent composition for color filters is prepared based on the pigment dispersion composition for color filters. [Means for solving the problem]

In order to solve the above problems, the present invention studies the alkali-soluble resin contained in the pigment dispersion composition for color filters. Therefore, the present invention is composed of the following compositions. 1. A pigment dispersion composition for color filters, which contains a coloring pigment, a pigment dispersing aid, an alkali-soluble resin and an organic solvent, wherein the alkali-soluble resin contains a block polymer. 2. The pigment dispersion composition for color filters according to 1, wherein the photopolymerizable compound is contained. 3. The pigment dispersion composition for color filters according to 1 or 2, wherein the block polymer is contained in an amount of 1 to 200% by mass relative to the coloring pigment. 4. The pigment dispersion composition for color filters according to any one of 1 to 3, wherein the block polymer is synthesized by living polymerization. 5. A pigment dispersion composition for a color filter according to any one of 1 to 4, wherein the alkali-soluble site is localized in the block polymer molecule. 6. A pigment dispersion composition for a color filter according to any one of 1 to 5, wherein the acid value of the block polymer is 5 to 250 mgKOH/g. 7. A pigment dispersion anti-corrosion agent composition for a color filter, comprising the pigment dispersion composition for a color filter according to any one of 1 to 6. [Effect of the invention]

According to the present invention, when an anti-corrosion agent composition for a color filter is prepared based on a pigment dispersion composition for a color filter, the viscosity stability, PGMEA resolubility and developer solubility of the anti-corrosion agent composition for a color filter can be improved.

Hereinafter, the pigment dispersion composition for color filter and the anti-corrosion agent composition for color filter of the present invention will be described in detail.

The present invention mainly relates to a pigment dispersion composition for color filters and an anti-corrosion agent composition for color filters used in display devices. The pigment dispersion composition for color filters may be a composition other than an anti-corrosion agent. In any case, the pigment dispersion composition for color filters and the anti-corrosion agent composition for color filters of the present invention are compositions mainly used for color filters of display devices. As an effect brought about by them, when preparing the anti-corrosion agent composition for color filters, the viscosity stability, PGMEA resolubility and alkaline developer solubility of the anti-corrosion agent composition for color filters can be improved. When PGMEA has poor redissolubility, a dry film may be produced after applying the anti-corrosion agent liquid with a coating machine. When it is difficult to redissolve in PGMEA, the dry film may become a foreign body during subsequent processing. When the solubility of the alkaline developer is poor, that is, the solubility of the coating film relative to the alkaline developer is low or the coating film is not dissolved and peeled off, it may become difficult to form a pattern with excellent linearity during alkaline development. The present invention is a pigment dispersion composition for color filters and a pigment dispersion anti-corrosion agent composition for color filters formed by combining an alkali-soluble resin, a photopolymerizable compound, etc. with the pigment dispersion composition for color filters. Furthermore, the pigment dispersion composition for color filters includes a photocurable pigment dispersion composition and a non-photocurable pigment dispersion composition.

[A. Composition of the pigment dispersion composition for color filter] The pigment dispersion composition for color filter of the present invention is mainly composed of coloring pigment, pigment dispersing aid, alkali-soluble resin and organic solvent. The alkali-soluble resin may contain a block copolymer.

(Coloring pigments) Usable coloring pigments include various pigments such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, and brown pigments. In addition, as for their structures, in addition to organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazines, indanthresnes, and perylene pigments, inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, chromium yellow, red iron oxide, and chromium oxide can also be used. Examples of the above pigments are shown below.

As red pigment, it is C.I. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57: 2. 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 97, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 17 0, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 188, 190, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 230, 231, 23 2, 233, 235, 236, 237, 238, 239, 240, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.

Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 22, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 64, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among them, one or more of C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

The green pigment is one or more of C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55.

As yellow pigment, it is C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134 4. 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208.

The orange pigment is one or more of C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 51, 55, 59, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79.

The purple pigment is one or more of C.I. Pigment Purple 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, and 50.

In order to give high brightness and contrast to the pigment dispersion composition for the color filter of the present invention, it is preferred to use micronized pigments as the above-mentioned coloring pigments. By micronizing, the primary particle size of the coloring pigment can be made finer and more uniform. As the above-mentioned micronization treatment, for example, the following micronization treatment is preferably performed: a mixture containing an untreated coloring pigment, a water-soluble inorganic salt (such as sodium chloride, barium chloride, potassium chloride, etc., preferably sodium chloride, and the average particle size of the water-soluble inorganic salt used is preferably 50 μm or less) and a water-soluble dispersing medium (such as alkoxy alcohols, glycols, ethers, etc.) that does not substantially dissolve the above-mentioned water-soluble inorganic salt is kneaded by a kneader, a roll mill, a ball mill, an attritor, a sand mill, a planetary mixer described in Japanese Patent Application Publication No. 2006-192385, TRI-MIX (trade name) manufactured by Inoue Seisakusho Co., Ltd., a continuous single-shaft mixer, and a miracle mixer manufactured by Asada Iron Works Co., Ltd. After kneading by a kneading device such as KCK, a salt milling treatment is performed to remove the above-mentioned water-soluble inorganic salt and the above-mentioned water-soluble dispersion medium. Furthermore, from the viewpoint that the crystal growth of the coloring pigment can be suppressed and the pigment can be uniformly refined, it is preferred to perform the micronization treatment in the presence of a pigment dispersing aid described later. The amount of the pigment dispersing aid used at this time is 0.5 to 30 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the coloring pigment.

