JP2009079158A - Organic pigment fine particles and production method thereof, pigment dispersion composition containing the same, photocurable composition, inkjet ink, color filter using them, and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide organic pigment fine particles and a method for manufacturing the particles improving display characteristics of a color filter used for a liquid crystal display or the like, to provide a pigment dispersion composition, a photosetting composition and inkjet ink containing the particles, and to provide a color filter and a method for manufacturing the color filter using them. <P>SOLUTION: The organic pigment fine particles contain a polymer compound (1-1) and an organic compound (2-1) having an acidic group, and are characterized in that: the fine particles are obtained by mixing a solution prepared by dissolving an organic pigment together with the above polymer compound (1-1) and the organic compound (2-1) in a good solvent, and a poor solvent to the organic pigment, and precipitating the organic pigment into fine particles in a nanometer size; and the polymer compound (1-1) is a compound having affinity with the poor solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

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 with red (R), green (G), and blue (B) colored pixel portions formed on the 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. A photocurable pigment composition may be used to form the colored pixel portion. This pigment composition is prepared by adjusting a chemical characteristic by adding a resin or the like to a pigment dispersion liquid and a photocurable compound in which an organic pigment is dispersed, if necessary.

  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.

  By the way, as nanotechnology, for example, research for reducing the size of particles to a range of 10 to 100 nm and applying them to various uses has been vigorously advanced. It is intended to bring out new properties that could not be predicted in the past due to the effects that are manifested for the first time by using nanometer size. On the other hand, in the field of organic pigments, for example, research and development of paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like are underway. In particular, the above-described color filter and ink-jet ink have been developed for high performance using fine chemical technology, and the results are expected.

  Here, the organic pigment dispersion method includes various milling methods such as a bead mill method and a salt milling method, and a liquid phase method. In the milling method, it is difficult to sufficiently refine the organic pigment and disperse it in the composition (see Patent Document 1). In contrast, the liquid phase method is suitable for obtaining fine pigment particles. Specifically, a method of mixing a pigment solution and a poor solvent to precipitate nanoparticles and adding a predetermined polymer compound is disclosed. (See Patent Documents 2 to 5).

JP 2000-239554 A International Publication No. WO2006 / 121016 Pamphlet JP 2004-043776 A JP 2007-023169 A JP 2007-119586 A

  The present invention relates to organic pigment fine particles capable of improving the properties of color filters used in liquid crystal display devices and the like, a method for producing the same, a pigment dispersion composition containing the same, a photocurable composition, an inkjet ink, and a color using them It aims at providing a filter and its manufacturing method. In particular, organic pigment fine particles capable of increasing the contrast of a color filter and improving its production quality and realizing good display characteristics in a liquid crystal display device, a method for producing the same, a pigment dispersion composition containing the same, and a photocurable composition The object is to provide a product, inkjet ink, a color filter using them, and a method for producing the same.

The above problems have been achieved by the following means.
(1) Organic pigment fine particles containing a polymer compound (1-1) and an organic compound (2-1) having an acidic group, wherein the fine particles contain an organic pigment in a good solvent as the polymer compound (1). -1) and a solution dissolved together with the organic compound (2-1) and a poor solvent for the organic pigment are mixed, and the organic pigment is precipitated as nanometer-sized fine particles. Organic pigment fine particles characterized in that (1-1) is a compound having affinity for the poor solvent.
(2) Organic pigment fine particles having a polymer compound (1-2) and an organic compound (2-2) containing a basic group or an acidic group, the fine particles containing the organic pigment in a good solvent. A solution obtained by dissolving together with the molecular compound (1-2) and the organic compound (2-2) and a poor solvent for the organic pigment are mixed to precipitate the organic pigment as nanometer-sized fine particles. Organic pigment fine particles, wherein the polymer compound (1-2) is a compound not containing a nitrogen atom having an affinity for the poor solvent.
(3) The organic pigment fine particles according to (1) or (2), wherein the polymer compound (1-1) or (1-2) has a mass average molecular weight of 1000 to 500,000.
(4) The polymer compound (1-1) or (1-2) is a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, a silicone polymer, The organic pigment fine particles according to any one of (1) to (3), wherein the organic pigment fine particles are at least one polymer compound selected from these modified products and copolymers.
(5) The solution of the organic pigment and the poor solvent are mixed under a condition that the Reynolds number Re represented by the following formula (1) is 50 or more: (1) to (4) Organic pigment fine particles given in any 1 paragraph.
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 when the organic pigment solution and the poor solvent meet, and L represents the organic pigment solution and the poor solvent. Represents the equivalent diameter of the flow path or the supply port of the part where and meet, and μ represents the viscosity coefficient of the organic pigment solution. ]
(6) Any one of (1) to (5), wherein the good solvent is at least one selected from the group consisting of an organic acid, an organic base, a sulfoxide solvent, and an amide solvent. 2. Organic pigment fine particles according to item 1.
(7) The organic pigment fine particles according to any one of (1) to (6), wherein the good solvent is at least one selected from the group consisting of an aqueous solvent and an alcohol solvent. .
(8) The organic pigment solution contains the polymer compound (1-1) and / or (1-2) in an amount of 1 part by mass to 1000 parts by mass with respect to 100 parts by mass of the organic pigment. The organic pigment fine particles according to any one of (1) to (7).
(9) A pigment dispersion comprising the organic pigment fine particles according to any one of (1) to (8) and a third solvent different from both the good solvent and the poor solvent Composition.
(10) The third solvent is at least one solvent selected from the group consisting of ether solvents, ester solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents. The pigment dispersion composition according to (9).
(11) The pigment dispersion composition according to (9) or (10), further comprising a pigment dispersant.
(12) A photocurable composition comprising the pigment dispersion composition according to any one of (9) to (11), a photopolymerizable compound, and a photopolymerization initiator.
(13) The photocurable composition as described in (12), further comprising an alkali-soluble resin.
(14) The photocurable composition as described in (12) or (13), which is used for a color filter.
(15) A color filter comprising a colored pattern using the photocurable composition according to (14) on a substrate.
(16) A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to (14) directly or via another layer to a substrate, and the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development.
(17) An inkjet ink characterized in that the organic pigment fine particles according to any one of (1) to (8) are contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer.
(18) The inkjet ink as described in (17), which is used for a color filter.
(19) Organic pigment fine particles having a polymer compound (1-1) and an organic compound (2-2) containing a basic group or an acidic group, wherein the fine particles contain the organic pigment in a good solvent. A solution obtained by dissolving together with the molecular compound (1-1) and the organic compound (2-2) and a poor solvent for the organic pigment are mixed to precipitate the organic pigment as nanometer-sized fine particles. Organic pigment fine particles, wherein the polymer compound (1-1) is a compound having an affinity for the poor solvent.

