JP2010095693A - Organic pigment microparticle, method for manufacturing the same, pigment-dispersed composition containing the same, photocurable composition, inkjet ink, color filter using them and method for manufacturing the same - Google Patents

Abstract

An organic pigment fine particle capable of improving the characteristics of a color filter used in a liquid crystal display device and the like and a method for producing the same.
Self-dispersible organic pigment fine particles having an organic pigment and a polymer compound, the organic pigment fine particles comprising an organic pigment solution in which the organic pigment and the polymer compound are dissolved in a first solvent; The second solvent is a nanometer-sized fine particle which is mixed with a second solvent which becomes a poor solvent for the organic pigment and is compatible with the first solvent, and is precipitated in the mixed solution. Organic pigment fine particles that can be self-dispersed in a third solvent different from both the first solvent and the second solvent by using a compound insoluble in water.
[Selection figure] None

Description

  The present invention relates to organic pigment fine particles and a method for producing the same, a pigment dispersion composition containing the same, a photocurable composition, an inkjet ink, a color filter using them, and a method for producing the same.

  Color filters used in cutting-edge image-related equipment such as liquid crystal color displays and video cameras are precision members in which red (R), green (G), and blue (B) colored pixel portions are formed on a substrate. is there. Each of these colored pixel portions has a fine structure in which a thin film of resin in which an organic pigment of each color is dispersed is provided on a substrate so that a predetermined color display is reproduced. Then, the photocurable pigment composition used to form the colored pixel portion is obtained by adding a resin or the like to the pigment dispersion in which the organic pigment is dispersed and the photocurable compound as necessary. It is prepared by adjusting chemical properties.

  In order to satisfy the demand as a precision member used in the image-related equipment as described above, extremely high member characteristics are required. Color filters are also required to have high performance and high quality, and attempts have been made to improve organic pigments used in the production thereof. Specifically, in preparation of the pigment dispersion composition, those having excellent storage stability and those having excellent contrast of the coating film of the color filter colored pixel portion using the pigment dispersion composition are required.

  For this purpose, for example, pigment particles are reduced in size to a range of 10 to 100 nm, and research for applying them to various uses has been vigorously advanced. This is an attempt to bring out new characteristics that could not be predicted in the past due to the effects that are manifested for the first time by the nanometer size. For example, research and development of paints, printing inks, electrophotographic toners, ink jet inks, color filters, etc. are underway. Especially, the above-mentioned color filters and ink jet inks have improved performance using fine chemical technology. Efforts are made and the results are expected.

  Here, regarding the dispersion method of organic pigments, there are various milling methods (breakdown method) such as bead mill method and salt milling method, and liquid phase method. It is difficult to disperse with (see Patent Document 1). The liquid phase method is suitable for obtaining fine pigment particles. Specifically, a pigment solution obtained by dissolving a pigment in a good solvent (first solvent) and a poor solvent (second solvent) are mixed to form nanoparticles. A method of precipitating and adding a predetermined polymer compound has been proposed (see Patent Documents 2 to 5). However, in the above prior art, the first solvent and the second solvent are efficiently removed, the pigment fine particles produced in the third solvent different from these are sufficiently redispersed, and the fine particles produced with respect to the third solvent are dispersed. Providing spontaneous dispersibility (self-dispersibility) is not disclosed. For example, in Patent Document 5, polyvinyl pyrrolidone is dissolved in a pigment solution to form particles, but this is soluble in an aqueous medium used as the second solvent (poor solvent). It is difficult to take out the polymer from the fine particle dispersion obtained by mixing the second solvent. In order to disperse the pigment fine particles in the new third solvent, it is usually necessary to add a dispersant other than the polymer.

JP 2000-239554 A International Publication No. WO2006 / 121016 Pamphlet JP 2004-43776 A JP 2007-119586 A JP 2007-23169 A

  An object of the present invention is to provide organic pigment fine particles capable of improving the characteristics of a color filter used in a liquid crystal display device and the like, and a method for producing the same. In particular, organic pigment fine particles capable of increasing the contrast of color filters, improving the manufacturing quality, manufacturing efficiency, and environmental compatibility, and realizing good display characteristics in a liquid crystal display device, and a method for manufacturing the same are obtained. An object is to provide a dispersion composition, a photocurable composition, an inkjet ink, a color filter using them, and a method for producing the same.

（式中、Ｒ^１は水素原子またはメチル基を表す。Ｊは−ＣＯ−、−ＣＯＯ−、−ＣＯＮＲ^６−、−ＯＣＯ−、フェニレン基、または−Ｃ_６Ｈ_４ＣＯ−基を表し、Ｒ^６は水素原子、アルキル基、アリール基、またはアラルキル基を表す。Ｗ^１は、直鎖，分岐，もしくは環状のアルキレン基、アラルキレン基、または単結合を表す。Ｐは複素環基を表す。）
（６）前記高分子化合物が、さらに下記一般式（２）または（３）で表される繰り返し単位を有することを特徴とする（１）〜（５）のいずれか１項に記載の有機顔料微粒子。

（Ｒ^１は水素原子またはメチル基を表す。Ｙは−ＮＨ−、−Ｏ−、または−Ｓ−を表す。Ｗ^２は単結合または２価の連結基を表す。Ｐは複素環基をあらわす。）
（７）前記一般式（１）、（２）、または（３）中のＰが、一般式（４）またはその互変異性体構造で表されることを特徴とする（５）または（６）に記載の有機顔料微粒子。

（Ｒ^２は、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、または水素原子を表す。Ｒ^３は、水素原子、アルキル基、アリール基、ハロゲン原子、またはアゾ基を表す。）
（８）前記高分子化合物が、末端にエチレン性不飽和２重結合を有する重合性オリゴマーがなす側鎖を有するグラフト共重合体であることを特徴とする（１）〜（７）のいずれか１項に記載の有機顔料微粒子
（９）
前記有機顔料溶液中に、さらに塩基性基もしくは酸性基を有する有機化合物を少なくとも１種以上含有させたことを特徴とする（１）〜（８）のいずれか１項に記載の有機顔料微粒子。
（１０）前記有機顔料溶液と第２溶媒とを、下式（１）で表されるレイノルズ数Ｒｅが５０以上となる条件下で混合したことを特徴とする（１）〜（９）のいずれか１項に記載の有機顔料微粒子。
Ｒｅ＝ρＵＬ／μ ・・・ （１）
［数式（１）中、Ｒｅはレイノルズ数を表し、ρは有機顔料溶液の密度を表し、Ｕは有機顔料溶液と第２溶媒とが出会うときの相対速度を表し、Ｌは有機顔料溶液と第２溶媒とが出会う部分の流路もしくは供給口の等価直径を表し、μは有機顔料溶液の粘性係数を表す。］
（１１）前記第１溶媒が、有機酸、有機塩基、スルホキシド化合物溶媒、及びアミド化合物溶媒よりなる群から選択される少なくとも１種以上であることを特徴とする（１）〜（１０）のいずれか１項に記載の有機顔料微粒子。
（１２）前記第２溶媒が水性媒体及びアルコール化合物溶媒よりなる群から選択される少なくとも１種以上であることを特徴とする（１）〜（１１）のいずれか１項に記載の有機顔料微粒子。
（１３）前記第３の溶媒が、エーテル化合物溶媒、エステル化合物溶媒、芳香族炭化水素化合物溶媒、及び脂肪族炭化水素化合物溶媒よりなる群から選択される少なくとも１種以上の溶媒であることを特徴とする（１）〜（１２）のいずれか１項に記載の有機顔料微粒子。
（１４）前記有機顔料溶液中に、前記高分子化合物を前記有機顔料１００質量部に対して１０〜３００質量部含有させたことを特徴とする請求項１〜１３のいずれか１項に記載の有機顔料微粒子。
（１５）第１溶媒に有機顔料および高分子化合物を溶解した有機顔料溶液と、前記有機顔料に対して貧溶媒となり前記第１溶媒と相溶する第２溶媒とを混合し、その混合液中に前記有機顔料と前記高分子化合物とを有するナノメートルサイズの微粒子を析出させるに当たり、前記高分子化合物として前記第２溶媒に対して不溶性の化合物を用い、前記微粒子を前記第１溶媒及び第２溶媒のいずれとも異なる第３の溶媒に自己分散しうるものとすることを特徴とする有機顔料微粒子の製造方法。
（１６）（１）〜（１４）のいずれか１項に記載の有機顔料微粒子を前記第３の溶媒に自己分散させたことを特徴とする顔料分散組成物。
（１７）さらに、顔料分散剤を含有させたことを特徴とする（１６）に記載の顔料分散組成物。
（１８）（１６）または（１７）に記載の顔料分散組成物と、光重合性化合物と、光重合開始剤とを含有させたことを特徴とする光硬化性組成物。
（１９）さらに、アルカリ可溶性樹脂を含有させたことを特徴とする（１８）に記載の光硬化性組成物。
（２０）カラーフィルタ用であることを特徴とする（１８）又は（１９）に記載の光硬化性組成物。
（２１）基板上に、（１８）〜（２０）のいずれか１項に記載の光硬化性組成物を用いて形成した着色パターンを有することを特徴とするカラーフィルタ。
（２２）（１８）〜（２０）のいずれか１項に記載の光硬化性組成物を直接もしくは所定の層を介して基板上に付与して感光性膜を形成する感光性膜形成工程と、形成された感光性膜にパターン露光及び現像を順次行なうことにより着色パターンを形成する着色パターン形成工程とを有することを特徴とするカラーフィルタの製造方法。
（２３）重合性モノマーおよび／または重合性オリゴマーを含む媒体に、（１）〜（１４）のいずれか１項に記載の有機顔料微粒子を含有させたことを特徴とするインクジェットインク。
（２４）カラーフィルタ用であることを特徴とする（２３）に記載のインクジェットインク。 The above problems have been achieved by the following means.
(1) Self-dispersible organic pigment fine particles having an organic pigment and a polymer compound,
The organic pigment fine particles are prepared by mixing an organic pigment solution in which the organic pigment and the polymer compound are dissolved in a first solvent, and a second solvent that is a poor solvent for the organic pigment and is compatible with the first solvent. , Nanometer-sized fine particles deposited in the mixed solution, and a third compound different from both the first solvent and the second solvent by using a compound insoluble in the second solvent as the polymer compound. Organic pigment fine particles characterized in that they can be self-dispersed in a solvent.
(2) The organic pigment fine particles according to (1), wherein the polymer compound has a mass average molecular weight of 1,000 to 500,000.
(3) The polymer compound is at least one polymer compound selected from the group consisting of polymers and copolymers of vinyl monomers, ester polymers, ether polymers, and modified products and copolymers thereof. The organic pigment fine particles according to (1) or (2), which are characterized.
(4) The high molecular compound is a polymer or copolymer of a vinyl monomer having a hydrocarbon group having 4 or more carbon atoms, according to any one of (1) to (3), Organic pigment fine particles.
(5) The organic pigment fine particles according to any one of (1) to (4), wherein the polymer compound has a repeating unit represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group; J represents —CO—, —COO—, —CONR ⁶ —, —OCO—, a phenylene group, or —C ₆ H ₄ CO— group; ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ¹ represents a linear, branched, or cyclic alkylene group, an aralkylene group, or a single bond, and P represents a heterocyclic group.
(6) The organic pigment according to any one of (1) to (5), wherein the polymer compound further has a repeating unit represented by the following general formula (2) or (3): Fine particles.

(R ¹ represents a hydrogen atom or a methyl group. Y represents —NH—, —O—, or —S—. W ² represents a single bond or a divalent linking group. P represents a heterocyclic group. .)
(7) P in the general formula (1), (2), or (3) is represented by the general formula (4) or a tautomer structure thereof (5) or (6) Organic pigment fine particles as described in).