(Pigment dispersing aid) As a pigment dispersing aid used in the pigment dispersing composition for the color filter of the present invention, it is preferred to introduce an acidic group that can improve the affinity with organic solvents into the basic skeleton having the same or similar molecular structure as C.I. Pigment Blue 15:6 (ε copper phthalocyanine pigment), thereby preparing a pigment dispersing aid having an acidic group. Such a pigment dispersing aid has the effect of improving the micronization of the pigment during dispersion and the dispersion stability over time after dispersion, because part of the basic skeleton is adsorbed on the pigment surface during the process of micronizing and dispersing the pigment, and the acidic group can improve the affinity with organic solvents and pigment dispersing agents. In addition, the pigment dispersing aid itself is dissolved or dispersed in microparticles in the organic solvent, and is further preferred because it can be adsorbed in a wider range on the surface of the pigment. Among them, when a pigment dispersing aid having a sulfonic acid group is used as an acidic group, good results can be obtained. In the pigment dispersing composition for the color filter of the present invention, the amount of the pigment dispersing aid having an acidic group is 0.5 to 30 parts by mass relative to 100 parts by mass of the coloring pigment. When the content of the above-mentioned pigment dispersing aid having an acidic group is less than 0.5 parts by mass, the pigment dispersing effect is reduced. On the other hand, when it exceeds 30 parts by mass, the pigment dispersing effect is not further improved.

The pigment dispersing aid having an acidic group is, for example, as follows: (1) When a coloring pigment that has been micronized in the absence of a pigment dispersing aid having an acidic group is used, when the micronized coloring pigment is dispersed, 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, of the pigment dispersing aid having an acidic group is used relative to 100 parts by mass of the coloring pigment. (2) When using a coloring pigment that has been micronized in the presence of a pigment dispersing aid having an acidic group, 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, of the pigment dispersing aid is used relative to 100 parts by mass of the coloring pigment during the micronization process, and 0 to 29.5 parts by mass, preferably 0 to 12 parts by mass, of the pigment dispersing aid having an acidic group is used relative to 100 parts by mass of the coloring pigment during the dispersion of the micronized coloring pigment. Furthermore, the sum of the amount of the pigment dispersing aid with an acidic group used in the micronization treatment and the amount of the pigment dispersing aid with an acidic group used in the pigment dispersion of the micronized coloring pigment is 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, relative to 100 parts by mass of the coloring pigment. More specifically, the case of using a pigment dispersing aid with a sulfonic acid group as a pigment dispersing aid with an acidic group is described. When dispersing C.I. Pigment Blue 15:6 as a blue pigment, as described above, a pigment and/or a sulfonate of a pigment having an anthraquinone skeleton having the same skeleton as C.I. Pigment Blue 15:6 as an ε copper phthalocyanine pigment is used as a pigment dispersing aid.

(Polymer pigment dispersant) A polymer pigment dispersant can be added to the pigment dispersion composition for color filters of the present invention. As such a polymer pigment dispersant, a polymer pigment dispersant having a basic group that has been used in the field of color filters can be used. In the pigment dispersion composition for color filters of the present invention, the amount of the polymer pigment dispersant used is preferably 1 to 100 parts by mass, and more preferably 1 to 60 parts by mass, relative to 100 parts by mass of the coloring pigment. When the content of the above-mentioned polymer pigment dispersant is less than 1 part by mass, the pigment dispersion effect may be reduced. On the other hand, when it exceeds 100 parts by mass, there is a possibility that the developability may be reduced.