  The organic pigment fine particles, the pigment dispersion composition, the photocurable composition, and the ink-jet ink containing the organic pigment fine particles of the present invention have a high contrast and a high quality and high production efficiency of the color filter produced using them. Good display characteristics can be realized in the liquid crystal display device. Moreover, according to the production method of the present invention, the above-described excellent organic pigment fine particles can be produced efficiently and with high purity. Furthermore, the color filter produced using the organic pigment fine particles of the present invention, the pigment dispersion composition containing the organic pigment fine particles, the photocurable composition, and the ink-jet ink suppresses color unevenness in the liquid crystal display device, and the black color, It has an excellent effect of showing good characteristics in the depiction of.

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

  In the present invention, a solution in which organic pigment fine particles (hereinafter sometimes simply referred to as pigment fine particles or pigment nanoparticles) are dissolved in the above organic pigment in a good solvent (first solvent), and a poor solvent for the organic pigment (second In order to control the particle size of the pigment particles at the nanometer scale, the organic pigment solution has a high molecular compound (1-1) or an affinity for the poor solvent. The high molecular compound (1-2) which does not contain the nitrogen atom which has affinity with the said poor solvent is contained.

  The polymer compound (1-1) or (1-2) used in the present invention is soluble in a good solvent (first solvent) and a poor solvent (second solvent), and the organic pigment solution and the above When the pigment is precipitated by mixing with the second solvent, the polymer compound is preferably a polymer compound that quickly adsorbs to the deposited pigment. In the present invention, when the solubility of the polymer compound in the solvent is 4.0% by mass or more, the polymer compound is defined as having an affinity for the solvent.

  The mass average molecular weight of the polymer compound (1-1) or (1-2) is not particularly limited, but is preferably 1000 to 500000, more preferably 2000 to 300000, and 3000 to 200000. It is particularly preferred. The shape of the polymer compound may be linear or branched (for example, graft, star shape, etc.). Moreover, when a polymer is a copolymer, any of a random copolymer, an alternating copolymer, and a block copolymer may be sufficient. In the present invention, when simply referred to as molecular weight, it means mass average molecular weight, and unless otherwise specified, the mass average molecular weight is a mass average molecular weight in terms of polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran).

The polymer compound is not particularly limited, but a vinyl monomer polymer or copolymer (for example, a homopolymer of acrylic acid, a homopolymer of allylamine hydrochlorides, a copolymer of alkyl methacrylate / methacrylic acid, Polyvinyl alcohol), ester polymers (for example, polycaprolactone), ether polymers (for example, polyethylene oxide), urethane polymers (for example, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amide polymers ( For example, polyamide 6, polyamide 66, etc.), silicone polymer (eg, polydimethylsiloxane), carbonate polymer (eg, polycarbonate synthesized from bisphenol A and phosgene) Etc., 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 preferably a polymer or copolymer of vinyl monomers.

  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.

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

  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 monomer having a basic nitrogen atom, (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1- (N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N- Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acryl Piperidinoethyl acid, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -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) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) Ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1, Examples thereof include 1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like. Examples of styrenes include N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene.

  Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone 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.

Further, a polymerizable oligomer having an ethylenically unsaturated bond at the terminal (hereinafter sometimes referred to as a macromonomer) may be used. Here, the polymerizable oligomer is composed of a polymer chain portion and a polymerizable functional group portion having an ethylenically unsaturated double bond at its terminal. The polymer chain portion 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 group having an ethylenically unsaturated double bond is preferably a (meth) acryloyl group.
Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
Preferable examples of the macromonomer include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and poly-i-butyl (meth) acrylate, and a (meth) acryloyl group bonded to one molecular terminal of polystyrene. Mention may be made of polymers. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei 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 acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

  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.

Of these, water-soluble polymer compounds are preferred.
Specific examples of the water-soluble polymer compound include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol- Partial butyral, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylic acid, polyacrylic acid sodium salt, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine , polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, a diallylamine monomer / SO ₂ copolymer, diaryl Rylamine hydrochloride / maleic acid copolymer, polydiallylmethylamine hydrochloride, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymer, condensed naphthalenesulfonate, cellulose derivatives (hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, Carboxymethylcellulose, etc.) and starch derivatives. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tongant gum, lignin sulfonate, etc. can 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 polymer compounds can be used alone or in combination of two or more.

  The polymer compound (1-1) or (1-2) preferably has a mass average molecular weight of 1,000 to 500,000, more preferably 10,000 to 500,000. It is particularly preferably from 000 to 100,000.

  Examples of the anionic water-soluble polymer compound (anionic surfactant) include N-acyl amino acid salts, polyoxyethylene, alkyl ether carboxylates, acylated peptides, N-acyl-N-alkyl taurine salts, fatty acid salts, Alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, α-olefin sulfonate, N-acyl sulfonate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxy Ethylene alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, alkyl amide sulfate, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, polyoxyethylene Alkyl ether phosphate, bispolyoxyethylene alkyl ether phosphate, tris polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl ether phosphate, bis polyoxyethylene alkyl aryl ether phosphate, tris polyoxy And ethylene alkylaryl ether phosphate. 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 polymer compounds can be used alone or in combination of two or more.

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

  The amphoteric polymer compound is a polymer compound having both an anion group part in the molecule of the anionic polymer compound and a cation group part in the molecule of the cationic polymer compound.

  Nonionic polymer compounds (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine And glycerin fatty acid ester. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic polymer compounds can be used alone or in combination of two or more.

  The polymer compound (1-2) not containing nitrogen is typically one that does not contain a nitrogen atom among the polymer compounds listed above. These polymer compounds containing nitrogen were used as color filters. In some cases, it may be colored by baking.

  In the present invention, the amount of the polymer compound (1-1) and / or (1-2) used is not particularly limited, but the viewpoint of controlling the particle diameter of the organic pigment fine particles to a nanometer size, and the precipitated organic From the viewpoint of the take-out property of the pigment fine particles, it is preferably in the range of 0.1 to 1000% by mass, more preferably in the range of 1.0 to 1000% by mass, and 1.0 to 500% based on the pigment. It is particularly preferable that the mass range. Within the above range, the particle diameter of the organic pigment fine particles can be controlled to a nanometer size, and the take-out property of the precipitated organic pigment fine particles is also good. The polymer compounds may be used alone or in combination of two or more.