(R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a hydrogen atom. R ³ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an azo group.)
(8) Any one of (1) to (7), wherein the polymer compound is a graft copolymer having a side chain formed by a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal. Organic pigment fine particles according to item 1 (9)
The organic pigment fine particles according to any one of (1) to (8), wherein the organic pigment solution further contains at least one organic compound having a basic group or an acidic group.
(10) Any one of (1) to (9), wherein the organic pigment solution and the second solvent are mixed under a condition where the Reynolds number Re represented by the following formula (1) is 50 or more. 2. Organic pigment fine particles according to item 1.
Re = ρUL / μ (1)
[In formula (1), Re represents the Reynolds number, ρ represents the density of the organic pigment solution, U represents the relative speed at which the organic pigment solution and the second solvent meet, and L represents the organic pigment solution and the second solvent. 2 represents the equivalent diameter of the flow path or supply port where the solvent meets, and μ represents the viscosity coefficient of the organic pigment solution. ]
(11) Any one of (1) to (10), wherein the first solvent is at least one selected from the group consisting of an organic acid, an organic base, a sulfoxide compound solvent, and an amide compound solvent. 2. Organic pigment fine particles according to item 1.
(12) The organic pigment fine particles according to any one of (1) to (11), wherein the second solvent is at least one selected from the group consisting of an aqueous medium and an alcohol compound solvent. .
(13) The third solvent is at least one solvent selected from the group consisting of ether compound solvents, ester compound solvents, aromatic hydrocarbon compound solvents, and aliphatic hydrocarbon compound solvents. The organic pigment fine particles according to any one of (1) to (12).
(14) In the organic pigment solution, the polymer compound is contained in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the organic pigment. Organic pigment fine particles.
(15) An organic pigment solution in which an organic pigment and a polymer compound are dissolved in a first solvent and a second solvent that is a poor solvent for the organic pigment and is compatible with the first solvent are mixed, In order to deposit nanometer-sized fine particles having the organic pigment and the polymer compound on the surface, a compound insoluble in the second solvent is used as the polymer compound, and the fine particles are separated from the first solvent and the second solvent. A method for producing organic pigment fine particles, which is capable of self-dispersing in a third solvent different from any of the solvents.
(16) A pigment dispersion composition, wherein the organic pigment fine particles according to any one of (1) to (14) are self-dispersed in the third solvent.
(17) The pigment dispersion composition according to (16), further comprising a pigment dispersant.
(18) A photocurable composition comprising the pigment dispersion composition according to (16) or (17), a photopolymerizable compound, and a photopolymerization initiator.
(19) The photocurable composition as described in (18), further comprising an alkali-soluble resin.
(20) The photocurable composition as described in (18) or (19), which is used for a color filter.
(21) A color filter having a colored pattern formed using the photocurable composition according to any one of (18) to (20) on a substrate.
(22) A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to any one of (18) to (20) onto a substrate directly or via a predetermined layer; And a colored pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development on the formed photosensitive film.
(23) An inkjet ink characterized in that the organic pigment fine particles according to any one of (1) to (14) are contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer.
(24) The inkjet ink as described in (23), which is for a color filter.

  The organic pigment fine particles of the present invention and the pigment dispersion composition, photocurable composition, and ink-jet ink containing the same improve the characteristics of the color filter, in particular, increase the contrast of the color filter, and the production quality and production efficiency. In addition, it has an excellent effect of improving environmental compatibility and realizing good display characteristics in the liquid crystal display device. According to the production method of the present invention, the organic pigment fine particles having the above-mentioned excellent characteristics can be produced efficiently and with high purity, and a color filter having a good display quality using the organic pigment fine particles can be produced at low cost and efficiently. Can be manufactured.

Hereinafter, the present invention will be described in detail.
The organic pigment used in the present invention is not limited in terms of hue. For example, perylene pigments, perinone pigments, quinacridone pigments, quinacridone quinone pigments, anthraquinone pigments, anthanthrone pigments, benzimidazolones Pigments, disazo condensation pigments, disazo pigments, azo pigments, indanthrone pigments, phthalocyanine pigments, triarylcarbonium pigments, dioxazine pigments, aminoanthraquinone pigments, diketopyrrolopyrrole pigments, thioindigo pigments And pigments, isoindoline pigments, isoindolinone pigments, pyranthrone pigments, isoviolanthrone pigments, and mixtures thereof.
Among these, quinacridone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, or azo pigments are preferable, and diketopyrrolopyrrole pigments, phthalocyanine pigments, or dioxazine pigments are more preferable. .

Examples of the organic pigment include the following.
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 37, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;

Although it does not specifically limit as a pigment in this invention, The following pigment is more preferable.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 37,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 36
C. I. Pigment Black 7

  In the present invention, two or more kinds of organic pigments or solid solutions of organic pigments may be used in combination, or may be used in combination with organic dyes.

The polymer compound used in the present invention has a function of imparting self-dispersibility to the third solvent to the organic pigment fine particles (from this viewpoint, the polymer compound is referred to as “self-dispersing polymer compound”). The compound is not particularly limited as long as the compound is soluble in the first solvent and insoluble in the second solvent, that is, the second solvent becomes a poor solvent. Among them, a polymer compound that functions as a dispersant and quickly adsorbs to the deposited pigment fine particles when the pigment is precipitated by mixing the organic pigment solution and the second solvent is preferable. . Here, in the present invention, when the solubility of a compound in a solvent is 2.0% by mass or less, the compound is insoluble in the solvent, that is, the solvent is defined as a poor solvent for the compound. To do.
Although the mass mean molecular weight of the said high molecular compound is not specifically limited, It is preferable that it is 1000-500000, It is more preferable that it is 2000-300000, It is especially preferable that it is 3000-200000. The shape of the polymer compound may be linear or branched (for example, graft, star shape, etc.). When the polymer is a copolymer, any of a random copolymer, an alternating copolymer, a block copolymer, and a terminal-modified copolymer may be used. In the present invention, the molecular weight means a mass average molecular weight unless otherwise specified, and the mass average molecular weight (Mw) is a polystyrene equivalent mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

  The polymer compound is not particularly limited, but a vinyl monomer polymer or copolymer (for example, an alkyl methacrylate homopolymer, a styrene homopolymer, an alkyl methacrylate / styrene copolymer), Polyvinyl butyral, etc.), ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amides Polymer (for example, polyamide 6, polyamide 66, etc.), silicone-based polymer (for example, polydimethylsiloxane), carbonate-based polymer (for example, polycarbonate synthesized from bisphenol A and phosgene) And the like.

  Among these, the polymer compound is preferably a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, or a modified product or copolymer thereof. From the viewpoints of adjusting solubility in a solvent, cost, ease of synthesis, and the like, the polymer compound is particularly preferably a vinyl monomer polymer or copolymer.

  Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like are preferable examples.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate Ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylic acid Vinyl, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) acrylic Benzyl acid, (meth) acrylic acid diethylene glycol monomethyl ether (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol Monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylic acid Trifluoroethyl, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic Tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N-methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

  Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

  Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinylcaprolactone and the like can also be used.

  The polymer compound is more preferably a polymer or copolymer of a vinyl monomer having a hydrocarbon group having 4 or more carbon atoms, and further having a hydrocarbon group having 6 to 24 carbon atoms. A monomer polymer or copolymer is particularly preferred. Examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate T-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl (meth) acrylate, Specific examples include octadecyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, and adamantyl (meth) acrylate.

  In addition to the above, preferred examples of the vinyl monomer include a vinyl monomer having an acidic group and a vinyl monomer having a basic group.

  Examples of the vinyl monomer having an acidic group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. And acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, (meth) acrylic acid ω- Carboxy-polycaprolactone can also be used. Examples of the carboxyl group precursor include anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  As a vinyl monomer having a basic nitrogen atom, as its (meth) acrylic acid ester, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acrylic Acid 1- (N, N-dimethylamino) -1,1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylic acid N , N-diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, ( Piperidinoethyl (meth) acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2- (meth) acrylate Examples thereof include lolidylaminoethyl and N, N-methylphenylaminoethyl (meth) acrylate. Examples of (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- ( N ', N'-dimethylaminoethyl) methacrylamide, N- (N', N'-diethylaminoethyl) acrylamide, N- (N ', N'-diethylaminoethyl) methacrylamide, N- (N', N ' -Dimethylaminopropyl) acrylamide, N- (N ', N'-dimethylaminopropyl) methacrylamide, N- (N', N'-diethylaminopropyl) acrylamide, N- (N ', N'-diethylaminopropyl) methacryl Amide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, -Diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide Examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene and the like.

It is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Furthermore, a monomer containing an ionic functional group can be used. Among the ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers), as the anionic vinyl monomer, alkali metal salts of vinyl monomers having the acidic group, organic amines (for example, triethylamine, dimethylaminoethanol, etc.) A salt with a tertiary amine), and as the cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom): Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1 18); dialky sulfate (Alkyl group: C1 -4) that is quaternized with such, like dialkyl diallyl ammonium salts.

  The polymer compound is preferably a monomer having an organic dye structure or a heterocyclic structure. Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolino , Mention may be made of benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, a monomer having a heterocyclic structure anthraquinone.

（式中、Ｒ^１は水素原子またはメチル基を表す。Ｊは−ＣＯ−、−ＣＯＯ−、−ＣＯＮＲ^６−、−ＯＣＯ−、フェニレン基、または−Ｃ_６Ｈ_４ＣＯ−基を表し、Ｒ^６は水素原子、アルキル基、アリール基、またはアラルキル基を表す。Ｗ^１は単結合、直鎖、分岐、もしくは環状のアルキレン基、又はアラルキレン基を表す。Ｐは複素環基を表す。 Among these monomers having an organic dye structure or a heterocyclic structure, more specifically, the polymer compound is a monomer polymer or copolymer represented by the general formula (1) Is preferred. In the present invention, when the polymer compound is represented by a repeating unit structural formula, the terminal group may be any atom or any group, and may be simply a hydrogen atom, a polymerization terminator residue, or the like.

(Wherein R ¹ represents a hydrogen atom or a methyl group; J represents —CO—, —COO—, —CONR ⁶ —, —OCO—, a phenylene group, or —C ₆ H ₄ CO— group; ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ¹ represents a single bond, a linear, branched, or cyclic alkylene group, or an aralkylene group, and P represents a heterocyclic group.

In formula (1), J is preferably —CO—, a phenylene group, or a benzoyl group. R ⁶ is a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, a 2-hydroxyethyl group), an aryl Represents a group (for example, a phenyl group), preferably a hydrogen atom, a methyl group, or an ethyl group.

The alkylene group represented by W ¹ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a decylene group, and the like can be given. Among them, a methylene group, an ethylene group, or a propylene group is preferable. The aralkylene group represented by W ¹ is preferably an aralkylene group having 7 to 13 carbon atoms, and examples thereof include a benzylidene group and a cinnamylidene group. The arylene group represented by W ¹ is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group, a cumenylene group, a mesitylene group, a tolylene group, and a xylylene group, and among them, a phenylene group is particularly preferable. .

In the linear, branched or cyclic alkylene group and aralkylene group represented by W ¹ , —NR ³² —, —NR ³² R ³³ —, —COO—, —OCO—, —O—, —SO ₂ NH—, —NHSO ₂ —, —NHCOO—, —OCONH—, or a group derived from a heterocyclic ring may be interposed as a linking group. R ³² and R ³³ each independently represent hydrogen or an alkyl group, and preferred examples include hydrogen, a methyl group, an ethyl group, and a propyl group.

Among the linking groups represented by W ¹ , a single bond or an alkylene group is preferable, and a methylene group, an ethylene group, or a 2-hydroxypropylene group is more preferable.

  In formula (1), P represents a heterocyclic group, and among them, a heterocyclic residue constituting an organic pigment is preferable, and phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolo Examples thereof include heterocyclic residues that form pyrrole, anthrapyrimidine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, and quinophthalone pigments. The heterocyclic residues include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine , Pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, barbitur, thiobarbitur, carbazole, acridine, acridone Quinacridone, anthraquinone, phthalimide, quinaldine, quinophthalone, thiophene, furan, Ten, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, indole, quinoline, carbazole, acridine, acridone, quinacridone, anthraquinone, phthalimide, quinaldine, quinophthalone, etc. are preferred, benzimidazolone, indole, quinoline, barbitur Thiobarbitur, carbazole, acridine, acridone, anthraquinone, and phthalimide are particularly preferred. These heterocyclic residues can be appropriately selected in view of the structure or electronic properties of the pigment used.

Ｒ^１は水素原子またはメチル基を表す。Ｙは−ＮＨ−、−Ｏ−、または−Ｓ−をあらわす。Ｗ^２は単結合または二価の連結基を表し、単結合、直鎖、分岐もしくは環状のアルキレン基、またはアラルキレン基であることが好ましい。Ｐは複素環基をあらわす。上記式中、Ｗ^２の好ましい範囲は、一般式（１）中のＷ^１と同じである。上記式中Ｐは、一般式（１）中のＰと同じである。 Among the repeating units represented by the general formula (1), those represented by the general formulas (2) and (3) are preferable.

R ¹ represents a hydrogen atom or a methyl group. Y represents —NH—, —O—, or —S—. W ² represents a single bond or a divalent linking group, and is preferably a single bond, a linear, branched or cyclic alkylene group, or an aralkylene group. P represents a heterocyclic group. In the above formula, the preferred range of W ² is the same as W ¹ in the general formula (1). In the above formula, P is the same as P in the general formula (1).