As polymer pigment dispersants having alkaline groups, for example, the following substances can be cited. (1) Reaction products of amino groups and/or imino groups of polyamine compounds (e.g., poly(lower) alkylene amines such as polyallylamine, polyvinylamine, and polyethylene polyimine) and at least one selected from polyesters, polyamides, and polyesteramides having free carboxyl groups. (2) Carbodiimide compounds having at least one side chain selected from polyester side chains, polyether side chains, and polypropylene side chains and an alkaline nitrogen-containing group in the molecule. (3) Reaction products of low molecular weight amino compounds such as poly(lower) alkylene imines and methyliminobispropylamine and polyesters having free carboxyl groups. (4) A reaction product obtained by reacting the isocyanate group of a polyisocyanate compound with alcohols such as methoxypolyethylene glycol, polyesters having one hydroxyl group such as caprolactone polyester, compounds having 2 to 3 isocyanate-reactive functional groups, and aliphatic or heterocyclic hydrocarbon compounds having isocyanate-reactive functional groups and tertiary amino groups in sequence. (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 amino group. (6) A reaction product obtained by adding a low molecular weight amino compound to a polyether chain. (7) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group. (8) A reaction product obtained by reacting a polyepoxide with a linear polymer having a free carboxyl group and an organic amine compound having one diamino group. (9) A reaction product obtained by reacting a polycarbonate compound having a functional group reactive with an amino group at one end thereof and a polyamine compound. (10) A copolymer of at least one methyl acrylate or acrylate selected from methyl methacrylate, ethyl methyl acrylate, propyl methyl acrylate, butyl methyl acrylate, stearyl methyl acrylate, benzyl methyl acrylate, methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, etc., and at least one polymerizable monomer containing a basic group such as acrylamide, methacrylamide, N-hydroxymethylamide, vinylimidazole, vinylpyridine, a monomer having an amino group and a polycaprolactone skeleton, and at least one polymerizable monomer selected from styrene, a styrene derivative, or other polymerizable monomers. (11) Acrylic block copolymers composed of blocks having alkaline groups such as tertiary amino groups and quaternary ammonium bases and blocks having no alkaline functional groups. (12) Pigment dispersants obtained by subjecting polyallylamine to a Michael addition reaction with a polycarbonate compound. (13) Carbodiimide compounds each having at least one polybutadiene chain and an alkaline nitrogen-containing group. (14) Carbodiimide compounds each having at least one side chain having an amide group and an alkaline nitrogen-containing group in the molecule. (15) Polyurethane compounds having constituent units containing ethylene oxide chains and propylene oxide chains and having amino groups quaternary ammonated by a quaternary ammonating agent. (16) Compounds obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in its molecule with an active hydrogen group of a compound having an active hydrogen group in its molecule and having an oxazole ring and/or an azobenzene skeleton, wherein the amount of the oxazole ring and the azobenzene skeleton is 15 to 85% relative to the total amount of the isocyanate group of the isocyanate compound having an isocyanurate ring and the carbamate bond and urea bond formed by the reaction of the isocyanate group with the active hydrogen group in the molecule of the compound, etc.

(Alkali-soluble resin) An alkali-soluble resin is added to the pigment dispersion composition for the color filter of the present invention. Such a resin acts as a binder for the pigment and is particularly preferably soluble in an alkaline developer used in the development process when manufacturing the color filter. Such an alkali-soluble resin needs to be a block copolymer. By using a block copolymer, the pigment dispersion ability is improved compared to other copolymers, and solubility in PGMEA or alkaline developer can be imparted. Among the block copolymers, block copolymers having carboxyl groups are preferred, and block copolymers having blocks composed of ethylenically unsaturated monomers having one or more carboxyl groups and blocks composed of other copolymerizable ethylenically unsaturated monomers are particularly preferred. Such block copolymers are not particularly limited, and conventionally used block copolymers can be used. Specifically, copolymers of at least one ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid and monomers and oligomers selected from styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methyl acrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methyl acrylate, cyclohexyl acrylate, cyclohexyl methyl acrylate, glyceryl monoacrylate, glyceryl methyl acrylate, N-phenylmaleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, carboepoxy diacrylate, etc., which are copolymerizable with the ethylenically unsaturated monomer having a carboxyl group. Among them, it is preferred not to use N-vinyl pyrrolidone or monomers containing sulfur elements. As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used. In addition, a block portion of a part of the block copolymer can be composed of a random copolymer. In addition, the alkali-soluble resin can also have a photopolymerizable functional group.

The acid value of the alkali-soluble resin in the present invention is preferably 5 to 250 mgKOH/g, more preferably 10 to 200 mgKOH/g, and more preferably 60 to 150 mgKOH/g from the perspective of developing properties. In the present invention, the acid value is a theoretical acid value, which is a value arithmetically calculated based on the ethylenically unsaturated monomer having a carboxyl group and its content. In addition, generally, from the perspective of developing properties and solubility in organic solvents, the weight average molecular weight of the alkali-soluble resin in the present invention is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and more preferably 7,000 to 20,000. In the present invention, the weight average molecular weight of the alkali-soluble resin is a weight average molecular weight based on polystyrene conversion obtained by GPC. In the present invention, Water 2690 (manufactured by Waters Corporation) is used as an apparatus, and PLgel 5μm MIXED-D (manufactured by Agilent Technologies Corporation) is used as a chromatographic column. The amount of the alkali-soluble resin used in the present invention is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the coloring pigment used. At this time, when the amount of the alkali-soluble resin used is less than 1 part by mass, there is a possibility that the developing characteristics are reduced. On the other hand, when it exceeds 200 parts by mass, since the coloring agent concentration is relatively reduced, there is a possibility that it is difficult to achieve the target color density as a film. In addition, as an alkali-soluble resin, it does not contain any amino group of the primary amino group, the secondary amino group, and the tertiary amino group, and it is further preferred that it does not contain a quaternary ammonium group. It is further preferred that it does not have a basic group. Also, within the scope of not impairing the effects brought about by the present invention, an alkali-soluble resin having a structure other than a block copolymer may be added.