  In the present invention, when the organic pigment fine particles are precipitated, the organic pigment solution is subjected to (i) the polymer compound (1) in order to control the particle size of the pigment particles at the nanoscale and to perform acid-base treatment on the surface of the pigment particles. -1) and an organic compound (2-1) having an acidic group, (ii) the polymer compound (1-2) and an organic compound (2-2) having an acidic group or basicity, or (iii) the high It is preferable to contain the molecular compound (1-1) and the organic compound (2-2) having an acidic group or a basic group. Thereby, the effect of improving the filterability in the middle of the process and improving the redispersibility in the third solvent can be expected by treating the pigment particles with the acid-base. Among them, the combination of (i) or (ii) above preferable. However, in the combination of the polymer compound (1-1) or (1-2) and the organic compound (2-1) or (2-2), the same compound is not combined. Furthermore, it is more preferable to use a water-soluble polymer compound among the polymer compounds (1-1) and (1-2), and i) the water-soluble polymer compound (1-1) and an acidic group. The combination of the organic compound (2-1) and (ii) the water-soluble polymer compound (1-2) and the organic compound (2-2) having an acidic group or basicity is most preferable. Hereinafter, the organic compounds (2-1) and (2-2) will be described in more detail.

  In the present invention, in preparing a dispersion by depositing organic pigment nanoparticles, pigments are used for the purpose of controlling the particle size of pigment particles at the nanoscale level, imparting pH responsiveness, and basic treatment (improving redispersibility). The solution preferably contains an organic compound A having a basic group (also referred to as a crystal growth inhibitor). The organic compound A having a basic group preferably has a structure composed of a basic group and a long-chain alkyl group having 4 or more carbon atoms. The organic compound A having a basic group includes a dissociative compound having a hydrogen atom in the basic group and a non-dissociable compound having no hydrogen atom, and which is used when the good solvent is acidic. However, when the good solvent is basic, it is preferable to use a dissociable one. In the state of cationization or anionization at the time of particle formation, the crystal nuclei of the organic nano pigment particles are surrounded like a surfactant, and the nanometer size particle size can be controlled.

  Examples of the basic group of the organic compound A having the basic group include a primary amino group, a secondary amino group, and a tertiary amino group. A primary amino group, a secondary amino group, and a tertiary amino group are The thing of the state introduce | transduced in the heterocyclic ring may be sufficient. One or a plurality of these basic groups may be present. These basic organic compounds may be used alone or in combination of two or more. Examples of the organic compound A 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. , Triazine derivatives and the like, preferably alkylamine, arylamine and imidazole derivatives.

  As carbon number of the organic compound A 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 A having the basic group, examples of the alkylamine include butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecyl. Amine, 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 Ethylhexyl) 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 '' -Pentamethyldi Ethylenetriamine, cyclohexylamine, cycloheptylamine, cyclohexylamine, cyclododecylamine, 1-adamandanamine and the like can be mentioned, preferably octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine Decylamine, tetradecylamine, octadecylamine, t-octylamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N -Methyloctadecylamine, 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 are more preferable. Examples include decylamine, dodecylamine, tridecylamine, tetradecylamine, didecylamine, N-methyloctadecylamine, N, N-dimethyldodecylamine, and tridodecylamine. Also suitable are organic polymer compounds having a basic group such as polyallylamine and polyvinylamine.

  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 amount of the organic compound A having a basic group added to the pigment solution is preferably 0.1 parts by weight to 1000 parts by weight, more preferably 5 parts by weight to 500 parts by weight with respect to 100 parts by weight of the pigment. More preferably, it is 10 to 300 parts by weight. When the addition amount is too small, aggregation for isolation described later becomes insufficient. If the amount is too large, excessive agglomeration occurs and redispersion described later becomes difficult.

  In addition to the organic compound A having a basic group as described above, for the purpose of imparting further pH responsiveness and basic treatment (improving redispersibility) of the organic nano pigment particles, the following organic compound B ( It is preferable to add an organic compound composed of a basic group and a heterocyclic group, such as a base treating agent.

  By using the organic compound B having a basic group as described above, at the same time as the production of the organic pigment fine particles, the particles can be adsorbed by the heterocyclic group and the particles can be subjected to a basic treatment. The organic compound B having a basic group includes a dissociative compound having a hydrogen atom in the basic group and a non-dissociable compound having no hydrogen atom, either of which can be used when the good solvent is acidic. However, when the good solvent is basic, it is desirable to use a dissociable one.

  For example, 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-aminoacridine, ASTRA blue 6GLL (basic Phthalocyanine derivatives), 2- Mino 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 amount of the organic compound B added to the organic pigment solution is preferably 0.1 to 1000 parts by weight, more preferably 5 to 5000 parts by weight, and still more preferably 100 parts by weight of the pigment. 10 parts by weight to 3000 parts by weight. If the amount added is too small, the effect of strengthening the basic treatment is small, and if it is too large, the dispersibility during redispersion is lowered.

  In an organic compound having an acidic group, examples of the acidic group 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. 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 Examples thereof include 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, kofoic acid, metanilic acid, toluenesulfonic acid, and octanesulfonic acid.

  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, 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.

  Examples of the compound having a hydroxyl group include diethylene glycol, triethylene glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, decyl alcohol (including all isomers), undecyl alcohol (including all isomers), and dodecyl. Alcohol (including all isomers), tridecyl alcohol (including all isomers), tetradecyl alcohol, heptadecenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, phenol, o-cresol, p-cresol, octyl gallate, lauryl gallate, cetyl gallate, stearyl gallate, behenyl gallate, etc., 3,4-dihydroxybenzoic acid butyl ester, 3,4-dihydroxybenzoic acid benzyl ester, 3,4 Dihydroxy-5-chlorobenzoic acid benzyl ester, 3,4-dihydroxybenzoic acid-α-phenylethyl ester, 3,4-dihydroxy-4-methyldiphenylsulfone, 4-dihydroxybenzoic acid propyl ester, 2,4-dihydroxybenzoic acid Acid butyl ester, 2,4-dihydroxybenzoic acid cyclohexyl ester, 2,4-dihydroxybenzoic acid benzyl ester 2,4-dihydroxybenzoic acid-p-methylbenzyl ester, 2,4-dihydroxybenzoic acid-p-chlorobenzyl ester 2,4-dihydroxybenzoic acid-α-phenylethyl ester, 2,4-dihydroxybenzoic acid-β-phenylethyl ester, 2,4-dihydroxy-6-methylbenzoic acid ethyl ester, 2,4-dihydroxy-6 -Methyl repose Acid propyl ester, 2,4-dihydroxy-6-isopropylbenzoic acid ethyl ester, 2,4-dihydroxy-6-pentylbenzoic acid ethyl ester, 2,4-dihydroxy-6-methoxybenzoic acid butyl ester, 2,4- Dihydroxy-6-methylbenzoic acid cyclohexyl ester, 2,4-dihydroxy-6-methylbenzoic acid benzyl ester, 2,4-dihydroxy-6-propylbenzoic acid p-chlorobenzyl ester, 2,4-dihydroxy-6-methoxy Benzoic acid p-methylbenzyl ester, 2,4-dihydroxy-6-methylbenzoic acid p-isopropylbenzyl ester, 2,4-dihydroxy-6-methylbenzoic acid p-methylphenoxyethyl ester, 2,4-dihydroxy-5 -Chlorobenzoic acid-p-chloroben Examples thereof include a diester and 2,4-dihydroxybenzophenone.