上記例示したものとともに、前記一般式（１）、（２）、及び（３）で表される繰返し単位中のＰが、下記一般式（４）またはその互変異性体構造で表されることもまた好ましい。

Ｒ^２は、水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表す。Ｒ^３は水素原子、アルキル基、アリール基、ハロゲン原子、またはアゾ基を表す。 Specific examples preferable as the structures represented by the formulas (1), (2), and (3) are given below. Note that the present invention is not limited to this.

Along with those exemplified above, P in the repeating unit represented by the general formulas (1), (2), and (3) is represented by the following general formula (4) or a tautomer structure thereof. Is also preferred.

R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an azo group.

  Here, tautomerism will be described. Tautomerism is reversible interconversion between isomers, and is a phenomenon in which hydrogen atoms are rearranged mainly by proton rearrangement. The tautomers are those that can reach an equilibrium state in which both isomers can coexist with each other, and the isomers that can convert each other have a high isomerization rate. As a common example, it occurs by a rearrangement reaction of a hydrogen atom, that is, a proton accompanied by conversion of a single bond and a double bond. The rate of isomerization and the equilibrium ratio vary depending on the temperature, pH, liquid phase or solid phase, and in the case of a solution, the type of solvent. Even when equilibrium is reached for several hours to several days, it is often referred to as tautomerism.

In the present invention, the chemical structure (part) exhibiting the above tautomerism in the polymer compound is referred to as a tautomer structure (part), and the tautomerization in the repeating unit represented by the general formula (4) is performed. The chemical structure (tautomer structure) obtained by the reaction is as shown in the following formulas (a) to (h).

Among these, R ² is preferably a hydrogen atom, a methyl group, an ethyl group, a 2-ethylhexyl group, or a phenyl group.
Among them, the substituent represented by R ³ preferably has an azo structure represented by the following general formula (7).

R ²³ represents a substituted or unsubstituted aromatic ring or a hetero atom-containing heterocycle (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.). Among these, the aromatic ring and heterocyclic ring structure is preferably a 5-membered to 6-membered monocyclic or bicondensed ring. Among them, benzene ring, pyridine ring, pyrimidine ring, imidazole ring, isoxazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring, tetrazole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, benzisoxazole ring A benzothiazole thiadiazole ring is preferred.

Specific examples of the repeating unit having the group represented by the general formula (4) as the heterocyclic group P are listed below, but the present invention is not limited thereto. In addition, the structure given in this specific example is an example of possible tautomeric structures, and other tautomeric structures can be taken.

  The polymer compound is preferably a graft copolymer containing a repeating unit obtained by copolymerizing a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal. Such a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. This specific polymerizable oligomer is preferably composed of a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-20000, and the range of 2000-10000 is especially preferable.
The polymer chain part is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.
The polymerizable oligomer is preferably an oligomer represented by the following general formula (5).

However, R < ⁹ > and R < ¹¹ > represents a hydrogen atom or a methyl group each independently, R < ¹⁰ > is a C1-C12 alkylene group (preferably C2-C4 alkylene group, a substituent ( For example, it may have a hydroxyl group and may be further linked via an ester bond, an ether bond, an amide bond, etc.), and Z represents a phenyl group or an alkyl group having 1 to 4 carbon atoms. A phenyl group or —COOR ¹² (wherein R ¹² represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 to 10 carbon atoms), and q is from 20 to 200 is there. Z is preferably a phenyl group or —COOR ¹² (wherein R ¹² is an alkyl group having 1 to 12 carbon atoms).
Preferred examples of the polymerizable oligomer (macromonomer) include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and one molecular end of polystyrene (meth). A polymer having an acryloyl group bonded thereto can be exemplified. As such a polymerizable oligomer available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl methacrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

The polymerizable oligomer is preferably not only a polymerizable oligomer represented by the general formula (5) but also a polymerizable oligomer represented by the following general formula (6).

In the general formula (6), R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200.
In the general formula (6), R ¹³ represents a hydrogen atom or a methyl group. R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 18 carbon atoms. Moreover, n represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

Examples of the polymerizable oligomer represented by the general formula (6) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol monomethacrylate. These may be commercially available products or may be appropriately synthesized.
As described above, the polymerizable monomer represented by the general formula (6) is also available as a commercial product, and as a commercial product, methoxypolyethylene glycol methacrylate (trade names: NK ester M-40G, M-90G, M -230G (manufactured by Shin-Nakamura Chemical Co., Ltd.); trade names: Blemmer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, NOF Corporation) Manufactured)), polyethylene glycol monomethacrylate (trade names: Blemmer PE-90, PE-200, PE-350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: Blemmer PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polypropylene glycol mono Tacrylate (trade name: Blemmer 70PEP-350B, manufactured by NOF Corporation), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BREMMER 55PET-800, manufactured by NOF Corporation), polypropylene glycol polytetramethylene glycol mono Methacrylate (trade name: Bremmer NHK-5050, manufactured by NOF Corporation), and the like.
In addition to the polymerizable oligomers of the above general formulas (5) and (6), polycaprolactone monomers are also preferable, and commercially available products include polycaprolactone monomethacrylate (trade name: Plaxel FM2D, FM3, FM5, FA1DDM, FA2D, Daicel Chemical). Kogyo Co., Ltd.).

  For the production of a polymer or copolymer of vinyl monomers, for example, a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.

  The polymer or copolymer of the vinyl monomer may be a polymer compound having a functional group at the terminal. The functional group is preferably a functional group excellent in adsorbability to the deposited pigment.

  The polymer compound having a functional group at the terminal can be polymerized using, for example, a method of performing radical polymerization using a chain transfer agent containing a functional group, or a polymerization initiator containing a functional group (eg, radical polymerization, cationic polymerization). , Anionic polymerization, etc.).

  Examples of the chain transfer agent capable of introducing a functional group at the terminal of the polymer compound include mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propanol, 3-mercapto-2- (Tanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Examples thereof include disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  Examples of the polymerization initiator capable of introducing a functional group at the terminal of the polymer compound include 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4, 4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane ], 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -Propionamide] etc. And derivatives thereof.

  The amount of the self-dispersing polymer compound used is not particularly limited, but when the organic pigment fine particles are precipitated, the amount to be contained in the organic pigment solution is in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the pigment. Preferably, the range is 10 to 120 parts by mass, and particularly preferably 20 to 100 parts by mass. Within the above range, the particle diameter of the organic pigment fine particles can be effectively controlled to a nanometer size, and the precipitated organic pigment fine particles can be efficiently taken out as a floc. Furthermore, the third solvent Self-dispersibility can be imparted. The polymer compounds may be used alone or in combination of two or more.

  In the present invention, the term “self-dispersibility” is different from that in which fine particles present in a predetermined dispersion (dispersion) substantially remove the dispersion medium (continuous phase) constituting the predetermined dispersion. When the fine particles are present in a dispersion medium (third dispersion medium), the particles are spontaneously applied to the different dispersion medium (third dispersion medium) without adding another dispersant or surfactant. It means showing good dispersibility. At this time, it is preferable to remove 70% by mass or more and 100% by mass or less of the entire medium, and add the switched third dispersion medium. It is preferable that it is -10 mass%. A specific method for removing and concentrating the solvents (first solvent and second solvent) used for producing the fine particles will be described later.

  The amount of the polymer compound contained in the organic pigment fine particles is not particularly limited. For example, when the fine particles are taken out as flocs or redispersed in the third solvent, the amount of the pigment in the organic pigment fine particles is 100 mass. It is practical that about 10 to 100 parts by mass are incorporated and contained with respect to parts. Further, the total amount of the self-dispersing polymer compound in the redispersed dispersion is not particularly limited, but includes the amount of the polymer compound in the fine particles with respect to 100 parts by mass of the pigment in the dispersion, It is preferably 10 to 200 parts by mass, and more preferably 10 to 100 parts by mass. On the other hand, the content of the organic pigment is not particularly limited, but is practically 20 to 90% by mass in the organic pigment fine particles.

Examples of the polymer compound that can be used in the present invention are shown below, but the present invention is not limited thereto.
(1) Polymethyl methacrylate (2) Polypropylene glycol (3) Polyε caprolactone (4) Methyl methacrylate / styrene copolymer (5) Benzyl methacrylate / acrylic acid copolymer (6) Methyl methacrylate / dimethylamino Propylacrylamide copolymer (7) Methyl methacrylate / monomer copolymer giving the above constituent Q-17 (8) Methyl methacrylate / monomer giving the above constituent Q-17 / Terminal methacryloylated polymethyl methacrylate copolymer (9) Monomer / Styrene / Methacrylic Acid Copolymer Providing Component M-1 (10) Monomer / Terminal Methacryloylated Polymethyl Methacrylate / Methacrylic Acid Copolymer Providing Component M-1 (11) Configuration Monomer / terminal methacrylate giving component M-1 Ilylated polymethyl methacrylate / dimethylaminopropyl acrylamide copolymer (12) Monomer providing the above component Q-22 / terminal methacryloylated polystyrene / methacrylic acid copolymer (13) Monomer / terminal providing the above component Q-10 Methacryloylated polybutylmethacrylate / methacrylic acid copolymer (14) Monomer / terminal (meth) acryloylated polyethylene glycol polypropylene glycol / methacrylic acid copolymer (15) giving the constituent component M-1 Monomer to give / terminal (meth) acryloylated polyethylene glycol / methacrylic acid copolymer (16) On monomer / terminal (meth) acryloylated polypropylene glycol / methacrylic acid copolymer (17) to give component Q-1 Monomer / terminal methacryloylated polycaprolactone / methacrylic acid copolymer (18) that gives component M-1 Monomer / terminal methacryloylated polystyrene / methacrylic acid / dimethylaminopropylacrylamide copolymer (18) that gives constituent Q-21 19) Monomer / terminal methacryloylated polymethyl methacrylate copolymer that provides the above component M-1 (20) Monomer / styrene / dimethylaminopropylacrylamide copolymer that provides the above component Q-22 (21) Component M -1 monomer / N, N-dimethyl-4-vinylbenzamide / methacrylic acid copolymer (22) Monomer giving the above constituent Q-23 / 4-tbutylstyrene / methacrylic acid copolymer (23) Monomer that provides component M-3 / Tacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (24) Monomer / terminated methacrylic acid / terminated methacryloylated polycaprolactone copolymer (25) Monomer / terminated to provide component M-2 Methacryloylated polymethyl methacrylate / terminated (meth) acryloylated polyethylene glycol polypropylene glycol copolymer (26) Monomer / methacrylic acid / terminated methacryloylated polymethyl methacrylate / polyethylene glycol mono (meth) acrylate copolymer to give the above component M-7 Polymer (27) Monomer that gives component Q-9 / 4-vinylpyridine / terminal methacryloylated polymethyl methacrylate copolymer (28) Monomer / terminal that gives component M-10 Tacryloylated polybutyl methacrylate / N-vinylimidazole copolymer (29) Monomer / methacrylic acid / terminal methacryloylated poly n-butyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (30) to give the above component M-1 Monomer / acrylic acid / terminated methacryloylated polymethylmethacrylate copolymer (31) giving the above constituent component Q-4 Monomer / styrene / methacrylic acid copolymer (32) giving the above constituent component M-13 1 monomer / methacrylic acid / terminated methacryloylated polymethyl methacrylate / dodecyl methacrylate copolymer (33) Monomer / methacrylic acid / terminal methacryloylated polystyrene / stearyl methacrylate copolymer giving the above component Q-1 Copolymer (34) Methacrylic acid / Terminal methacryloylated polymethyl methacrylate / Isobornyl methacrylate copolymer (35) Cyclohexyl cyclohexyl / 4-vinylpyridine copolymer (36) Monomer / butyl methacrylate giving the above component Q-1 Copolymer (37) Monomer giving the above component M-1 / styrene / methacrylic acid / methyl methacrylate copolymer (38) Monomer giving the above component M-2 / styrene / butyl methacrylate copolymer ( 39) Monomer giving the above component Q-21 / methacrylic acid tbutyl ester / methacrylic acid copolymer (40) Monomer giving the above component Q-10 / styrene / butylacrylamide copolymer (41) Methyl methacrylate / Methacrylic acid copolymer A commercially available polymer compound may be used. Examples of commercially available block polymers include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.
Examples of commercially available graft polymers include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.
Examples of commercially available terminal-modified polymers include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all commercially available polymers are trade names).