(Other resins) As the resin used in the pigment dispersion composition for color filters of the present invention, resins 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 can be used. As these resins, thermosetting resins, thermoplastic resins, alkali-soluble resins, and the following photopolymerizable compounds can be used. The total amount of such resins used is preferably in the range of 5 to 94% by mass, more preferably 20 to 50% by mass, based on the total solid content of the pigment dispersion composition for color filters. Examples of thermosetting resins and thermoplastic resins include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, phenolic resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclic rubbers, epoxy resins, cellulose resins, polybutadiene, polyimide resins, benzoguanamine resins, melamine resins, urea resins, and the like. In addition, the photopolymerizable resin described below may be added to the color filter pigment dispersion anticorrosive composition as appropriate.

(Organic Solvent) As the organic solvent used in the color filter pigment dispersion composition of the present invention, organic solvents conventionally used in the field of anti-corrosion agents for liquid crystal color filters can be suitably used. Specifically, ester organic solvents, ether organic solvents, ether ester organic solvents, ketone organic solvents, aromatic hydrocarbon organic solvents, nitrogen-containing organic solvents, etc., having a boiling point of 100 to 220°C at normal pressure (1.013×10 ² kPa). When a large amount of an organic solvent having a boiling point exceeding 220°C is contained, when a coating film formed by coating a color filter pigment dispersion composition or a composition containing the composition is pre-baked, the organic solvent cannot be fully evaporated and remains in the dried coating film, and the heat resistance of the dried coating film may be reduced. In addition, when a large amount of an organic solvent having a boiling point below 100°C is contained, it is difficult to apply uniformly without unevenness, and there is a possibility that a coating film with excellent surface smoothness cannot be obtained.

Examples of the organic solvent used in the pigment dispersion composition for the color filter of the present invention include, specifically, ether organic solvents such as 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 monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; and ether ester organic solvents 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. ; Ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone, etc.; Ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-pentyl formate, etc.; Alcohol solvents such as methanol, ethanol, isopropanol, butanol, etc.; Nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These can 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, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-pentyl formate, etc. are preferred in terms of solubility, dispersibility, and coating properties, and propylene glycol monomethyl ether acetate is more preferred.

(Barium sulfate) In order to improve the heat resistance (brightness) of the pigment dispersion composition for the color filter of the present invention, barium sulfate having a primary particle size of 5 to 20 nm can be used. The amount of barium sulfate used is 0 to 25 parts by mass relative to 100 parts by mass of the coloring pigment, preferably 5 to 20 parts by mass. The above-mentioned barium sulfate is used during or after the dispersion of the micronized coloring pigment.

The pigment dispersion composition for color filter of the present invention is mainly composed of coloring pigment, pigment dispersing aid, resin and organic solvent, and the above components account for 90-100% by weight of the pigment dispersion composition for color filter. In addition, a polymer pigment dispersant can be further added, and any of the above substances can be used as such a polymer pigment dispersant. In addition, the pigment dispersion composition for color filter of the present invention can also be used as an anti-corrosion agent composition in a state without photocurability.

(Additives that can be added as needed) Depending on the method for producing the pigment dispersion composition for color filters, various additives such as photopolymerization initiators, heat-resistant polymerization agents, ultraviolet light absorbers, antioxidants, etc. can be used appropriately. Examples of the above-mentioned photopolymerization initiators include the following substances.

(Method for producing the pigment dispersion composition for color filter of the present invention) The method for producing the pigment dispersion composition for color filter using the above raw materials is described. In addition, in the case of a non-photocurable pigment dispersion anti-corrosion agent composition for color filter, it is not necessary to add a photopolymerizable compound. Therefore, first, a pigment dispersion composition is prepared as described below. A mixture consisting of a pigment micronized in the presence or absence of a pigment dispersing aid, a resin, a polymer pigment dispersant as required, an organic solvent, barium sulfate, and other additives as required is obtained. The obtained mixture is kneaded and dispersed using various dispersers such as a roller mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure disperser, etc. to obtain a pigment dispersion composition.