  Examples of the compound having a sulfide group include 4-mercaptopyridine, 2-mercaptoethyloctanoic acid ester, 2-mercaptopropionic acid, trimethylolpropane tristhiopropionate, thioglycolic acid, octyl thioglycolate, and the like.

  The addition amount of the organic compound having an acidic group to the organic pigment solution 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. A range of 0.05 to 15% by mass is particularly preferable.

  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 here is derived from a pigmentation reaction of a pigment derivative compound or a chemically modified pigment precursor which is derived from an organic pigment as a parent substance and is produced by chemically modifying the parent structure. Refers to a pigment derivative type compound. Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol, and the like. 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 good solvent (first solvent) is not particularly limited as long as it can dissolve the organic pigment and the polymer compound and is compatible with or uniformly mixed with the poor solvent (second 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 on 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 polymer compound (1-1) or (1-2) 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, An organic acid (For example, formic acid, dichloroacetic acid, methanesulfonic acid etc.), an organic base (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. Acidity is used when there are many atoms in the molecule. For example, quinacridone, diketopyrrolopyrrole, 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 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 second 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. 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.
The solubility of the polymer compound (1-1) or (1-2) in the second solvent is preferably 4% by mass or more (that is, has an affinity), and preferably 10% 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. In the present invention, as described above, by using the polymer compound (1-1) or (1-2) having an affinity for a poor solvent, an excess polymer compound (1-1) that is not adsorbed on the pigment fine particles. ) Or (1-2) can be washed away in the next filtration step. If there is an excessive polymer compound that is not adsorbed on the pigment particles, there is a concern that there will be various adverse effects in later processes such as deterioration of redispersibility in the third solvent and increase in viscosity. These conditions are effective.

  Although it does not specifically limit as a 2nd solvent, An aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), an alcoholic solvent (for example, methanol, ethanol, n-propanol, etc.), a ketone 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 (Eg, ethyl acetate, acetic acid-n-butyl, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (eg, octane, etc.), nitrile solvents (eg, acetonitrile, etc.), halogen solvents (eg, carbon tetrachloride, dichloromethane, etc.), ionic liquids (eg, And 1-ethyl-3-methylimidazolium tetrafluoroborate), a carbon disulfide solvent, or a mixture thereof.

  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 common ones listed as specific examples of the first solvent and those listed as the second solvent, the same ones as the first solvent and the second solvent are not combined. For each organic pigment and polymer compound employed, the solubility in the first solvent is preferably sufficiently higher than the solubility in the second solvent. For the pigment, for example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% 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 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 and the second solvent meet. 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 refers to the diameter of the equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to the 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 Formula (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 0.8 to 2.0 kg / m ³ , for example. 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 controlled and obtained by adjusting 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 diameter 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 more preferably 5 to 80 nm. It is particularly preferred that 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.
The amount of the polymer compound (1-1) and / or (1-2) contained in the organic pigment fine particles of the present invention is not particularly limited, but is practically 5 to 100 parts by mass with respect to 100 parts by mass of the pigment. It is. Moreover, it is practical that it is 1-100 mass parts with respect to 100 mass parts of pigments about organic compound (2-1) and / or (2-2). The organic pigment fine particles of the present invention may be in the form of powder or in a state of being included in a dispersion, paste, or solid dispersion.

In the present invention, it is preferable to contain the third solvent different from both the good solvent and the poor solvent used for the precipitation of the pigment fine particles in the mixed solution after the pigment nanoparticle precipitation. 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. At this time, it is preferable to incorporate the polymer compound having a mass average molecular weight of 1000 or more into the third solvent and introduce it together to redisperse the pigment fine particle concentrate or its powder.
In the present invention, not only the above-mentioned third solvent, but also a fourth solvent, which will be described later, is a medium of the composition, and collectively referred to as a solvent different from both the good solvent and the poor solvent, This is referred to as a “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, and ethanol are preferable, and ethyl lactate is 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 the addition of the third solvent is not particularly limited as long as it is after the precipitation of the pigment nanoparticles, but a part of the solvent in the mixed liquid in which the pigment nanoparticles are precipitated is removed (concentrated) in advance (first removal). It is preferable to add after that. That is, it is preferable that the third solvent is 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 is substituted with the third solvent.

In addition, when a pigment dispersion composition to be 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 ( It is preferable to remove the solvent by the second removal) and pulverize. And a binder and / or a solvent can be added after that, and it can be set as a desired pigment dispersion composition.
The addition amount of the third solvent 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 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 binder used for nanoparticle formation and the binder used for redispersion may be the same or different.

  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 polymer compound (1-1) and / or (1-2) and the content of the organic compound (2-1) and / or (2-2) in the pigment dispersion composition of the present invention are: The amount of the organic pigment fine particles described above is the same.

    The organic pigment fine particles of the present invention are preferably subjected to a predetermined treatment / operation in the dispersion composition to form soft aggregates of fine particles. Here, soft agglomeration is an agglomeration that is weak enough to be redispersed as necessary, and the soft agglomerates are sometimes called flocs. In this way, for example, organic pigment fine particles precipitated in an aqueous dispersion composition can be quickly separated by filtration or the like. Then, the separated soft agglomerates can be re-dispersed in an organic solvent suitable for production of a color filter, and an organic solvent-based dispersion composition can be efficiently obtained. That is, when the mixed solvent of the good solvent and the poor solvent is an aqueous solvent, the dispersion medium (continuous phase) can be switched by efficiently replacing it with a third solvent made of an organic solvent. The average particle size of the aggregate is not particularly limited, but is preferably 0.5 to 500 μm and preferably 5 to 100 μm in consideration of the filterability described above and redispersibility in the third solvent in the subsequent step. More preferred.

As a method of redispersing the pigment nanoparticles (floc) in such a soft aggregation 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, or the like.
There are no particular limitations on the disperser used when dispersing the pigment nanoparticles by applying physical energy, for example, dispersers such as kneaders, roll mills, atriders, super mills, dissolvers, homomixers, and sand mills. Can be mentioned. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  The photocurable composition of the present invention is preferably the following colored photosensitive resin composition. The colored photosensitive resin composition (pigment-dispersed photoresist) contains the organic pigment nanoparticles and a monomer or oligomer (polymerizable compound), and preferably further contains a binder and a photopolymerization initiator or photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

  The organic pigment fine particles and the method for producing the powder have already been described in detail. The content of the pigment nanoparticles in the colored photosensitive resin composition is 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). Preferably, 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, the 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 monomer or oligomer is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers 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 dipentaerythritol hexa (meth) acrylate, 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, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated. 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.