  The polymer compound may coexist with an organic compound having a basic group or an acidic group in the organic pigment solution, but a nitrogen-containing polymer compound and a polymer compound having an acidic group are used in combination. It is preferable not to coexist. When the two kinds of compounds are used in combination, the organic pigment fine particles may easily aggregate because the nitrogen atom of the nitrogen-containing polymer compound interacts with the acidic group of the polymer compound having an acidic group. When the color filter is used, the contrast may decrease. Further, when the polymer compound contains a nitrogen-containing polymer compound, it is preferable not to allow a compound having a basic nitrogen atom to coexist in the pigment solution. If this is coexisted, the color filter may be colored by baking.

  The first solvent (good solvent) is not particularly limited as long as it is capable of dissolving the organic pigment and the polymer compound and is compatible (mixed uniformly) with the second solvent (poor solvent). The solubility of the organic pigment in the first solvent is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 50% by mass or less in consideration of a commonly used organic pigment. The solubility of the self-dispersing polymer compound in the first solvent is preferably 4.0% by mass or more, and more preferably 10.0% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 70% by mass or less in consideration of a commonly used polymer compound.

  As for the compatibility of the first solvent and the second solvent, the amount of the first solvent dissolved in the second solvent is preferably 30% by mass or more, and more preferably 50% by mass or more. There is no particular upper limit on the amount of the first solvent dissolved in the second solvent, but it is practical to mix them in an arbitrary ratio.

Although it does not specifically limit as a 1st solvent, For example, formic acid, dichloroacetic acid, methanesulfonic acid, etc., organic bases (for example, diazabicycloundecene (DBU), tetrabutylammonium hydroxide, sodium methoxide) Etc.), aqueous solvents (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvents (for example, methanol, ethanol, n-propanol, etc.), ketone solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) , Ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.) Ester solvents (for example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), ionic liquids (for example, And 1-ethyl-3-methylimidazolium tetrafluoroborate), a carbon disulfide solvent, or a mixture thereof.

  Among these, an organic acid, an organic base, an aqueous solvent, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, an amide solvent, or a mixture thereof is more preferable, and an organic acid, an organic base , Sulfoxide solvents, amide solvents, or mixtures thereof are particularly preferred.

  Examples of the organic acid include, but are not limited to, sulfonic acid compounds, carboxylic acid compounds, acid anhydride compounds, and the like.

  Examples of the sulfonic acid compound include alkyl sulfonic acid, halogenated alkyl sulfonic acid, and aromatic sulfonic acid. The alkyl chain and the aromatic ring may be unsubstituted or substituted with a substituent T. The substituent T here may be any substituent as long as it can be substituted with the sulfonic acid compound.

  Examples of the substituent T include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, a nitro group, an amino group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, and an aliphatic group. Oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl Group, aliphatic sulfonamido group, aryl sulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, hetero Ring oxycarbonyl Group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoyl Examples thereof include an amino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

  Specific examples of the sulfonic acid compound used in the present invention include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nona. Fluorobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, chlorobenzenesulfonic acid, aminobenzenesulfonic acid, 1,5-naphthalenedisulfonic acid tetrahydrate, etc. It is done.

  Examples of the carboxylic acid compound include alkyl carboxylic acids, halogenated alkyl carboxylic acids, and aromatic carboxylic acids. The alkyl chain and the aromatic ring may be unsubstituted or substituted with the substituent T. Specific examples of carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, difluoroacetic acid, dichloroacetic acid, dibromoacetic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, chlorodifluoroacetic acid , Cyanoacetic acid, phenoxyacetic acid, diphenylacetic acid, thioacetic acid, mercaptoacetic acid, mercaptopropionic acid, 2-chloropropionic acid, 2,2-dichloropropionic acid, 3-chloropropionic acid, 2-bromopropionic acid, 3-bromopropion Acid, 2,3-dibromopropionic acid, 2-chlorobutyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, isobutyric acid, 2-bromoisobutyric acid, cyclohexanecarboxylic acid, nitroacetic acid, phosphonoacetic acid, pyruvic acid, oxalic acid, propargyl Acid, trimethylammonium acetic acid Benzoic acid, tetrafluorobenzoic acid, pentafluorobenzoic acid, 2-chlorobenzoic acid, 2-fluorobenzoic acid, benzoyl formate, benzoylbenzoic acid, 2-dimethylaminobenzoic acid, 2,6-dihydroxybenzoic acid, picolinic acid, Citric acid, cysteine, sulfanilic acid, squaric acid and the like can be mentioned.

  In the present invention, in addition to carboxylic acid and sulfonic acid, an acid anhydride can be used as the acid, and specifically, acetic anhydride, propionic acid anhydride, trifluoromethanesulfonic acid anhydride, trichloro And acid anhydrides such as acetic anhydride. Examples of organic acids other than these include isopropyl phosphate, methyl phosphate, phenylphosphonic acid, ethylenediaminetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and methylenediphosphonic acid.

  As the organic acid, alkylsulfonic acid, alkylcarboxylic acid, halogenated alkylcarboxylic acid, and aromatic sulfonic acid are preferable, and methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid. Formic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are more preferable.

  Examples of organic bases include primary amines, secondary amines, tertiary amines, quaternary amines, anilines, piperidines, piperazines, amidines, formamidines, pyridines, Examples include, but are not limited to, guanidines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like. Among these, tertiary amines, quaternary amines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like are preferable.

  Specifically, aniline, 2-chloroaniline, 3-fluoroaniline, 2,4-difluoroaniline, 2-nitroaniline, N, N-diethylaniline, 2,6-diethylaniline, 2,4-dimethoxyaniline, p-phenylenediamine, pyridine, 2-aminopyridine, pyrimidine, pyridazine, pyrazine, 2,2-dipyridyl, pyrrolidine, piperidine, imidazole, pyrazole, thiazole, benzothiazole, oxazole, diazabicycloundecene, diazabicyclononene, Diazabicyclooctane, 1-cyanoguanidine, N, N′-diphenylguanidine, cyclohexylamine, butylamine, cyclopropylamine, t-butylamine, benzylamine, diisopropylamine, trimethylamine, triethylamine , Tributylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, morpholine, thiomorpholine, N-methylmorpholine, hexamethylphosphoramide, 1-methyl -4-piperidone, N- (2-aminoethyl) piperazine, ethylenediamine, diethylenetriamine, bis- (3-aminopropyl) ether, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium Examples include ethoxide and potassium t-butoxide.

  Among these, aniline, 2,4-difluoroaniline, pyridine, diazabicycloundecene, diazabicyclononene, diazabicyclooctane, triethylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethyl Ammonium hydroxide, tetrabutylammonium hydroxide, N-methylmorpholine, N- (2-aminoethyl) piperazine, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium -T-butoxide is preferred, 2,4-difluoroaniline, diazabicycloundecene, diazabicyclononene, tetrahydroquinoline, phenyltrimethylammonium Hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, N- methylmorpholine, sodium methoxide, potassium -t- butoxide preferred.

  More specific examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.

  More specifically, examples of the amide solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε -Caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

  There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  When the organic pigment is uniformly dissolved in the first solvent, generally, in the case of a pigment having an alkaline and dissociable group in the molecule, there is no alkali, but there is no alkaline and dissociable group, and nitrogen is easily added with protons. When there are many atoms in the molecule, it is preferable to use acidity. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  In addition to the organic base, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide can also be used as the base used when dissolving in an alkaline manner. The amount of the base to be used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents relative to the organic pigment. It is particularly preferably 0 to 20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the organic pigment.

  In addition to the organic acid, an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like can be used as an acid used when the acid is dissolved. The amount of the acid to be used is not particularly limited, but it is often used in excess compared to the base, and is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents with respect to the organic pigment. 30 to 200 molar equivalents are particularly preferred.

When an inorganic base or an inorganic acid is mixed with an organic solvent and used as a good solvent (first solvent) for an organic pigment, the alkali or acid is completely dissolved. On the other hand, a solvent having a high solubility can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the organic pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

  The viscosity of the organic pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

The organic pigment solution is not particularly limited as long as the organic pigment and the polymer compound are dissolved in the first solvent, and may contain other components.
Although it does not specifically limit as another component, The organic compound which has an acidic group, the organic compound which has basicity etc. are mentioned suitably. These components have the action of adsorbing quickly to the deposited pigment and treating the pigment surface to be acidic or basic when the pigment is precipitated by mixing the organic pigment solution and the second solvent. Is. The solubility of the other components in the second solvent is not particularly limited, but is preferably a compound that makes the second solvent a poor solvent.

  Examples of the acidic group of the organic compound having an acidic group that can be used in the present invention include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a phosphonic acid group, a hydroxyl group, and a sulfide group. Is not to be done. Moreover, 1 type may be individual in a molecule | numerator, or 2 or more types may contain the same or different functional group. These organic compounds having an acidic group may be used alone or in combination of two or more. Among these, those having a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are preferable.

  Examples of the organic compound having a carboxylic acid group include behenic acid, 13-docosenoic acid, oleic acid, linoleic acid, stearic acid, isostearic acid, 2-hexyldecanoic acid, palmitic acid, myristic acid, lauric acid, decanoic acid, and octane. Acid, 3,5,5-trimethylhexanoic acid, 1,12-todecanedicarboxylic acid, sebacic acid, 1-adamantanecarboxylic acid, 1-naphthoic acid, 2-naphthoic acid, pyromellitic acid, p-benzoylaminobenzoic acid , Terephthalic acid, isophthalic acid, phthalic acid, benzoic acid, trimellitic acid, 1-hydroxy-2-naphthoic acid, β-oxynaphthoic acid, p-octyloxybenzoic acid, triphenylacetic acid, mandelic acid, perfluorooctanoic acid , P-nitrobenzoic acid, o-benzoylbenzoic acid, 4-sulfamoylbenzoate Acid, o-benzoylaminobenzoic acid, 2,6-pyridinedicarboxylic acid, tetrahydrofurantetracarboxylic acid, 2-quinolinecarboxylic acid, 4,4-biphenyldicarboxylic acid, 4-hydroxybiphenyl-3-carboxylic acid, 2-naphthylacetic acid 2,6-naphthalenedicarboxylic acid, 6-hydroxy-2-naphthoic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,8-naphthalic acid, 3,4,9,10-perylenetetracarboxylic acid Indole-3-butyric acid, 3,7-dicarboxylic acid diphenyl oxide, tetrachlorophthalic acid, phthalic acid, folic acid, benzylic acid, naphthenic acid, diphenylacetic acid, 2,4-dichlorobenzoic acid and the like.

  Examples of the organic compound having a sulfonic acid group include β-naphthalenesulfonic acid, dodecylbenzenesulfonic acid, cetylsulfuric acid, C acid, J acid, γ acid, diaminostilbene disulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, and naphthalenesulfone. Examples thereof include acid, naphthalene disulfonic acid, chlorobenzene sulfonic acid, 1-naphthylamine-4-sulfonic acid (naphthoic acid), dobias acid, peric acid, jaic acid, kofu acid, metanilic acid, toluenesulfonic acid, octanesulfonic acid and the like.

  Examples of the compound having a sulfinic acid group include p-toluenesulfinic acid, benzenesulfinic acid, p-carboxybenzenesulfinic acid, octylsulfinic acid, ethylsulfinic acid, 4-chloro-3-nitrobenzenesulfinic acid, and 4-acetamidobenzenesulfinic acid. Thiophene-2-sulfinic acid, methylsulfinic acid, isobutylsulfinic acid, hexadecylsulfinic acid, hydroxylmethanesulfinic acid and the like.

Examples of the sulfenic acid compound include benzenesulfenic acid and p-toluenesulfenic acid.
Examples of phosphonic acid compounds include stearyl phosphonic acid and lauryl phosphonic acid.

  In the present invention, the addition amount of the organic compound having an acidic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, based on the pigment. It is especially preferable that it is in the range of 0.05 to 15% by mass.

  Organic compounds having a basic group include alkylamines, arylamines, aralkylamines, pyrazole derivatives, imidazole derivatives, triazole derivatives, tetrazole derivatives, oxazole derivatives, thiazole derivatives, pyridine derivatives, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, triazines. Derivatives and the like can be mentioned, and alkylamine, arylamine and imidazole derivatives are preferable.