When multiple pigments are used together, the following method can be adopted. (1) A pigment dispersion composition of each pigment is obtained in advance, the above-mentioned pigment dispersion composition is mixed in an arbitrary ratio, and then a resin, barium sulfate, an organic solvent, and other additives are added as needed to produce the pigment dispersion composition for the color filter of the present invention. (2) A process of mixing a color-correcting pigment as needed in the pigment dispersion composition produced as described above to make it a prescribed ratio is performed in advance, and then a resin, barium sulfate, an organic solvent, and other additives are added as needed to produce a pigment dispersion composition. Regarding the pigment dispersion composition containing other pigments, the pigment dispersion composition for the color filter of the present invention is also produced by the process of mixing the pigment dispersion composition after the pigment dispersion composition is produced. In addition, a resin, barium sulfate, an organic solvent, or other additives may be added to the color filter pigment dispersion composition obtained by (1) and (2) as needed to prepare a color filter pigment dispersion composition. Then, a color-correcting pigment is mixed with the prepared color filter pigment dispersion composition in a predetermined ratio relative to the pigment contained therein, thereby obtaining a color filter pigment dispersion composition.

In the production methods of (1) and (2), when a micronized pigment that has been micronized in the presence of a pigment dispersing aid having an acidic group is used, the micronized pigment may be produced without containing the pigment dispersing aid having an acidic group during dispersion. In addition, in the production methods of (1) and (2), the resin and barium sulfate may be added during and/or after the pigment dispersion composition is prepared. In addition, in the production methods of (1) and (2), it is preferred to use a pigment that has been micronized in the presence of a pigment dispersing aid having an acidic group from the viewpoint of obtaining high coloring power and high brightness.

At present, as a method for manufacturing a color filter using a color filter pigment dispersion anti-etching agent composition, the main method is a photoresist method using a photocurable composition. Hereinafter, the color filter is divided into a photocurable pigment dispersion composition for a color filter used in the photoresist method and a non-photocurable pigment dispersion composition for a color filter different from the above, and the components contained in each are explained below.

The total amount of such resins used is preferably in the range of 5 to 94 mass %, more preferably 20 to 50 mass %, based on the total solid content of the pigment dispersion composition for color filters.

[B. Case where the pigment-dispersed anti-corrosion agent composition for color filters is photocurable] Next, the case where the pigment-dispersed anti-corrosion agent composition for color filters of the present invention is photocurable is described. When the pigment-dispersed anti-corrosion agent composition for color filters of the present invention is photocurable, the composition has active energy ray curability and is an anti-corrosion agent composition that can be alkaline developed, and is mainly composed of a pigment, a pigment dispersing aid, a resin, and an organic solvent, and contains barium sulfate as a photopolymerizable compound of the resin, and may further contain an alkali-soluble resin. The types and amounts of the pigment, pigment dispersing aid, polymer pigment dispersing agent, resin other than the photopolymerizable compound, barium sulfate and organic solvent used are the same as those described for the pigment dispersion composition for the color filter.

Furthermore, regarding the organic solvent, from the viewpoints of the solubility of the above-mentioned alkali-soluble resin, the dispersibility of the coloring pigment, the coating property, etc., it is preferably contained in the color filter pigment dispersion anti-corrosion agent composition of the present invention in an amount of 50 mass % or more, and more preferably 70 mass % or more.

(Photopolymerizable compound) As the photopolymerizable compound used in the pigment dispersion anti-corrosion agent composition for color filters of the present invention, the same photopolymerizable compounds as those described in the above-mentioned pigment dispersion composition for color filters, such as monomers, oligomers, photopolymerizable resins, etc., having one or more photopolymerizable unsaturated bonds in the molecule can be used. Monomers, oligomers, etc. having photopolymerizable unsaturated bonds refer to monomers and oligomers having unsaturated bonds that can be polymerized and resinified by the action of free radicals and cations generated when the photopolymerization initiator described later is decomposed by active energy rays such as ultraviolet rays and electron rays. As the photopolymerizable compound, as the monomer having one photopolymerizable unsaturated bond in the molecule, there can be exemplified alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc.; aralkyl methacrylates or acrylates such as benzyl methacrylate, benzyl methacrylate, etc.; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate, butoxyethyl methacrylate, etc.; N , aminoalkyl methyl acrylate or acrylate such as N-dimethylaminoethyl methyl acrylate, N,N-dimethylaminoethyl acrylate, etc.; methyl acrylate or acrylate of polyalkylene glycol alkyl ether such as diethylene glycol ethyl ether, triethylene glycol butyl ether, dipropylene glycol methyl ether, etc.; methyl acrylate or acrylate of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether, etc.; isobornyl methyl acrylate or acrylate; glyceryl methyl acrylate or acrylate; 2-hydroxyethyl methyl acrylate or acrylate, etc. Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule of the photopolymerizable compound include bisphenol A methyl diacrylate, 1,4-butanediol methyl diacrylate, 1,3-butanediol methyl diacrylate, diethylene glycol methyl diacrylate, glyceryl methyl diacrylate, neopentyl glycol methyl diacrylate, polyethylene glycol methyl diacrylate, polypropylene glycol methyl diacrylate, tetraethylene glycol methyl diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol methyl triacrylate, pentaerythritol methyl tetraacrylate, dipentaerythritol methyl tetraacrylate, Dipentaerythritol methyl hexaacrylate, dipentaerythritol methyl pentaacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glyceryl diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. These monomers can be used alone or in combination of two or more. In addition, oligomers obtained by polymerizing photopolymerizable compounds can be used. As a photopolymerizable resin of a photopolymerizable compound, a resin having a photocrosslinkable group such as a (meth)acrylic acid compound or cinnamic acid introduced into a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group via an isocyanate group, an aldehyde group, an epoxy group, or the like can be used. A polymer in which a linear polymer containing anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth)acrylic acid compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate can also be used. The photopolymerizable compound that can form the above resin can be used alone or in combination of two or more. In the present invention, the amount of the photopolymerizable compound used is preferably in the range of 3 to 50% by mass relative to the total solid content in the pigment-dispersed anti-corrosion agent composition for color filters in terms of mass fraction.