  Monomers or oligomers may be used alone or in admixture of two or more. The content of the colored photosensitive resin 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 the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing the inkjet ink for color filter or the colored photosensitive resin composition, but when producing the pigment nanoparticle dispersion composition, or pigment nanoparticle It is also preferable to add at the time of formation. It is also possible to add a binder to both or one of the poor solvent for adding the organic pigment solution and the organic pigment solution to form pigment nanoparticles. Alternatively, it is also preferable to add the binder solution in a separate system when forming the pigment nanoparticles.

  The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. 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 binder may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer, and the addition amount relative to 100 parts by mass of pigment nanoparticles is generally 10 to 200 parts by mass. And 25-100 mass parts is preferable.

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

  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), US 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, combinations of 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 colored photosensitive resin 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.

  In the colored photosensitive resin composition, in addition to the above components, an organic solvent for preparing a resin composition (fourth solvent) may be further used. Examples of the fourth solvent include, but are not limited to, esters, ethers, and ketones. Among these, 1,3-butylene glycol diacetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. 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 a 4th solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

  Moreover, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition. Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less with respect to the total amount of the resin composition.

  The colored photosensitive resin 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 based on the total amount of the resin composition.

  In addition to the colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition as necessary. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less. 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 content of the auxiliary dye or pigment is preferably 5% by mass or less based on the total amount of the resin composition.

  The colored photosensitive resin composition may 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 resin composition whole quantity.

  Further, in the colored photosensitive resin composition, in addition to the above additives, “adhesion aid” described in JP-A-11-133600, other additives, and the like can be contained.

The colored photosensitive resin composition can be made into an inkjet ink by appropriately adjusting the composition. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing. Among them, the inkjet ink for the color filter is preferable.
The ink-jet ink of the present invention only needs to contain 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 colored photosensitive resin 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 adding a surfactant or 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 temperature and time of heating depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to the point of obtaining 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 shape such as a 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 colored photosensitive resin composition are the same as those already described. Moreover, although the thickness of the coating film using a colored photosensitive resin composition can be suitably determined according to the use, it is preferable that it is 0.5-5.0 micrometers, and is 1.0-3.0 micrometers. It is more preferable. In the coating film using this colored photosensitive resin composition, the above-mentioned monomer or oligomer is polymerized to form a colored photosensitive resin composition polymerized film, and a color filter having the same can be prepared (of the color filter). The production will be described later.) Polymerization of the polymerizable monomer or polymerizable oligomer 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 colored photosensitive resin composition with a normal application method, in this invention, it has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply by a slit 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 colored photosensitive resin 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 manufacturing 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.

  Since slit coating forms a coating film with a much larger area than spin coating, it is necessary to maintain a certain relative speed between the coater and the object to be coated when discharging the coating liquid from the wide slit exit. is there. For this reason, good fluidity is required for the coating liquid used in the slit coating method. In addition, the slit coating is particularly required to keep the conditions of the coating solution supplied to the substrate from the slit of the coating head constant over the entire coating width. Insufficient liquid properties such as fluidity and viscoelastic properties of the coating liquid tend to cause coating unevenness, making it difficult to keep the coating thickness constant in the coating width direction and obtaining a uniform coating film. The problem of not being able to occur.

  For these reasons, many attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform coating film without unevenness. However, as mentioned above, the molecular weight of the polymer is reduced, a polymer with excellent solubility in the solvent is selected, various solvents are selected to control the evaporation rate, and a surfactant is used. Means have been proposed, but none were sufficient to improve the above problems.

  The photosensitive transfer material is preferably formed using a photosensitive resin transfer material described in JP-A-5-72724, that is, an integral film. An example of the structure of the integral film is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film are laminated in this order, and the photosensitive transfer material is colored as described above. A photosensitive resin is provided by using a photosensitive resin composition.

  In the photosensitive transfer material, it is necessary that the temporary support has flexibility and does not cause significant deformation, contraction or elongation even under pressure, or under pressure and heat. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

In the photosensitive transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from ordinary ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

The photosensitive transfer material is provided with a thermoplastic resin layer by applying a coating solution (thermoplastic resin coating solution) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the resin layer, and then the photosensitive resin layer is prepared by applying and drying with a solvent that does not dissolve the intermediate layer. Can do.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In the photosensitive transfer material, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

  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 size 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.

xy 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 is particularly preferably a VA system. 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.

Example 1
EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted.
<Pigment dispersion composition 1>
While heating 2500 ml of methanesulfonic acid [first solvent] (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “MSA”) to 80 ° C., the pigment C.I. I. Pigment violet 23 (manufactured by Clariant, Hostaperm Violet RL-NF) 112.5 g and polyvinylpyrrolidone K-30 (trade name: manufactured by Wako Pure Chemical Industries, Ltd.) 64.0 g, EFKA6745 (trade name: manufactured by EFKA) 16.0 g The pigment solution 1 was prepared by adding.
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 a poor solvent [second solvent].

  Here, the temperature of the solution was controlled at 25 ° C., and NP was added to the pigment solution 1 at 80 ° C. in 2000 ml of poor solvent water stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). -KX-500 type large capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) was used for injection. By setting the flow path diameter and the supply port diameter of the liquid feeding pipe of the pigment solution 1 to 2.2 mm, placing the supply port in a poor solvent, and injecting 220 ml at a flow rate of 200 ml / min to form organic pigment particles, the pigment dispersion liquid 1 was prepared. When the particle diameter and monodispersity of this pigment dispersion were measured using Nikkiso Nanotrack UPA-EX150, the number average particle diameter was 32 nm and Mv / Mn was 1.55.

  The pigment dispersion 1 prepared by the above procedure was concentrated at 3000 rpm for 90 minutes using an H-110A type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. The solvent content was removed from the solution and reduced (first concentration / removal step), and the pigment nanoparticle concentrated paste was recovered. The pigment content of the paste was measured using an Agilent 8453 type spectrophotometer and found to be 16.3% by mass.

  A solution obtained by adding 2.62 g of solsperse 39000 (manufactured by Lubrizol) to 80.0 cc of ethyl lactate [third solvent] was added to 16.1 g of the pigment nanoparticle concentrated paste. This was stirred at 1200 rpm for 80 minutes with a dissolver, further 30.0 cc of ethyl acetate was added, and stirred at 500 rpm for 10 minutes with a dissolver to obtain a dispersion.

  By filtering this dispersion using an FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co., Ltd. (second concentration / removal step), paste-like concentrated pigment liquid 1 (nano-pigment concentration 31.0% by mass) Got.