As carbon number of the organic compound which has the said basic group, 6 or more are preferable, More preferably, it is 8 or more, More preferably, it is 10 or more.
In the organic compound having a basic group, examples of the alkylamine include butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, isobutylamine, t-butylamine, 1-methylbutylamine, 1-ethylbutylamine, t-amylamine, 3-aminoheptane, t-octylamine, 1,4 -Diaminobutane, 1,6-hexadiamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dibutylamine, dihexylamine, dioctylamine, bis (2- Tylhexyl) amine, didecylamine, N-methyloctadecylamine, triethylamine, tripropylamine, N, N-dimethylbutylamine, N-methyldibutylamine, tributylamine, tripentylamine, N, N-dimethylhexylamine, N, N- Dimethyloctylamine, N-maledioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyl-N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N-methylcyclohexylamine, N, N, N ′, N ′, N '' -Pentamethyldiethylenetria , Cyclohexylamine, cycloheptylamine, cyclohexylamine, cyclododecylamine, 1-adamandanamine, etc., preferably octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecyl Amine, tetradecylamine, octadecylamine, t-octylamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N- Methyl octadecylamine, N, N-dimethyloctylamine, N-mail dioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyl -N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N -Methylcyclohexylamine, N, N, N ', N', N ''-pentamethyldiethylenetriamine, cyclododecylamine, 1-adamandanamine and the like, more preferably decylamine, undecylamine, dodecylamine, Examples include tridecylamine, tetradecylamine, didecylamine, N-methyloctadecylamine, N, N-dimethyldodecylamine, and tridodecylamine. Organic polymer compounds having a basic group such as polyallylamine and polyvinylamine are also suitable.

  As the arylamine, for example, N, N-dibutylaniline, 4-butylaniline, 4-pentylamine, 4-hexylamine, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4 -Tetradecylaniline, 4-hexadecylaniline, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, and the like, preferably 4-octylaniline, 4-decylaniline 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, etc., more preferably 4-decylaniline, 4 -Dodecylaniline, 4 Tetradecyl aniline, 4-hexadecyl aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline.

  Examples of the imidazole derivative include 1- (10-hydroxydecyl) imidazole, 1-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and the like.

  The organic compound having a basic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, and more preferably 0.05 to 15% with respect to the pigment. It is particularly preferable to be in the range of mass%.

It is also preferable to add an organic compound composed of a basic group and a heterocyclic group.
Examples of such an organic compound include 2-aminopyridine, 3-aminopyridine, 1- (2-aminophenyl) pyrrole, 5-aminopyrazole, 3-amino-5-methylpyrazole, 5-amino-1- Ethylpyrazole, 3-aminotriazole, 2-aminothiazole, 5-aminoindole, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, phthalimide, 5-aminobenzimidazolone N, N-dimethyl-5-aminobenzimidazolone, 5-aminouracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, aminopyrazine, 8-aminoquinoline, 3-aminoquinoline, 9-amino Acridine, ASTRA blue 6GLL (base Phthalocyanine derivative), 2-amino-anthraquinone, 3-amino-anthraquinone, acridone, N- acridone, quinacridone, NILE Red, and the like methylene violet naphthalimide is. Preferably, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone, 5-amino Uracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, 8-aminoquinoline, 3-aminoquinoline, 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoanthraquinone, 3-amino Anthraquinone, acridone, N-acridone, quinacridone, NILE red, methylene violet naphthalimide, and more preferably 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoan Laquinone, 3-aminoanthraquinone, acridone, N-acridone, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone , 5-aminouracil, 6-aminouracil, NILE red, and methylene violet naphthalimide.

  The addition amount of the organic compound composed of the basic group and the heterocyclic group is preferably in the range of 0.01 to 30% by mass, and in the range of 0.05 to 20% by mass with respect to the pigment. It is more preferable that it is in the range of 0.05 to 15% by mass.

  In addition to the above, pigment derivatives described in JP-A No. 2007-9096 and JP-A No. 7-331182 can be exemplified. The pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor. Refers to a pigment derivative type compound. Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA and “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names). When a pigment derivative is used, the amount used is preferably in the range of 0.5 to 30% by mass, more preferably in the range of 3 to 20% by mass, and 5 to 15% by mass with respect to the pigment. It is especially preferable that it is in the range.

  The second solvent (poor solvent) is not particularly limited, but the solubility of the organic pigment in the second solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the second solvent, 0.0001% by mass or more is practical in consideration of a commonly used organic pigment. The solubility of the self-dispersing polymer compound in the second solvent is 2.0% by mass or less (insoluble), and preferably 1.0% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the second solvent, 0.001% by mass or more is practical in consideration of a commonly used polymer compound.

Although it does not specifically limit as a 2nd solvent, An aqueous solvent (For example, water, hydrochloric acid, sodium hydroxide aqueous solution), Alcohol-type solvent (For example, methanol, ethanol, n-propanol etc.), Ketone-type solvent (For example, methyl ethyl ketone) , Methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents (For example, ethyl acetate, acetic acid-n-butyl, ethyl lactate, etc.), amide solvents (for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), ionic liquids (for example, 1-ethyl-3
-Methylimidazolium tetrafluoroborate etc.), carbon disulfide solvent, or a mixture thereof is preferably mentioned.
Among these, an aqueous solvent, an alcohol solvent, a ketone solvent, a sulfoxide solvent, an ester solvent, an amide solvent, a nitrile solvent, or a mixture thereof is more preferable, and an aqueous solvent, an alcohol solvent, or a mixture thereof. Is particularly preferred.

Examples of the aqueous solvent include water, hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like.

  Although there are some which are common between those listed as specific examples of the first solvent and those listed as the second solvent, the same thing is not combined as the first solvent and the second solvent, The solubility in the first solvent should be sufficiently higher than the solubility in the second solvent in relation to the molecular compound. For the pigment, for example, the solubility difference is preferably 0.2% by mass or more, and 0.5% by mass. More preferably. There is no particular upper limit to the difference in solubility between the first solvent and the second solvent, but it is practical that the difference is 50% by mass or less in consideration of a commonly used organic pigment. For the polymer compound, for example, the solubility difference is preferably 2.0% by mass or more, and more preferably 5.0% by mass or more. There is no particular upper limit to the difference in solubility between the first solvent and the second solvent, but it is practical that the difference is 70% by mass or less in consideration of a commonly used polymer compound.

  The state of the second solvent is not particularly limited, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C. The viscosity of the organic pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  When mixing the organic pigment solution and the second solvent, either of them may be added and mixed. However, the organic pigment solution is preferably jetted into the second solvent and mixed, and in this case, the second solvent is mixed. Is preferably in a stirred state. The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

By adjusting the Reynolds number when mixing the organic pigment solution and the second solvent, it is possible to control the particle diameter of the pigment nanoparticles to be deposited. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Formula (1), Re represents the Reynolds number, ρ represents the density [kg / m ³ ] of the organic pigment solution, and U represents the relative speed [m / s] when the organic pigment solution meets the second solvent. L represents the equivalent diameter [m] of the flow path or supply port where the organic pigment solution and the second solvent meet, and μ represents the viscosity coefficient [Pa · s] of the organic pigment solution.

The equivalent diameter L is the diameter of an equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to a flow path. The equivalent diameter L is expressed by the following equation (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting the organic pigment solution into the second solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

  The relative speed U when the organic pigment solution and the second solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the organic pigment solution is injected and mixed in the stationary second solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the organic pigment solution is a value determined by the type of material selected, but is practically, for example, 0.8 to 2.0 kg / m ³ . Also, the viscosity coefficient μ of the organic pigment solution is a value determined by the material used, the environmental temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the organic pigment solution described above.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.

  The mixing ratio of the organic pigment solution and the second solvent is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8. The particle concentration in the liquid when organic fine particles are precipitated is not particularly limited, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, with respect to 1000 ml of the solvent. Preferably it is the range of 50-25000 mg. Moreover, the preparation scale at the time of producing | generating a pigment fine particle is although it does not specifically limit, The mixing amount of a 2nd solvent is preferable that it is a preparation scale of 10-2000L, and it is more preferable that it is a preparation scale of 50-1000L.

  Regarding the particle size of organic particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common use, the mode diameter indicating the maximum value of the distribution, the median value of the integral distribution curve Median diameter, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle diameter is the number average. The diameter.

  In the present invention, the average particle size of the pigment fine particles (primary particles) is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, further preferably 2 to 100 nm, and 5 to 80 nm. Particularly preferred. The formed particles may be crystalline particles, amorphous particles, or a mixture thereof.

  In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. In the present invention, the monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, -1.5 is particularly preferred.

  Examples of the method for measuring the particle size of the organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus by the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. and Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd.

  In preparing a dispersion by precipitating pigment fine particles, at least one of the pigment solution and the second solvent is such that at least the second solvent is a good solvent (solubility in the second solvent is 4.0% by mass or more). (Hereinafter, it may be referred to as a particle size adjusting agent).

Examples of the polymer particle size adjusting agent include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-part. Butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylic acid, sodium polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, a diallylamine monomer / SO ₂ copolymers, diallylamine hydrochloride / Ma Examples thereof include oleic acid copolymer, polydiallylmethylamine hydrochloride, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymer, condensed naphthalene sulfonate, cellulose derivative, starch derivative and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone, polyacrylic acid, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, diallylamine monomer / SO ₂ copolymer, and the like are preferable. These particle size adjusting agents can be used singly or in combination of two or more.
The mass average molecular weight is preferably 1,000 to 500,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 100,000.

  As an anionic particle size adjusting agent (anionic surfactant), N-acyl-N-alkyl taurine salt, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl Examples thereof include phosphoric acid ester salts, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts and the like. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyltaurine salt, those described in JP-A-3-273067 are preferable. These anionic particle size regulators can be used alone or in combination of two or more.

  Cationic particle size modifiers (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines derived from aliphatic amines and fatty alcohols, and Examples include salts of cationic substances of imidazoline derived from polyamines and fatty acids. These cationic particle size regulators can be used alone or in combination of two or more.

  The amphoteric particle size regulator is a particle size in which the anionic particle size regulator has both an anion group moiety in the molecule and a cationic group moiety in the molecule of the cationic particle size modifier. It is a regulator.

  Nonionic particle size adjusting agents (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include alkylamines and glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic particle size regulators may be used alone or in combination of two or more.

  The content of the particle size adjusting agent is preferably in the range of 0.1 to 100% by mass, more preferably 0.1 to 50% with respect to the pigment in order to further improve the particle size control of the pigment fine particles. It is the range of mass%, More preferably, it is the range of 0.1-20 mass%. In addition, the particle size adjusting agents may be used alone or in combination.

Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or Aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents.
In the present invention, the good solvent (first solvent) and the poor solvent (second solvent), which are used as the medium of the dispersion composition, including the fourth solvent described later without being limited to the third solvent described above. Solvents different from both are collectively referred to as “third solvent”.

  Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include methanol, ethanol, n-butanol, isobutanol and the like. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane.

  Of these, ethyl lactate, ethyl acetate, ethanol, and 2- (1-methoxy) propyl acetate are preferable, and ethyl lactate and 2- (1-methoxy) propyl acetate are more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the first solvent or the second solvent.

The timing of adding the third solvent is not particularly limited as long as it is after the precipitation of the pigment nanoparticles, but it may be added to the mixed liquid in which the pigment nanoparticles are deposited, or a part of the solvent in the mixed liquid is removed. It may be added after that, or it may be added after removing (concentrating) all in advance.
That is, the third solvent can be used as a substitution solvent, and the solvent component composed of the first solvent and the second solvent in the dispersion liquid in which the pigment nanoparticles are precipitated can be substituted with the third solvent.
Alternatively, the first solvent and the second solvent can be completely removed (concentrated) and taken out as pigment particle powder, and then the third solvent can be added.

In addition, when the pigment dispersion composition described later is used, after the first solvent removal step (first removal), the third solvent is added to replace the solvent, and the second solvent removal step ( The solvent may be removed and powdered by the second removal). Thereafter, a pigment dispersant and / or a solvent can be added to obtain a desired pigment dispersion composition.
Alternatively, the first solvent and the second solvent can be completely removed (concentrated) and taken out as pigment particle powder, and then the third solvent and / or pigment dispersant can be added to obtain a desired pigment dispersion composition. .
The amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the pigment nanoparticles.

The process for removing the solvent from the mixed liquid after the organic pigment fine particles are deposited is not particularly limited, and examples thereof include a method of filtering with a filter and the like, a method of precipitating and concentrating the organic pigment fine particles by centrifugation.
As an apparatus for filter filtration, for example, an apparatus such as reduced pressure or pressure filtration can be used. Examples of preferable filters include filter paper, nanofilters, and ultrafilters.
Any device may be used as the centrifuge as long as the organic pigment fine particles can be precipitated. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be mentioned. Centrifugation conditions are preferably 50 to 10,000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravitational acceleration is applied). Although the temperature at the time of centrifugation is based on the solvent seed | species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, and 0-60 degreeC is especially preferable.
In addition, as the solvent removal step, a method of concentrating the solvent by sublimation by vacuum freeze-drying, a method of drying and concentrating the solvent by heating or decompression, a method combining them, or the like can also be used.