(Photopolymerization initiator) The photopolymerization initiator used in the pigment dispersion anti-corrosion agent composition for the color filter of the present invention is not particularly limited as long as it can generate free radicals and cations by irradiating active energy rays such as ultraviolet rays and electron rays. Examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzoyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxy isobutyl benzophenone, thiothione, 2-chlorothiothione, 1-hydroxycyclohexyl benzophenone, tertiary butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzathraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, triazine-based photopolymerization initiators, etc. These photopolymerization initiators can be used alone 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 mass % based on the total solid content in the color filter pigment dispersion anti-corrosion agent composition.

The pigment dispersion anti-corrosion agent composition for color filter of the present invention mainly consists of coloring pigment, pigment dispersion aid, polymer pigment dispersant, alkali soluble resin, photopolymerizable compound, photopolymerization initiator, barium sulfate and organic solvent, and the above components together account for 90-100% by mass in the pigment dispersion anti-corrosion agent composition for color filter.

(Additives that can be added as needed) When the pigment dispersion anti-corrosion agent composition for the color filter of the present invention is photocurable, various additives such as heat-resistant polymerization agents, ultraviolet absorbers, antioxidants, etc. can be appropriately used as needed.

[C. When the pigment dispersion anti-corrosion agent composition for color filters is non-photocurable] When the pigment dispersion anti-corrosion agent composition for color filters is non-photocurable, it does not contain the photopolymerizable compound and photopolymerization initiator used in the above B. When the pigment dispersion anti-corrosion agent composition for color filters is photocurable, and a resin other than the photopolymerizable compound shown in the composition description of the above pigment dispersion composition for color filters can be further added as needed.

(Additives that can be added as needed) When the pigment dispersion anti-corrosion agent composition for the color filter of the present invention is non-photocurable, various additives such as ultraviolet absorbers and antioxidants can be appropriately used as needed.

(Method for producing the pigment dispersion anti-corrosion agent composition for color filters of the present invention) The method for producing the pigment dispersion anti-corrosion agent composition for color filters using the above materials is described. When the pigment dispersion anti-corrosion agent composition for color filters is photopolymerizable, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin as required, barium sulfate, an organic solvent, and other additives are further added to the pigment dispersion anti-corrosion agent composition for color filters obtained above, thereby obtaining the pigment dispersion anti-corrosion agent composition for color filters of the present invention. In addition, when it is non-photopolymerizable, any one of an alkali-soluble resin, barium sulfate, an organic solvent, and other additives can be further added to obtain the pigment dispersion anti-corrosion agent composition for the color filter of the present invention. The same is true in the above-mentioned manufacturing method. Specifically, for example, it can be obtained by the above-mentioned manufacturing methods (1) and (2). In addition, as a method for manufacturing a color filter using the pigment dispersion composition for the color filter of the present invention, a method including the necessary apparatus and the structure other than the pigment dispersion composition can be adopted to manufacture it. [Example]

The present invention is further described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition, unless otherwise stated, "%" means "mass %" and "part" means "mass part".