Using the paste-like concentrated pigment liquid 1, a pigment dispersion composition 1 having the following composition was prepared.
21.1 g of the paste-like concentrated pigment liquid 1
1-Methoxy-2-propyl acetate 43.2g

  Pigment dispersion composition 1 having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 2 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

[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 manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) were used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka etc.). Two polarizing plates, a sample, and a color luminance meter are installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and light transmitted through this. 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 amount of light 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 1-2.

(Examples 2 to 27)
In Example 1, pigment dispersion compositions 2 to 27 were prepared and the contrast was measured in the same manner except that the component composition of each agent used was changed to that shown in Table 1-1 below. The results are shown in Table 1-2. However, when the first solvent is methanesulfonic acid / formic acid, 2000 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 500 ml of formic acid (manufactured by Wako Pure Chemical Industries, Ltd.) are heated to 60 ° C. as the first solvent. Dissolved.

(Example 28)
To 1500 ml of dimethyl sulfoxide [first solvent], at room temperature (about 25 ° C.), 50.0 ml of 28% sodium methoxide methanol solution, pigment C.I. I. Pigment Red 254 (trade name, Irgafore Red BT-CF manufactured by Ciba Specialty Chemicals Co., Ltd.) 80 g, polyvinylpyrrolidone 45.4 g, EFKA6745, 11.4 g were added to prepare pigment solution 28. Separately, 1500 ml of water [second solvent] containing 20 ml of 1 mol / l hydrochloric acid was prepared.

  Here, the temperature of the solution was controlled at 18 ° C., and the pigment solution 28 was NP-KX-500 type in a second solvent stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Injection was performed using a large-capacity non-pulsating pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). The flow path diameter and the supply port diameter of the liquid feeding pipe for the pigment solution 28 are 0.5 mm. The supply port is placed in a poor solvent and injected at a flow rate of 50 ml / min to inject 100 ml of organic pigment fine particles. Was prepared. When the particle size and monodispersity of this pigment dispersion were measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., the number average particle size was 36 nm and Mv / Mn was 1.50.

The pigment dispersion liquid 28 obtained by the above-described method and obtained as a pigment nanoparticle dispersion liquid was subjected to 60 at 3500 rpm using a H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. After concentration, the resulting pigment nanoparticle concentrated paste was recovered. The pigment content of the paste was measured using an Agilent 8453 type spectrophotometer and found to be 13.1% by mass.
By adding 70.0 cc of ethyl lactate to 25.0 g of the above pigment nanoparticle preparation paste, stirring at 1500 rpm for 60 minutes with a dissolver, and then filtering using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer Co., Ltd. Concentration pigment liquid 28 (nano pigment concentration 28 mass%) was obtained.

Using the paste, the following composition was prepared, and dispersed with a motor mill M-50 (manufactured by Eiger Japan) at a peripheral speed of 9 m / s for 1 hour using 0.65 mm diameter zirconia beads. A pigment dispersion composition 27 was prepared.
22.4 g of the paste-like concentrated pigment liquid 27
solsperse 39000 6.3 g
1-methoxy-2-propyl acetate 42.6g

(Examples 29 to 31),
In Example 28, pigment dispersion compositions 29 to 31 were prepared and the contrast was measured in the same manner except that the component composition of each agent used was changed to that shown in Table 1-1 below. The results are shown in Table 1-2. However,

(Comparative Examples 1-4)
In Example 1, pigment dispersion compositions 32 and 33 (Comparative Examples 1 and 2) for comparison were prepared in the same manner except that the composition of each agent used was changed to that shown in Table 1-1 below. Prepared and measured contrast. The results are shown in Table 1-2. However,
In Example 27, pigment dispersion compositions 34 and 35 (Comparative Examples 3 and 4) for comparison were prepared in the same manner except that the component composition of each agent used was changed to that shown in Table 1-1 below. Prepared and measured contrast. The results are shown in Table 1-2. However,

  From the above results, the specific polymer compound and the specific organic compound in the present invention are combined (the combination of the polymer compound (1-1) and the organic compound (2-1): the polymer composition such as the dispersion composition 1). Combination of (1-2) and organic compound (2-2): Dispersion composition 8, etc. Combination of polymer compound (1-1) and organic compound (2-2): Organic prepared by dispersion composition 27) It can be seen that by using the pigment fine particles, a high contrast can be realized without the dispersion gelling.

・ＰＶＰ：ポリビニルピロリドン（和光純薬、商品名：Ｋ３０、質量平均分子量４００００）、水に親和性がある含窒素高分子化合物
・ＥＦＫＡ６７４５（商品名、ＥＦＫＡ社製）、酸性基を有する有機化合物
・ｓｏｌｓｐｅｒｓｅ５０００（商品名、ルーブリゾール社製）、酸性基を有する有機化合物
・ＰＰＧ：ポリプロピレングリコール（和光純薬社製、質量平均分子量３０００）、水に親和性がある窒素を含まない高分子化合物、酸性基を有する有機化合物
・ＰＥＧ：ポリエチレングリコール（和光純薬社製、質量平均分子量４０００）、水に親和性がある窒素を含まない高分子化合物、酸性基を有する有機化合物
・ＰＶＡ：ポリビニルアルコール（質量平均分子量２００００）、水に親和性がある窒素を含まない高分子化合物
・ＰＡＡ：ポリアリルアミン塩酸塩（日東紡社製、質量平均分子量１０００００）、水に親和性がある含窒素高分子化合物
・ＰＡＡｃ：ポリアクリル酸（和光純社製、質量平均分子２５０００）、水に親和性がある窒素を含まない高分子化合物、酸性基を有する有機化合物
・ＭＭＡ／ＭＡＡ共重合体：メタクリル酸メチル／メタクリル酸共重合体、組成比、２０／８０質量％（質量平均分子量３００００）、水に親和性がある窒素を含まない高分子化合物
・ＤＭＤＡ：ジメチルドデシルアミン（東京化成社製）、塩基性基を有する有機化合物
・ｐ−オクチルオキシ安息香酸（Ａｌｄｒｉｃｈ社製）、酸性基を有する有機化合物
・ｓｏｌｓｐｅｒｓｅ３９０００（商品名、グラフト型、塩基性）

PVP: polyvinylpyrrolidone (Wako Pure Chemicals, trade name: K30, mass average molecular weight 40000), nitrogen-containing polymer compound having affinity for water EFKA6745 (trade name, manufactured by EFKA), organic compound having an acidic group solsperse 5000 (trade name, manufactured by Lubrizol), organic compound having an acidic group PPP: polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., mass average molecular weight 3000), nitrogen-free polymer compound having affinity for water, acidic Group-containing organic compound PEG: polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 4000), nitrogen-containing polymer compound having affinity for water, organic group-containing organic compound PVA: polyvinyl alcohol (mass Average molecular weight 20000), polymer compound that does not contain nitrogen and has affinity for water, PA : Polyallylamine hydrochloride (manufactured by Nittobo Co., Ltd., mass average molecular weight 100,000), nitrogen-containing polymer compound having affinity for water, PAAc: polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., mass average molecule 25000), affinity for water A high molecular compound containing no nitrogen, an organic compound having an acidic group, MMA / MAA copolymer: methyl methacrylate / methacrylic acid copolymer, composition ratio, 20/80 mass% (mass average molecular weight 30000), water -Non-containing polymer compound with affinity to DMDM: dimethyldodecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), organic compound having basic group, p-octyloxybenzoic acid (manufactured by Aldrich), organic compound having acidic group Compound ・ solperse 39000 (trade name, graft type, basic)