  The pigment nanoparticles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the polymer compound used at the time of nanoparticle formation and / or the pigment dispersant used for redispersion are collectively referred to as a binder.

  The pigment nanoparticle concentration of the pigment nanoparticle dispersion composition after redispersion is appropriately determined according to the purpose, but preferably the pigment nanoparticle content is 2 to 30% by mass with respect to the total amount of the dispersion composition. More preferably, it is 4-20 mass%, and it is especially preferable that it is 5-15 mass%. In the case of dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

  The content of the organic pigment fine particles (the self-dispersing polymer compound or the like may be incorporated therein) is not particularly limited, but is not particularly limited in the pigment dispersion composition of the present invention. It is preferable that it is 0.0-35.0 mass%, and it is more preferable that it is 5.0-25.0 mass%.

  When the organic pigment fine particles of the present invention are re-dispersed in the third solvent, the aggregation state of the organic pigment fine particles is spontaneously solved in the third solvent without adding another dispersing agent or the like. It has a property of dispersing, and as described above, this property is referred to as “self-dispersible” or “self-dispersing”. However, in order to further improve the redispersibility in the present invention, a pigment dispersant or the like may be added during redispersion of the organic pigment fine particles.

As a method of redispersing the organic pigment fine particles in such an aggregated state, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs, so the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
There are no particular limitations on the disperser used when dispersing the pigment nanoparticles by applying physical energy. Can be mentioned. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants may be added to the pigment dispersion composition of the present invention as long as the effects of the present invention are not impaired. it can.
Examples of pigment dispersants include polymer dispersants (for example, linear polymers, block polymers, graft polymers, terminal-modified polymers, etc.), surfactants (polyoxyethylene alkyl phosphate ester, poly Oxyethylene alkylamine, alkanolamine, etc.), pigment derivatives and the like. The dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
Examples of the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like. Examples of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.
Examples of the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).

  In the present invention, the pigment derivative (hereinafter also referred to as “pigment derivative type dispersant”) is derived from an organic pigment as a parent substance, and is manufactured by chemically modifying the parent structure, or It is defined as a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. Generally, it is also called a synergist type dispersant.

  Although not particularly limited, for example, a functional group such as a pigment derivative having an acidic group, a pigment derivative having a basic group, or a phthalimidomethyl group described in JP-A-2007-9096, JP-A-7-331182, or the like. The introduced pigment derivative is preferably used.

Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)” manufactured by Lubrizol (any) Product name).
Examples of the linear polymer include an alkali-soluble resin described later, and it is also preferable to use the linear polymer in combination with the pigment derivative.
Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.

  The photocurable composition of the present invention comprises the organic pigment fine particle dispersion composition, a photopolymerizable compound, and a photopolymerization initiator (hereinafter sometimes referred to as a photopolymerization initiator system), preferably Furthermore, an alkali-soluble resin is included. Hereinafter, each component of the photocurable composition will be described.

  The organic pigment fine particles and the method for producing the dispersion composition have already been described in detail. The content of the organic pigment fine particles in the photocurable composition is preferably 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content refers to the total composition excluding the organic solvent). 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

  The photopolymerizable compound (hereinafter sometimes referred to as a polymerizable monomer or a polymerizable oligomer) is a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Is preferred. Examples of such a photopolymerizable compound include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned. Further, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  The photopolymerizable compound may be used alone or in combination of two or more. The content of the photocurable composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

  As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds), U.S. Pat. No. 2,367,660 Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon-substituted fragrances described in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones, Benzothiazole compounds and trihalomethyl-s-triazines described in Japanese Patent No. 51-48516 Compound, trihalomethyl are described in U.S. Patent No. 4239850 - triazine compounds include U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

  In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.

  The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced. The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the photocurable composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

  The alkali-soluble resin can be added at the time of preparing the photocurable composition or the inkjet ink for the color filter, but is added when the dispersion composition of the organic pigment fine particles is produced or when the organic pigment fine particles are formed. Is also preferable. An alkali-soluble resin can also be added to both or one of the second solvent for adding the organic pigment solution and the organic pigment solution to form organic pigment fine particles. Alternatively, it is also preferable to add an alkali-soluble resin solution in a separate system when forming organic pigment fine particles.

  As the alkali-soluble resin, a binder having an acidic group is preferable, and an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

  The alkali-soluble resin may be used alone or may be used in the state of a composition used in combination with a normal film-forming polymer. The amount added to 100 parts by mass of the organic pigment fine particles is 10 to 200 parts by mass. Generally, 25-100 mass parts is preferable.

  In addition, in order to improve the crosslinking efficiency, the side chain of the alkali-soluble resin may have a polymerizable group, and a UV curable resin, a thermosetting resin, or the like is also useful. Furthermore, as the alkali-soluble resin, a resin having a water-soluble atomic group in a part of the side chain can be used.

In the photocurable composition, an organic solvent (fourth solvent) for preparing the photocurable composition may be used in addition to the above components. Examples of the fourth solvent include, but are not limited to, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbons. Preferable examples include a system solvent, a nitrile solvent, or a mixture thereof. Among them, a ketone solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or these More preferably, a mixture of
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane.
These solvents may be used alone or in combination of two or more. Moreover, the solvent whose boiling point is 180 to 250 degreeC can be used if needed. As for content of an organic solvent, 10-95 mass% is preferable with respect to photocurable composition whole quantity.

  Moreover, it is preferable to contain an appropriate surfactant in the photocurable composition. Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600. As for content of surfactant, 5 mass% or less is preferable with respect to photocurable composition whole quantity.

  The photocurable composition preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less with respect to the total amount of the photocurable composition.

  In addition to the colorant (pigment), a colorant (dye, pigment) can be added to the photocurable composition as necessary. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the photocurable composition. Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The auxiliary dye or pigment content is preferably 5% by mass or less based on the total amount of the photocurable composition.

  The photocurable composition can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the photocurable composition whole quantity.

  In addition to the above additives, the photocurable composition may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like.

The photocurable composition can be made into an inkjet ink by adjusting the composition appropriately. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing, but among them, the inkjet ink for the color filter is preferable.
The ink-jet ink of the present invention is not limited as long as it contains the organic pigment fine particles, and the organic pigment fine particles are contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer. Here, as the polymerizable monomer and / or polymerizable oligomer, those described above for the photocurable composition can be used.
At this time, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by the addition of a surfactant and the type of solvent. For example, the surface tension is platinum by using a measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

  As the ink jet head (hereinafter also simply referred to as a head), a normal one can be applied, and a continuous type and a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

In addition, after each pixel is formed, a heating step of performing heat treatment (so-called baking treatment) can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The heating temperature and time depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to obtain sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix stripe shape, a lattice shape, or a delta arrangement. May be.

  In the present invention, it is preferable to prepare a partition wall in advance before the pixel forming step using the color filter inkjet ink described above, and to apply the ink to a portion surrounded by the partition wall. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.

  The components contained in the coating film using the photocurable composition are the same as those already described. Moreover, although the thickness of the coating film using a photocurable composition can be suitably determined with the use, it is preferable that it is 0.5-5.0 micrometers, and it is 1.0-3.0 micrometers. Is more preferable. In the coating film using this photocurable composition, the above-mentioned monomer or oligomer can be polymerized to form a polymerized film of the photocurable composition, and a color filter having the polymerized film can be produced (about production of a color filter) Will be described later.) Polymerization of the photopolymerizable compound can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

  In addition, although the said coating film can be formed by apply | coating and drying a photocurable composition with a normal coating method, in this invention, it is a slit which has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply by a nozzle. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  As a method for applying the photocurable composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly and highly accurately applied, and can be widely used for producing color filters. However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

  In slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate. On the other hand, this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

  In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using the slit-shaped nozzle already demonstrated. Preferred specific examples of the slit coater are the same as described above.

The color filter of the present invention is excellent in contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, and this is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter of the present invention is used for a television, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below ( Hereinafter, in the present invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

  The liquid crystal display device provided with the color filter of the present invention has a high contrast and excellent descriptive power such as black spots, and the VA system is particularly preferable. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. The color filter of the present invention can be used for a CCD device and exhibits excellent performance.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted. In the examples, “part” and “%” are based on mass unless otherwise specified.

(Synthesis Example 1)
(Synthesis of Monomer M-1)
45.28 parts of 2-thiobarbituric acid and 13.82 parts of sodium hydroxide are dissolved in 200 parts of dimethyl sulfoxide and heated to 25 ° C. To this, 57.53 parts of chloromethylstyrene is dropped, and the mixture is further heated and stirred at 55 ° C. for 5 hours. After heating and stirring, 150 parts of methanol and 150 parts of distilled water are added to the reaction solution and stirred for 1 hour. Subsequently, this solution is poured into 2000 parts of distilled water while stirring, and the resulting precipitate is filtered and washed. As a result, 80.1 parts of a vinyl monomer (hereinafter, simply referred to as “monomer M-1”) forming the repeating unit M-1 was obtained.

(Synthesis of polymer P-1)
The following monomer solution was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (manufactured by Shinto Kagaku Co., Ltd., three-one motor “trade name”), heated to 78 ° C. while flowing nitrogen into the flask. Raise the temperature and stir for 30 minutes. Then, the following initiator solution is added to said liquid, and it heat-stirs at 78 degreeC for 2 hours. The following initiator solution is further added after heating and stirring, and the operation of heating and stirring at 78 ° C. for 2 hours is repeated twice in total. After the last 2 hours of stirring, the mixture is subsequently heated and stirred at 90 degrees for 2 hours. The obtained reaction solution was poured into 1500 parts of isopropanol while stirring, and the resulting precipitate was collected by filtration and dried by heating to obtain a graft polymer P-1.
(Monomer solution)
-Monomer M-1 2.0 parts-Styrene 16.0 parts-Methacrylic acid 2.0 parts-1-Methyl-2-pyrrolidone 46.67 parts (initiator solution)
2.2'-azobis (isobutyric acid) dimethyl (Wako Pure Chemical Industries, Ltd. V-601 "trade name")
0.6 parts 1-methyl-2-pyrrolidone 2 parts

(Synthesis Example 2)
(Synthesis of polymer P-2)
V-601 is added to the initiator solution by changing the styrene used in Synthesis Example 1 to polymethyl methacrylate having a methacryloyl group at the end (number average molecular weight 6000, AA-6 (trade name) manufactured by Toa Gosei Chemical Co., Ltd.). A graft polymer P-2 was obtained in the same manner as in Synthesis Example 1 except that the amount of was changed to 0.1 part.

ＡＳ−６：片末端メタクリロイル化ポリスチレンオリゴマー（Ｍｎ＝６０００、東亜合成化学工業（株）製）、
ＡＡ―６：片末端メタクリロイル化ポリメチルメタクリレートオリゴマー（Ｍｎ＝６０００、東亜合成化学工業（株）製）
ＡＢ−６：片末端メタクリロイル化ポリ−ｎ−ブチルメタクリレートオリゴマー（Ｍｎ＝６０００、東亜合成化学工業（株）製）
ＰＭＥ−１０００；ブレンマーＰＭＥ−１０００（商品名）、メトキシポリエチレングリコールメタクリレート（日油（株）製））、
ＰＥ−３５０；ブレンマーＰＥ−３５０（商品名），ポリエチレングリコールモノメタクリレート（日油（株）製）
ＰＰ−１０００；ブレンマーＰＰ−１０００（商品名）、ポリプロピレングリコールモノメタクリレート（日油（株）製）
ＰＥＰ−３５０Ｂ；ブレンマー７０ＰＥＰ−３５０Ｂ（商品名）、ポリエチレングリコールポリプロピレングリコールモノメタクリレート（日油（株）製）、
ＦＭ５；プラクセル ＦＭ５（商品名）、ポリカプロラクトンモノメタクリレート（ダイセル化学工業（株）製） (Synthesis Examples 3-35)
Polymers P-3 to P-35 were obtained in the same manner as in Synthesis Example 1 except that the component composition of the monomer solution and the component composition of the initiator solution shown in Synthesis Example 1 were changed as shown in Table 1.