＜Pigment dispersant＞ Phthalocyanine derivative: DISPER BYK-2100 (manufactured by Beck Chemical Co., Ltd.) ＜Alkaline soluble resin＞ ZAH110: manufactured by Soken Chemical Co., Ltd., acid value: 100 mgKOH/g, weight average molecular weight: about 15,000, solid content 35% by mass ＜Photopolymerizable compound＞ DPHA: dipentaerythritol hexaacrylate ＜Organic solvent＞ PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether

Based on the formulation shown in Table 1 below, a pigment dispersion composition for a color filter was obtained. Table 1

MMA: methyl methacrylate BMA: butyl methacrylate NPM: N-phenylmaleimide MAA: methacrylic acid

(Preparation of alkali-soluble resin solution 1) In a flask, add 3g of MMA, 5g of BMA, 2g of MAA, and 1200mg of AIBN, stir and degas. Next, add 10g of benzene and stir while filling with dry nitrogen. After reacting in a 60°C hot water bath for 24 hours, immerse in a dry ice methanol bath to stop the reaction. Dilute with the same amount of benzene and inject into 300ml of methanol to precipitate the generated resin. Collect the resin with filter paper and wash it several times with methanol, and dry it under reduced pressure at 60°C. The obtained resin (random copolymer of MMA, BMA and MAA) was added to a solvent of PGMEA/PGME=2/1 to obtain an alkali-soluble resin solution 1.

(Preparation of alkali-soluble resin solution 2) In a flask, add 3g of MMA, 5g of BMA, 2g of MAA, and 1700mg of AIBN, stir and degas. Next, add 10g of benzene and stir while filling with dry nitrogen. After reacting in a 60°C hot water bath for 24 hours, immerse in a dry ice methanol bath to stop the reaction. Dilute with the same amount of benzene and inject into 300ml of methanol to precipitate the generated resin. Collect the resin with filter paper and wash it several times with methanol, and dry it under reduced pressure at 60°C. The obtained resin (random copolymer of MMA, BMA and MAA) was added to a PGMEA solvent to obtain an alkali-soluble resin solution 2.

(Preparation of alkali-soluble resin solution 3) In a flask, add 3g of NPM, 3g of MMA, 2g of BMA, 2g of MAA, and 1200mg of AIBN, stir and degas. Next, add 10g of benzene and stir while filling with dry nitrogen. After reacting in a 60°C hot water bath for 24 hours, immerse in a dry ice methanol bath to stop the reaction. Dilute with the same amount of benzene and inject into 300ml of methanol to precipitate the generated resin. Collect the resin with filter paper and wash it several times with methanol, and dry it under reduced pressure at 60°C. The obtained resin (random copolymer of NPM, MMA, BMA and MAA) was added to a solvent of PGMEA/PGME=2/1 to obtain an alkali-soluble resin solution 3.

(Preparation of alkali-soluble resin solution 4) In a degassed glass apparatus, 30 g of MMA, 30 g of BMA, and 1 L of THF were added, and 4.5 mmol of n-butyl lithium hexane solution was added (here, the random copolymer of MMA and BMA was synthesized). Then, it was cooled to -78°C and stirred for 2 hours. Next, 20 g of MAA was added to synthesize the block part of MAA in which the random copolymer of MMA and BMA was partially bonded, and then 20 g of BMA was added to further bond the block copolymer part of BMA, and the reaction was stopped after stirring for 2 hours. The solution at the end of the synthesis was added dropwise to a large amount of methanol to precipitate. The resin was collected with filter paper and washed several times with methanol, and then dried under reduced pressure at 60°C. The obtained resin was added to a solvent of PGMEA/PGME=2/1 to obtain an alkali-soluble resin solution 4.

(Preparation of alkali-soluble resin solution 5) In a degassed glass apparatus, 30 g of MMA, 30 g of BMA, and 1 L of THF were added, and a 2.0 mmol hexane solution of n-butyl lithium was added (here, the random copolymer of MMA and BMA was synthesized). Then, the mixture was cooled to -78°C and stirred for 2 hours. Next, 20 g of MAA was added to synthesize a block polymer of MAA bonded to the random copolymer of MMA and BMA, and then 20 g of BMA was added to further bond the block copolymer of BMA. The reaction was stopped after stirring for 2 hours. The solution at the end of the synthesis was added dropwise to a large amount of methanol to precipitate. The resin was collected with filter paper and washed several times with methanol, and then dried under reduced pressure at 60°C. The obtained resin was added to a solvent of PGMEA/PGME=1/1 to obtain an alkali-soluble resin solution 5.

(Production of alkali-soluble resin solution 6) In a degassed glass apparatus, 30 g of MMA, 30 g of NPM, and 1 L of THF were added, and 4.5 mmol of n-butyl lithium hexane solution was added (here, the random copolymer of MMA and NPM was synthesized). Then, the mixture was cooled to -78°C and stirred for 2 hours. Next, 20 g of MAA was added to synthesize the block copolymer of MAA bonded to the random copolymer of MMA and NPM, and then 20 g of BMA was added to further bond the block copolymer of BMA, and the reaction was stopped after stirring for 2 hours. The solution at the end of the synthesis was added dropwise to a large amount of methanol to precipitate. The resin was collected with filter paper and washed several times with methanol, and then dried under reduced pressure at 60°C. The obtained resin was added to a solvent of PGMEA/PGME=2/1 to obtain an alkali-soluble resin solution 6.