[Table 1-2]
-----------------------------
Dispersion composition Contrast -----------------------------
Example 1 Dispersion Composition 1 13000
Example 2 Dispersion Composition 2 12500
Example 3 Dispersion Composition 3 8000
Example 4 Dispersion Composition 4 9000
Example 5 Dispersion Composition 5 7000
Example 6 Dispersion Composition 6 7500
Example 7 Dispersion Composition 7 8500
Example 8 Dispersion Composition 8 8000
Example 9 Dispersion Composition 9 7500
Example 10 Dispersion Composition 10 7500
Example 11 Dispersion Composition 11 8000
Example 12 Dispersion Composition 12 10000
Example 13 Dispersion Composition 13 12000
Example 14 Dispersion Composition 14 9500
Example 15 Dispersion Composition 15 8000
Example 16 Dispersion Composition 16 9500
Example 17 Dispersion Composition 17 9000
Example 18 Dispersion Composition 18 7500
Example 19 Dispersion Composition 198000
Example 20 Dispersion Composition 20 8500
Example 21 Dispersion Composition 21 7500
Example 22 Dispersion Composition 22 9000
Example 23 Dispersion Composition 23 12000
Example 24 Dispersion Composition 24 11500
Example 25 Dispersion Composition 25 10000
Example 26 Dispersion Composition 26 9000
Example 27 Dispersion Composition 27 8500
Example 28 Dispersion Composition 28 8000
Example 29 Dispersion Composition 29 7500
Example 30 Dispersion Composition 30 7000
Example 31 Dispersion Composition 31 10000
-----------------------------
Comparative Example 1 Dispersion Composition 32 *
Comparative Example 2 Dispersion Composition 33 *
Comparative Example 3 Dispersion Composition 34 *
Comparative Example 4 Dispersion Composition 35 *
-----------------------------
* Gelled during dispersion and could not be measured.

(Example 32)
[Preparation of color filter (preparation by application using slit 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., a glass substrate coater (manufactured by FAS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle, from the composition described in the table below. A colored photosensitive resin composition K1 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 A 4 μm photosensitive resin layer K1 was obtained.

[Table 2-1]
--------------------------------------
K pigment dispersion 1 (carbon black) 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization start Agent 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 photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials Co., Ltd.) was 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 in the same process as the formation of the black (K) image using the colored photosensitive resin composition R1 having the composition shown in the following table on the substrate on which the image K was formed.
The film thickness of the photosensitive resin layer R1 and the coating amount of pigments (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin 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 2-2]
--------------------------------------
R pigment dispersion 1 (C.P.P.254) 35 parts by mass R pigment dispersion 2 (C.I.P.P.177) 6.8 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by weight Binder 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 part by weight Surfactant 1 0.06 parts by weight Part -------------------------------------

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition shown in the following table 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 photosensitive resin layer G1 and the coating amounts of pigments (CIPG36 and CIPY150) are shown below.
Photosensitive resin 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 2-3]
--------------------------------------
G pigment dispersion 1 (C.I.P.G.36) 28 parts by mass Y pigment dispersion 1 (C.I.P.Y.150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 2.5 parts by mass DPHA solution 3.5 parts by mass Polymerization initiator B 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 part by mass 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 the colored photosensitive resin composition B1 having the composition shown in the following table, and is subjected to a heat-treated pixel 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 photosensitive resin layer B1 and the coating amount of pigments (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin 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 2-4]
--------------------------------------
B Pigment Dispersion 1 (C.I.P.B.15: 6) 15.0 parts by mass V Pigment Dispersion Composition A (C.I.P.V.23) 7.5 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 17 parts by mass DPHA solution 4.0 parts by mass Polymerization initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 1 0.06 parts by mass ------- -------------------------------

Here, the preparation of the colored photosensitive resin compositions K1, R1, G1, and B1 described in the above table will be described in more detail.
Colored photosensitive resin composition K1 first weighs K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in the table, mixes at a temperature of 24 ° C. (± 2 ° C.), and stirs at 150 rpm for 10 minutes. Next, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) in the amounts shown in the table ) 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 30 at 150 rpm at a temperature of 40 ° C. (± 2 ° C.). Obtained by stirring for minutes.

In addition, the composition was shown below about the following component among the compositions described in a table | surface.
<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
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 / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

The colored photosensitive resin composition R1 is prepared by weighing out the R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in the table, mixing at a temperature of 24 ° C. (± 2 ° C.), and 150 rpm. And then polymerization initiator B (methyl ethyl ketone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole) in the amount shown in the table ), Polymerization initiator A was 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 weighed, and the temperature was 24 ° C. (± 2 ° C.) was added, stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200.
Of the compositions described in the table, R pigment dispersions 1 and 2 were prepared using the method described in Example 1 of International Publication No. WO2006 / 121016 pamphlet so that the composition would be the following parts by mass. Each was prepared.

<R pigment dispersion 1>
・ C. I. P. R. 254
(Product name: Irgaphor Red BT-CF
Ciba Specialty Chemicals Co., Ltd.)
10 parts by mass-pigment dispersant A 1 part by mass-polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer, molecular weight 30,000)
10 parts by mass, 79 parts by mass of propylene glycol monomethyl ether acetate

<R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.)
22.5 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer, molecular weight 30,000)
15 parts by mass ・ Propylene glycol monomethyl ether acetate 62.5 parts by mass

<Binder 1>
-27 parts by mass of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 38/25/37 molar ratio, molecular weight 40,000)-73 parts by mass of propylene glycol monomethyl ether acetate

  The colored photosensitive resin composition G1 is first weighed in the amounts of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in the table, mixed at a temperature of 24 ° C. (± 2 ° C.), and 150 rpm. And then weigh out methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution, polymerization initiator B and polymerization initiator A in the amounts shown in the table and add them in this order at a temperature of 24 ° C. (± 2 ° C.). Then, the surfactant 1 in the amount shown in the table is weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200. Was obtained by

  In addition, among the compositions described in the table, as the G pigment dispersion 1, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used. As the Y pigment dispersion 1, “trade name: CF erotic-EX3393” manufactured by Mikuni Color Co., Ltd. was used.