AS-6: One-end methacryloylated polystyrene oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.),
AA-6: One-terminal methacryloylated polymethyl methacrylate oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
AB-6: One-terminal methacryloylated poly-n-butyl methacrylate oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
PME-1000; Bremer PME-1000 (trade name), methoxypolyethylene glycol methacrylate (manufactured by NOF Corporation)),
PE-350; Bremer PE-350 (trade name), polyethylene glycol monomethacrylate (manufactured by NOF Corporation)
PP-1000; Bremmer PP-1000 (trade name), polypropylene glycol monomethacrylate (manufactured by NOF Corporation)
PEP-350B; BLEMMER 70PEP-350B (trade name), polyethylene glycol polypropylene glycol monomethacrylate (manufactured by NOF Corporation),
FM5: Plaxel FM5 (trade name), polycaprolactone monomethacrylate (manufactured by Daicel Chemical Industries, Ltd.)

MAA; methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DMAPAAm; dimethylaminopropylacrylamide (Wako Pure Chemical Industries, Ltd.)
DMVBAm; N, N-dimethyl-4-vinylbenzamide tBuSt; 4-tbutylstyrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
4-Vpy; 4-vinylpyridine VIm; N-vinylimidazole AA; acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
NMP; 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
BMA: Butyl methacrylate (manufactured by Wako Pure Chemical Industries)
tBMA: t-butyl methacrylate (Wako Pure Chemical Industries, Ltd.)
BAAm: Butylacrylamide (Wako Pure Chemical Industries, Ltd.)
MAAm: Methylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
StMA: Stearyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
DMA: dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
IbMA: Isobornyl methacrylate (manufactured by Aldrich)
CyMA: cyclohexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
M-X and Q-X mean vinyl monomers corresponding to the above exemplified repeating units.

Example 1
While heating 2500 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as the first solvent to 80 ° C., the pigment C.I. I. Pigment Violet 23 (manufactured by Clariant, Hostaperm Violet RL-NF [trade name]) 112.5 g and polymethyl methacrylate (mass average molecular weight 20000) 80.0 g were added to prepare pigment solution 1.

  Separately, 2000 ml of water containing 20 ml of 1 mol / l sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as the second solvent.

  Here, the temperature of the solution was controlled at 25 ° C., and the pigment solution 1 at 80 ° C. was added to the second solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Infusion was performed using a KX-500 type large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). The pigment solution 1 feed pipe has a flow path diameter and a supply port diameter of 2.2 mm. The supply port is placed in a second solvent and injected at a flow rate of 200 ml / min to inject 220 ml, thereby forming organic pigment particles and dispersing the pigment. A liquid was prepared. The fine particles in the pigment dispersion were measured for particle size and monodispersity using Nanotrac UPA-EX150 [trade name] manufactured by Nikkiso Co., Ltd. The number average particle size was 35 nm and Mv / Mn 1.50, respectively. Met.

  The pigment dispersion prepared by the above procedure was used for 90 minutes at 3000 rpm using an H-110A type centrifugal filter manufactured by Kokusan Co., Ltd. [trade name] and a P89C type cloth manufactured by Shikishima Canvas Co. Concentrate, remove the solvent from the pigment dispersion, reduce (first concentration / removal step), and dry at 80 ° C. for 12 hours to obtain powder V-1 consisting of flocs of organic pigment fine particles (organic pigment content 59 0.0 mass%).

Using the organic pigment fine particle powder V-1, the following composition was prepared, and a motor mill M-50 (manufactured by Eiger Japan) was used with zirconia beads having a diameter of 0.65 mm and a peripheral speed of 9 m / s. The pigment dispersion composition 1 was produced by time dispersion. At this time, the organic pigment fine particles showed good self-dispersibility with respect to 1-methoxy-2-propyl acetate.
Organic Pigment Fine Powder V-1 20.4 g (Pigment 12.04 g)
1-methoxy-2-propyl acetate (PGMEA) “third solvent” 100.0 g

[Contrast measurement]
The obtained pigment dispersion composition 1 was applied on a glass substrate so as to have a thickness of 2 μm, thereby preparing a sample. As a backlight unit, a three-wavelength cold-cathode tube light source (FWL18EX-N [trade name] manufactured by Toshiba Lighting & Technology Co., Ltd.) having a diffuser plate is used, and two polarizing plates (polarized light manufactured by Sanritsu Co., Ltd.) This sample is placed between the plates HLC2-2518 [trade name], and the amount of transmitted light when the polarization axis is parallel and when the polarization axis is parallel is measured, and the ratio is defined as the contrast ("1990 7th Color” Optical conference, 512 color display 10.4 "size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka" etc.). Two polarizing plates, a sample, and a color luminance meter are installed at a position where the polarizing plate is 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is installed at a position of 40 mm to 60 mm. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The light quantity of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed. The obtained contrast measurement results are shown in Table 3.

(Examples 2 to 24) (Comparative Examples 1 and 2)
In Example 1, pigment dispersion compositions 2 to 24 and pigment dispersion compositions c1 and c2 for comparison were prepared in the same manner except that the composition of each agent used was changed to that shown in Table 2 below. The contrast was measured. The results are shown in Table 3. However, when the first solvent is methanesulfonic acid / formic acid, 2000 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries) and 500 ml of formic acid (manufactured by Wako Pure Chemical Industries) are heated to 60 ° C. as the first solvent to dissolve the pigment. A liquid was prepared. The same solvent as Example 1 was used for the second solvent and the third solvent. Moreover, when using the dispersing agent for redispersion, the following composition was prepared using the powder of each produced organic pigment fine particle, and a motor mill M-50 (made by Eiger Japan) made a diameter of 0.65 mm. By using zirconia beads and dispersing at a peripheral speed of 9 m / s for 2 hours, a pigment dispersion composition was obtained.

(Example 25)
To 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) as the first solvent, 35.9 ml of 26% methanol solution of tetramethylammonium hydroxide, pigment C.I. I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 50 g and Polymer P-1 50.0 g were added to prepare Pigment Solution 1. Separately, 1000 ml of water containing 16 ml of 1 mol / l hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as the second solvent.
Here, the temperature was controlled at 5 ° C., and the pigment solution 1 was added to 1000 ml of the second solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.), and NP-KX-500 type. Using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.), 100 ml is injected from a liquid feed pipe having a flow path diameter of 1.1 mm at a flow rate of 400 ml / min to form organic pigment fine particles. A particle dispersion 25 was prepared.
Using the H-112 type centrifugal filter machine (trade name) manufactured by Kokusan Co., Ltd. and the P89C type fabric cloth (trade name) manufactured by Shikishima Canvas Co., Ltd. Concentrate at 5000 rpm for 90 minutes, remove the solvent from the pigment dispersion, reduce (first concentration / removal step), and dry at 80 ° C. for 12 hours to obtain powder V-25 composed of flocs of organic pigment fine particles (organic Pigment content 59.0% by weight).
Using the organic pigment fine particle powder V-25, the following composition was prepared, and motor mill M-50 (manufactured by Eiger Japan) was used with zirconia beads having a diameter of 0.65 mm and a peripheral speed of 9 m / s and 12 The pigment dispersion composition 25 was produced by time dispersion.
Organic pigment fine particle powder V-25 20.4 g (pigment 12.04 g)
Solsperse 39000 "Product Name (described later)" 1.2g
98.8 g of 1-methoxy-2-propyl acetate (PGMEA) “third solvent”

(Examples 26 to 60) (Comparative Examples 3 and 4)
In Example 25, pigment dispersion compositions 26 to 60 (Examples 26 to 60), and pigment dispersion compositions for comparison, except that the composition of each agent used was changed to that shown in the table below. Products c3 and c4 (Comparative Examples 3 and 4) were prepared. The second solvent and the third solvent were the same as in Example 25.

Polymethyl methacrylate (polymer compound insoluble in water, mass average molecular weight 20000)
Polypropylene glycol (polymer compound insoluble in water, weight average molecular weight 3000)
・ Polyε-caprolactone (polymer compound insoluble in water, weight average molecular weight 10,000)
-Methyl methacrylate / styrene copolymer (polymer compound insoluble in water, composition ratio 80/20% by mass, mass average molecular weight 10,000)
Benzyl methacrylate / acrylic acid copolymer (polymer compound insoluble in water, composition ratio 95/5 mass%, mass average molecular weight 20000)
・ Methyl methacrylate / N, N-dimethylaminopropylacrylamide copolymer (polymer compound insoluble in water, composition ratio 90/10% by mass, mass average molecular weight 30000)
-PVP: polyvinylpyrrolidone (polymer compound soluble in water, Wako Pure Chemicals, trade name: K30, mass average molecular weight 40000)
EFKA6745 (trade name, manufactured by EFKA, pigment derivative)
・ Polyallylamine hydrochloride (manufactured by Nittobo Co., Ltd., mass average molecular weight 100,000)
・ Polyacrylic acid (mass average molecular weight 25000)
・ Solspers 55000 (trade name, manufactured by Lubrizol, Graft type dispersant)
・ Solspers 39000 (trade name, manufactured by Lubrizol, Graft type dispersant)
MSA: methanesulfonic acid MPA: 1-methoxy-2-propyl acetate DMSO: dimethyl sulfoxide SM-28: sodium methoxide 28% methanol solution TMAH: tetramethylammonium hydroxide 26% methanol solution

  As shown in Table 3, the organic pigment fine particles of the dispersion composition of the comparative example did not exhibit self-dispersibility and gelled, and the contrast could not be measured. On the other hand, the organic pigment fine particles (Examples) of the present invention showed good self-dispersibility and realized high contrast, and showed higher contrast by adding a dispersing agent for redispersion. Further, from the above results, according to the present invention, the polymer compound contained in the pigment solution and used for stabilizing the dispersion at the time of the fine particle folding is allowed to act on the stabilization of the dispersion of the third solvent as it is, so that the fine particles are self-dispersed. Therefore, it can be understood that the labor of taking out and switching the polymer compound can be largely omitted, and manufacturing with extremely high environmental compatibility can be realized along with the improvement of the process efficiency and the cost.

(Example 61)
[Preparation of color filter (preparation by application using slit-shaped nozzle)]
[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 4 below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. The photocurable composition K1 consisting of was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photocurable composition layer K1 was obtained.

[Table 4]
--------------------------------------
K pigment dispersion (carbon black) 25 parts by mass 1-methoxy-2-propyl acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Alkali-soluble resin 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 Part by mass polymerization initiator A 0.16 parts by mass surfactant 1 0.044 parts by mass ---------------------------- ----------
In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photocurable composition layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photocurable composition K1, and then a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1). , Manufactured by Fuji Film Electronics Materials Co., Ltd.) and subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

[Formation of red (R) pixels]
A heat-treated pixel R was formed on the substrate on which the image K was formed using the photocurable composition R1 having the composition shown in Table 5 below in the same process as the formation of the black (K) image.
The film thickness of the photocurable composition R1 and the coating amount of the pigments (CIPR 254 and CIPR 177) are shown below.
Photocurable composition film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.70
C. I. P. R. 177 coating amount (g / m ² ) 0.30

[Table 5]
--------------------------------------
R pigment dispersion A (CIPP.254) 35 parts by mass R pigment dispersion B (CIPP.177) 6.8 parts by mass 1-methoxy-2-propyl acetate 7. 6 parts by weight Methyl ethyl ketone 37 parts by weight Alkali-soluble resin 1 0.7 parts by weight DPHA solution 3.8 parts by weight Polymerization initiator B 0.12 parts by weight Polymerization initiator A 0.05 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.06 parts by mass -------------------------------------

[Formation of green (G) pixels]
Using the photocurable composition G1 having the composition shown in Table 6 below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. did. The film thickness of the photocurable composition layer G1 and the coating amounts of pigments (CIPG36 and CIPY150) are shown below.
Photocurable composition film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 6]
--------------------------------------
G pigment dispersion (C.I.P.G.36) 28 parts by mass Y pigment dispersion (C.I.P.Y.150) 15 parts by mass 1-methoxy-2-propyl acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Parts Cyclohexanone 1.3 parts by weight Alkali-soluble resin 2 2.5 parts by weight DPHA solution 3.5 parts by weight Polymerization initiator B 0.12 parts by weight Polymerization initiator A 0.05 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.07 parts by mass -------------------------------------

[Formation of blue (B) pixels]
The substrate on which the image K, the pixel R, and the pixel G are formed uses a photocurable composition B1 having the composition shown in Table 7 below, and is subjected to heat treatment in the same process as the formation of the black (K) image. B was formed, and the target color filter A was obtained.
The film thickness of the photocurable composition layer B1 and the coating amounts of the pigments (CIPB15: 6 and CIPVV23) are shown below.
Photocurable composition film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.45
C. I. P. V. 23 coating amount (g / m ² ) 0.30

[Table 7]
--------------------------------------
B Pigment Dispersion (CIPP.15: 6) 15.0 parts by mass V Pigment Dispersion 1 (CIPV.23) 7.5 parts by mass 1-methoxy-2-propyl Acetate 28 parts by weight Methyl ethyl ketone 26 parts by weight Alkali-soluble resin 3 17 parts by weight DPHA solution 4.0 parts by weight Polymerization initiator B 0.17 parts by weight Phenothiazine 0.02 parts by weight Surfactant 1 0.06 parts by weight ---- ----------------------------------

Here, the preparation of the photocurable compositions K1, R1, G1, and B1 described in the above table will be described in more detail.
The photocurable composition K1 was first weighed in the amount of K pigment dispersion listed in the table, 1-methoxy-2-propyl acetate, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, alkali-soluble resin 2, hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bis) in the amounts shown in the table Ethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine) and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and at a temperature of 40 ° C. (± 2 ° C.). It was obtained by stirring at 150 rpm for 30 minutes.