(Preparation of alkali-soluble resin solution 7) In a degassed glass apparatus, 30 g of MMA, 50 g of BMA, and 1 L of THF were added, and 4.5 mmol of n-butyl lithium hexane solution was added (here, the random copolymer of MMA and BMA was synthesized). Then, the mixture was cooled to -78°C and stirred for 2 hours. Next, 20 g of MAA was added to synthesize the block polymer of MAA bonded to the random copolymer of MMA and BMA, and then the reaction was stopped after stirring for 2 hours. The solution at the end of the synthesis was added dropwise to a large amount of methanol to precipitate. The resin was collected with filter paper and washed several times with methanol, and then dried under reduced pressure at 60°C. The obtained resin was added to a solvent of PGMEA/PGME=2/1 to obtain an alkali-soluble resin solution 7.

Table 2

The red pigment dispersion compositions for color filters of Examples A1 to A4 and Comparative Examples A1 to 3 were mixed to form a composition consisting of the components shown in Table 2, and the mixture was kneaded for 6 hours using 0.2 mm Φ zirconia beads in a paint conditioner to obtain the composition.

Table 3

The red pigment dispersion composition and other materials were uniformly mixed with a high-speed stirrer to form the composition shown in Table 2, and then filtered with a membrane filter having a pore size of 3 μm to obtain a pigment dispersion anti-corrosion agent composition for color filters. <Preparation of samples> The red pigment dispersion anti-corrosion agent composition for color filters of the embodiment and the comparative example was applied to a glass substrate using a spreader. Then, the sample was prepared by pre-baking at 100°C for 3 minutes and then exposed with a high-pressure mercury lamp.

<Color characteristics and contrast> For the samples of the embodiments and comparative examples, the color characteristics (x, y, Y) of each anti-corrosion agent were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2° viewing angle). The y, brightness Y, and contrast at chromaticity x=0.600 were obtained.

<Initial viscosity> The viscosity at 25°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., R100 type viscometer, model number RE100L).

<Viscosity stability> Regarding the pigment dispersion composition for color filters used in the anti-corrosion agent method of the above-mentioned embodiment and comparative example, each was collected in a glass bottle and sealed, and the state after being stored at 40°C, 5°C and room temperature (23°C) for 1 month was evaluated according to the following evaluation standards. ○: The viscosity change rate before and after storage is less than 10% ×: The viscosity change rate before and after storage exceeds 10%

<PGMEA re-dissolution test> The pigment dispersion anti-corrosion agent composition was applied to the glass substrate using a spreader. Then, it was pre-baked at 100°C for 3 minutes and then immersed in PGMEA, and the dissolution state was visually evaluated.

<Developer solubility test> The pigment dispersion anti-corrosion agent composition was applied to a glass substrate using a spreader. Then, it was pre-baked at 100°C for 3 minutes and then immersed in 0.05wt% KOH alkali, and the dissolution state was visually evaluated.

According to the results of each embodiment, the anti-corrosion agent composition can be surely dissolved by the re-solubility brought by PGMEA, while according to the results of each comparative example, the anti-corrosion agent composition cannot be re-solubilized and remains at the level of strong or weak peeling. As a result, according to the pigment dispersion composition for color filter of the present invention, the viscosity stability, PGMEA re-solubility and developer solubility of the anti-corrosion agent composition for color filter can be comprehensively improved. It can be seen that the patterning performance is excellent when the anti-corrosion agent composition is prepared.

Claims (6)

A pigment dispersion composition for color filters, comprising a coloring pigment, a pigment dispersing aid, an alkali-soluble resin and an organic solvent, wherein the content of the alkali-soluble resin is 1 to 200 parts by mass relative to 100 parts by mass of the coloring pigment, the alkali-soluble resin comprises a block polymer synthesized by living polymerization, does not contain any amino group of primary amino group, secondary amino group and tertiary amino group, and the alkali-soluble resin is a resin that does not contain a quaternary ammonium group. The pigment dispersion composition for color filter as described in Item 1 of the patent application further contains a photopolymerizable compound. The pigment dispersion composition for color filters as described in item 1 or 2 of the patent application, wherein the block polymer is contained in an amount of 1 to 200 mass % relative to the coloring pigment. A pigment dispersion composition for a color filter as described in item 1 or 2 of the patent application, wherein the alkali-soluble site is localized in the block polymer molecule. As described in item 1 or 2 of the patent application scope, the pigment dispersion composition for color filter, wherein the acid value of the block polymer is 5~250mgKOH/g. A pigment dispersion anti-corrosion agent composition for color filters, comprising a pigment dispersion composition for color filters as described in any one of items 1 to 5 of the patent application scope.