  The colored photosensitive resin composition B1 was first weighed in the amounts of B pigment dispersion 1, V pigment dispersion A, and propylene glycol monomethyl ether acetate in the amounts shown in the table, and mixed at a temperature of 24 ° C. (± 2 ° C.) to 150 rpm. Then, the amounts of methyl ethyl ketone, binder 3, DPHA solution and polymerization initiator B phenothiazine in the amounts shown in the table are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 30 minutes at ± 2 ° C, and the surfactant 1 in the amount shown in the table was weighed out, added at a temperature of 24 ° C (± 2 ° C), stirred for 5 minutes at 30 rpm, and nylon mesh # Obtained by filtering through 200.

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

The composition of the binder 3 is as follows.
<Binder 3>
-27 parts by mass of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 37,000)-73 parts by mass of propylene glycol monomethyl ether acetate

  The color filter 1 was produced as described above. A color filter except that the pigment dispersion composition 1 used in the color filter 1 is replaced with pigment dispersion compositions 2 to 27 (Examples 33 to 58) and pigment dispersion compositions 32 and 33 (Comparative Examples 5 and 6), respectively. In the same manner as in Example 1, color filters 2 to 27, 32, and 33 were produced. The results of measuring the contrast for each color filter in the same manner as in [Measurement of contrast] are shown in Table 2-5. The pigment dispersion compositions 32 and 33 were gel-like dispersion compositions having a very high viscosity, but they were used as they were.

[Table 2-5]
-----------------------------------
Color filter Color filter contrast -----------------------------------
Example 32 Color filter 1 11000
Example 33 Color filter 2 10000
Example 34 Color filter 3 7000
Example 35 Color filter 4 7500
Example 36 Color filter 5 6500
Example 37 Color filter 6 6000
Example 38 Color filter 7 7500
Example 39 Color filter 8 7000
Example 40 Color filter 9 6500
Example 41 Color filter 10 6000
Example 42 Color filter 11 7000
Example 43 Color filter 12 9000
Example 44 Color filter 13 10000
Example 45 Color filter 14 8000
Example 46 Color filter 15 7500
Example 47 Color filter 16 7000
Example 48 Color filter 17 8500
Example 49 Color filter 18 7000
Example 50 Color filter 19 7500
Example 51 Color filter 20 7000
Example 52 Color filter 21 6500
Example 53 Color filter 22 8500
Example 54 Color filter 23 10000
Example 55 Color filter 24 9500
Example 56 Color filter 25 9000
Example 57 Color filter 26 8000
Example 58 Color filter 27 8500
-----------------------------------
Comparative Example 5 Color filter 32 1500
Comparative Example 6 Color filter 33 1000
-----------------------------------

  From the above results, the color filter of the comparative example has a low contrast and a level that does not satisfy practical requirements. On the other hand, it can be seen that the color filters of the present invention are all good color filters that can greatly increase the contrast and enhance the display performance with stable manufacturing quality.

Claims (19)

  Organic pigment fine particles comprising a polymer compound (1-1) and an organic compound (2-1) having an acidic group, wherein the fine particles contain an organic pigment in a good solvent. And a solution dissolved together with the organic compound (2-1) and a poor solvent for the organic pigment, and the organic pigment is precipitated as nanometer-sized fine particles. Organic pigment fine particles characterized in that 1) is a compound having affinity for the poor solvent.   Organic pigment fine particles containing a polymer compound (1-2) and an organic compound (2-2) having a basic group or an acidic group, wherein the fine particles are obtained by using an organic pigment in a good solvent as the polymer compound ( 1-2) and a solution dissolved together with the organic compound (2-2) and a poor solvent for the organic pigment are mixed to precipitate the organic pigment as nanometer-sized fine particles. Organic pigment fine particles, wherein the molecular compound (1-2) is a compound that does not contain a nitrogen atom having an affinity for the poor solvent.   The organic pigment fine particles according to claim 1 or 2, wherein the polymer compound (1-1) or (1-2) has a mass average molecular weight of 1,000 to 500,000.   The polymer compound (1-1) or (1-2) is a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, a silicone polymer, and these The organic pigment fine particles according to any one of claims 1 to 3, which is at least one polymer compound selected from a modified product or a copolymer. The organic pigment solution and the poor solvent are mixed under a condition that the Reynolds number Re represented by the following formula (1) is 50 or more. Organic pigment fine particles as described.
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 when the organic pigment solution and the poor solvent meet, and L represents the organic pigment solution and the poor solvent. Represents the equivalent diameter of the flow path or the supply port of the part where and meet, and μ represents the viscosity coefficient of the organic pigment solution. ]   The said good solvent is at least 1 sort (s) or more selected from the group which consists of an organic acid, an organic base, a sulfoxide type solvent, and an amide type solvent, The any one of Claims 1-5 characterized by the above-mentioned. Organic pigment fine particles.   The organic pigment fine particles according to any one of claims 1 to 6, wherein the good solvent is at least one selected from the group consisting of an aqueous solvent and an alcohol solvent.   The organic pigment solution contains the polymer compound (1-1) and / or (1-2) in an amount of 1 part by mass to 1000 parts by mass with respect to 100 parts by mass of the organic pigment. The organic pigment fine particles according to any one of 1 to 7.   A pigment dispersion composition comprising the organic pigment fine particles according to any one of claims 1 to 8, and a third solvent different from both the good solvent and the poor solvent.   The third solvent is at least one solvent selected from the group consisting of ether solvents, ester solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents. Item 10. The pigment dispersion composition according to Item 9.   The pigment dispersion composition according to claim 9 or 10, further comprising a pigment dispersant.   A photocurable composition comprising the pigment dispersion composition according to any one of claims 9 to 11, a photopolymerizable compound, and a photopolymerization initiator.   Furthermore, alkali-soluble resin was contained, The photocurable composition of Claim 12 characterized by the above-mentioned.   The photocurable composition according to claim 12 or 13, wherein the photocurable composition is for a color filter.   A color filter comprising a colored pattern using the photocurable composition according to claim 14 on a substrate.   A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to claim 14 directly or through another layer onto a substrate, and pattern exposure to the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing development.   An inkjet ink comprising the organic pigment fine particles according to any one of claims 1 to 8 contained in a medium containing a polymerizable monomer and / or a polymerizable oligomer.   The inkjet ink according to claim 17, wherein the inkjet ink is used for a color filter.   Organic pigment fine particles comprising a polymer compound (1-1) and an organic compound (2-2) having a basic group or an acidic group, wherein the fine particles contain an organic pigment in a good solvent as the polymer compound ( 1-1) and a solution dissolved together with the organic compound (2-2) and a poor solvent for the organic pigment are mixed, and the organic pigment is precipitated as nanometer-sized fine particles. Organic pigment fine particles, wherein the molecular compound (1-1) is a compound having affinity for the poor solvent.