In addition, the composition was shown below about the following component among the compositions described in a table | surface.
<K pigment dispersion>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan)
13.1 parts by mass / Pigment Dispersant A 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 37,000) 6.72 parts by mass 1-methoxy-2-propyl acetate 79.53 parts by mass

<Alkali-soluble resin 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
(Random copolymer, molecular weight 38,000) 27 parts by mass 1-methoxy-2-propyl acetate 73 parts by mass <DPHA solution>
Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd.,
Product name: KAYARAD DPHA) 76 parts by mass 1-methoxy-2-propyl acetate 24 parts by mass <Surfactant 1>
・ Megafac F-780-F (Dainippon Ink Chemical Co., Ltd.)
C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ : 40 parts by mass;
H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ : 55 parts by mass;
H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ : Copolymer with 5 parts by mass (mass average molecular weight 30 million) 30 parts by mass / methyl ethyl ketone 70 parts by mass

  For the photocurable composition R1, first, R pigment dispersion A, R pigment dispersion B and 1-methoxy-2-propyl acetate in the amounts shown in the table are weighed and mixed at a temperature of 24 ° C. (± 2 ° C.). And then stirred for 10 minutes at 150 rpm, and then the amounts of methyl ethyl ketone, alkali-soluble resin 1, DPHA solution, polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) -1,3,4) listed in the table -Oxadiazole), polymerization initiator A, and phenothiazine were weighed out, added in this order at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and the surfactant 1 in the amount shown in the table was further added. It was obtained by weighing, adding at a temperature of 24 ° C. (± 2 ° C.), stirring at 30 rpm for 5 minutes, and filtering through nylon mesh # 200.

In addition, among the compositions described in the table, R pigment dispersion A and pigment dispersion B use the method described in Example 1 of International Publication No. WO2006 / 121016 pamphlet, and the composition becomes the following parts by mass. It was prepared as described above.
<R pigment dispersion A>
・ C. I. P. R. 254 (trade name: Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 10 parts by mass, 1 part by mass of pigment dispersant A, polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 30,000) 10 parts by mass, 1-methoxy-2-propyl acetate 79 parts by mass <R pigment dispersion B>
・ C. I. P. R. 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) 22.5 parts by mass. Polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 30,000) 15 1 part by mass, 62.5 parts by mass of 1-methoxy-2-propyl acetate

<Alkali-soluble resin 1>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, molecular weight 40,000) 27 parts by mass 1-methoxy-2-propyl acetate 73 parts by mass

  The photocurable composition G1 was first weighed in the amounts of G pigment dispersion, Y pigment dispersion and 1-methoxy-2-propyl acetate listed in the table, mixed at a temperature of 24 ° C. (± 2 ° C.) and 150 rpm. And then weigh out the amounts of methyl ethyl ketone, cyclohexanone, alkali-soluble resin 2, DPHA solution, polymerization initiator B, polymerization initiator A, and phenothiazine as shown in the table at a temperature of 24 ° C. (± 2 ° C.). Add in this order and stir at 150 rpm for 30 minutes, then weigh out the amount of surfactant 1 listed in the table, add it at a temperature of 24 ° C. (± 2 ° C.), stir at 30 rpm for 5 minutes, nylon mesh # Obtained by filtering through 200.

  In addition, among the compositions described in the table, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used as the G pigment dispersion. As the Y pigment dispersion, “trade name: CF erotic-EX3393” manufactured by Mikuni Color Co., Ltd. was used.

  The photocurable composition B1 was first weighed out the amounts of B pigment dispersion, V pigment dispersion 1, and 1-methoxy-2-propyl acetate listed in the table, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 rpm for 10 minutes, then weigh out the amounts of methyl ethyl ketone, alkali-soluble resin 3, DPHA solution, polymerization initiator B, phenothiazine, and add them in this order at a temperature of 25 ° C. (± 2 ° C.) Stir at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.), then weigh out the surfactant 1 in the amount shown in the table, add it at a temperature of 24 ° C. (± 2 ° C.), and stir for 5 minutes at 30 rpm. Obtained by filtration through nylon mesh # 200.

  Of the compositions shown in the table, “Brand Name: CF Bull-EX3357” manufactured by Mikuni Color Co., Ltd. was used as the B pigment dispersion. As the V pigment dispersion 1, the pigment dispersion composition 1 prepared in Example 1 was used.

The composition of the alkali-soluble resin 3 is as follows.
<Alkali-soluble resin 3>
・ 27 parts by mass of polymer (random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio, molecular weight 37,000) ・ 73 parts by mass of 1-methoxy-2-propyl acetate

  The color filter 1 was produced as described above. Color filters 2 to 24, c1, and c2 were prepared in the same manner as color filter A, except that V pigment dispersion composition 1 used in color filter 1 was replaced with V pigment dispersion compositions 2 to 24, c1, and c2, respectively. . The results of measuring the contrast for each color filter in the same manner as in [Measurement of contrast] are shown in Table 3 below. In addition, as the V pigment dispersion compositions c1 and c2, a gel-like dispersion composition having a very high viscosity was used as it was.

[Table 8]
---------------------------
Example Color filter Contrast ---------------------------
Example 61 # 1 6,200
Example 62 # 2 5,800
Example 63 # 3 6,500
Example 64 # 4 5,700
Example 65 # 5 6,300
Example 66 # 6 6,250
Example 67 # 7 6,800
Example 68 # 8 5,300
Example 69 # 9 5,300
Example 70 # 10 5,900
Example 71 # 11 5,800
Example 72 # 12 10,500
Example 73 # 13 7,300
Example 74 # 14 10,900
Example 75 # 15 10,300
Example 76 # 16 9,700
Example 77 # 17 9,700
Example 78 # 18 9,300
Example 79 # 19 10,000
Example 80 # 20 10,500
Example 81 # 21 8,000
Example 82 # 22 10,000
Example 83 # 23 11,000
Example 84 # 24 10,000
Comparative Example 5 # c1 250
Comparative Example 6 # c2 400
-------------------------

  From the results shown in Table 8, the color filters 1 to 24 of the present invention all have high contrast and can exhibit good display characteristics when incorporated in a display device. On the other hand, the color filters c1 and c2 of the comparative example had a low contrast and a level that did not satisfy practical requirements. From this result, according to the present invention, it is possible to manufacture the above-described high-performance color filter efficiently and at low cost by realizing environmental adaptation without using or switching unnecessary polymer compounds.

Claims (24)

Self-dispersible organic pigment fine particles having an organic pigment and a polymer compound,
The organic pigment fine particles are prepared by mixing an organic pigment solution in which the organic pigment and the polymer compound are dissolved in a first solvent, and a second solvent that is a poor solvent for the organic pigment and is compatible with the first solvent. , Nanometer-sized fine particles deposited in the mixed solution, and a third compound different from both the first solvent and the second solvent by using a compound insoluble in the second solvent as the polymer compound. Organic pigment fine particles characterized in that they can be self-dispersed in a solvent.   The organic pigment fine particles according to claim 1, wherein the polymer compound has a mass average molecular weight of 1,000 to 500,000.   The polymer compound is at least one polymer compound selected from the group consisting of polymers and copolymers of vinyl monomers, ester polymers, ether polymers, and modified products and copolymers thereof. The organic pigment fine particles according to claim 1 or 2. The organic pigment fine particles according to any one of claims 1 to 3, wherein the polymer compound is a polymer or copolymer of a vinyl monomer having a hydrocarbon group having 4 or more carbon atoms. The organic pigment fine particles according to any one of claims 1 to 4, wherein the polymer compound has a repeating unit represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group; J represents —CO—, —COO—, —CONR ⁶ —, —OCO—, a phenylene group, or —C ₆ H ₄ CO— group; ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ¹ represents a linear, branched, or cyclic alkylene group, an aralkylene group, or a single bond, and P represents a heterocyclic group. The organic pigment fine particles according to any one of claims 1 to 5, wherein the polymer compound further has a repeating unit represented by the following general formula (2) or (3).

(R ¹ represents a hydrogen atom or a methyl group. Y represents —NH—, —O—, or —S—. W ² represents a single bond or a divalent linking group. P represents a heterocyclic group. .) The organic compound according to claim 5 or 6, wherein P in the general formula (1), (2), or (3) is represented by the general formula (4) or a tautomer structure thereof. Pigment fine particles.

(R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a hydrogen atom. R ³ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an azo group.)   The said high molecular compound is a graft copolymer which has a side chain which the polymeric oligomer which has an ethylenically unsaturated double bond at the terminal makes | forms, The any one of Claims 1-7 characterized by the above-mentioned. Organic pigment fine particles.   The organic pigment fine particles according to any one of claims 1 to 8, wherein the organic pigment solution further contains at least one organic compound having a basic group or an acidic group. The said organic pigment solution and the 2nd solvent were mixed on the conditions from which the Reynolds number Re represented by the following Formula (1) becomes 50 or more, The any one of Claims 1-9 characterized by the above-mentioned. Organic pigment fine particles.
Re = ρUL / μ (1)
[In formula (1), Re represents the Reynolds number, ρ represents the density of the organic pigment solution, U represents the relative speed at which the organic pigment solution and the second solvent meet, and L represents the organic pigment solution and the second solvent. 2 represents the equivalent diameter of the flow path or supply port where the solvent meets, and μ represents the viscosity coefficient of the organic pigment solution. ]   The said 1st solvent is at least 1 or more types selected from the group which consists of an organic acid, an organic base, a sulfoxide compound solvent, and an amide compound solvent, The any one of Claims 1-10 characterized by the above-mentioned. Organic pigment fine particles.   The organic pigment fine particles according to any one of claims 1 to 11, wherein the second solvent is at least one selected from the group consisting of an aqueous medium and an alcohol compound solvent.   The third solvent is at least one solvent selected from the group consisting of ether compound solvents, ester compound solvents, aromatic hydrocarbon compound solvents, and aliphatic hydrocarbon compound solvents. Item 13. The organic pigment fine particles according to any one of Items 1 to 12.   The organic pigment fine particles according to any one of claims 1 to 13, wherein the organic pigment solution contains 10 to 300 parts by mass of the polymer compound with respect to 100 parts by mass of the organic pigment. .   An organic pigment solution in which an organic pigment and a polymer compound are dissolved in a first solvent and a second solvent that is a poor solvent for the organic pigment and is compatible with the first solvent are mixed, and the organic solvent is mixed in the mixed solution. In depositing nanometer-sized fine particles having a pigment and the polymer compound, a compound that is insoluble in the second solvent is used as the polymer compound, and the fine particles are added to either the first solvent or the second solvent. A method for producing organic pigment fine particles, which can self-disperse in a different third solvent.   A pigment dispersion composition, wherein the organic pigment fine particles according to claim 1 are self-dispersed in the third solvent.   The pigment dispersion composition according to claim 16, further comprising a pigment dispersant.   A photocurable composition comprising the pigment dispersion composition according to claim 16 or 17, a photopolymerizable compound, and a photopolymerization initiator.   Furthermore, alkali-soluble resin was contained, The photocurable composition of Claim 18 characterized by the above-mentioned.   The photocurable composition according to claim 18 or 19, wherein the photocurable composition is for a color filter.   A color filter comprising a colored pattern formed using the photocurable composition according to any one of claims 18 to 20 on a substrate.   A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to any one of claims 18 to 20 on a substrate directly or via a predetermined layer, and a formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development on the conductive film.   An inkjet ink comprising the organic pigment fine particles according to any one of claims 1 to 14 contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer.   The inkjet ink according to claim 23, wherein the inkjet ink is for a color filter.