JP2007231131A - Colored resin fine particle, water-based dispersion containing the colored resin particle, ink for inkjet printing or ink for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide colored resin fine particles excellent in color developability of printed matters, transparency and gloss and producing images having excellent image fastness such as light resistance, water resistance and fixing property, excellent in storage stability by itself upon preparing ink, being free from clogging of a print head and excellent in ejection stability upon printing and to provide a water-based dispersion containing the colored resin particles and ink for inkjet printing or ink for color filter, in respect to a colorant or dispersion of colorant as a precursor of ink for inkjet printing or for display of a color filter or a dispersion containing the colorant. <P>SOLUTION: The colored resin fine particles are resin fine particles containing a water-insoluble coloring material and having ≤100 nm average particle diameter and are each composed of a hydrophilic resin and a hydrophobic resin and average particle diameter of the water-insoluble coloring material is ≤50 nm. The water-based dispersion comprises the colored resin fine particles. The ink for inkjet printing and the ink for color filter are also provided in the present invention. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color material, a dispersion of color material, and an ink that are inks for inkjet recording and color filters. More specifically, an image having excellent color fastness, transparency and glossiness of the printed matter, and excellent image fastness such as light resistance, water resistance, and fixing property can be obtained, and excellent in storage stability during itself and ink preparation. The present invention relates to colored resin fine particles that are not clogged at the time of printing and excellent in ejection stability, aqueous dispersions containing the colored resin fine particles, ink jet recording ink, and color filter ink.

  Inkjet recording is small and has a low running cost, but enables high-quality color printing, and has rapidly been used in offices, the photographic market, and color filter applications. One of the most important factors in this ink jet recording is ink characteristics. In the past, dyes have been mainly used for this ink in view of ejection stability at the printer head, storage stability of the ink, and color development of the printed matter. However, in fields where preservation is required, such as offices and the photographic market, problems such as fading due to light, moisture in the atmosphere, or gases such as ozone are likely to occur.

  In recent years, therefore, water-insoluble colorants typified by pigments and oil-soluble dyes have been attracting attention for use in inkjet recording or color filters because they have excellent storage stability such as water resistance and light resistance. Since these water-insoluble colorants do not dissolve in an aqueous dispersion medium such as water, a water-based dispersion in which the water-insoluble colorant is dispersed at a high concentration is once prepared, and a surfactant, a water-soluble organic compound, It is prepared and used in an ink by adding an additive such as a pH adjusting agent and preservative and water.

  In a water-insoluble color material, an aqueous dispersion, or an ink prepared therefrom, a clear image cannot be obtained when the water-insoluble color material cannot be finely dispersed. Also, when used for printing on an OHP sheet projected by a backlight or for color filter display, a colorful projection image cannot be obtained unless a water-insoluble colorant is finely dispersed to ensure high transparency. Thus, in order to satisfy the same clarity and transparency as the dye, it is necessary to prevent the incident light from being scattered by the coloring material. This scattering depends on the particle size of the colorant, and the smaller the particle size, the more the scattering is suppressed, and it becomes almost negligible when the particle size becomes 1/10 or less of visible light. That is, when the particle size of the water-insoluble colorant is smaller than 50 nm, sharpness and transparency are exhibited. Further, when the crystal size of the water-insoluble colorant is finer, a more transparent dispersion or ink can be prepared. Further, when the water-insoluble colorant in the ink is finely dispersed and not stabilized, there is a problem of nozzle clogging in the printer head.

  However, it is very difficult to finely disperse the water-insoluble colorant. Usually, the water-insoluble colorant is dispersed by adding a dispersant to an aqueous dispersion medium and using a mechanical force with a pulverizing and dispersing machine such as a bead mill or a roll mill. Dispersions and inks obtained by this method can be dispersed only to an average particle diameter of a color material used as a raw material of about 100 nm, and an image having sufficient sharpness and transparency cannot be obtained. Furthermore, if pulverization is performed vigorously and dispersion is performed, the dispersion becomes unstable due to an increase in specific surface area and overdispersion caused by a local crystal structure change on the surface of the water-insoluble colorant, and the dispersion is stably maintained. It is difficult. Therefore, it was necessary to prepare an ultrafine water-insoluble colorant by a method different from pulverization, and at the same time, to achieve a high degree of dispersion stabilization and to be prepared.

  On the other hand, for the purpose of coloring a recording medium such as recording paper or photographic paper, a resin binder is required to improve the fixing property to the recording medium and to provide high color development and gloss. . Conventionally, a dissolved resin or a dispersed resin emulsion has been used as a resin binder, and it has been prepared by simply adding it to a dispersion or ink. However, the viscosity tends to increase due to the simple addition of the resin, and the dispersion of the water-insoluble colorant tends to become unstable due to the interaction with the water-insoluble colorant, which tends to cause clogging of the printer head.

  In summary, for water-insoluble colorants, water-based dispersions, or inks prepared from them, water-insoluble colorants with ultrafine particle sizes and crystal sizes are prepared by a method different from pulverization. Ideally, a resin binder that provides stable dispersion stabilization and gives fixing properties and glossiness should be satisfied at the same time without increasing the viscosity.

  Therefore, first, as a method for obtaining an ultrafine water-insoluble color material by a method different from pulverization, the water-insoluble color material is dissolved and poured into water to precipitate the water-insoluble color material to prepare fine particles. A method has been proposed. As a conventional technique, a technique called an acid pasting method in which a water-insoluble colorant is dissolved in sulfuric acid and poured into water (Patent Document 1), a water-insoluble colorant is dissolved in an aprotic polar organic solvent in the presence of an alkali. After that, a technique for obtaining a fine color material by neutralizing with an acid (Patent Document 2), a water-insoluble color material and a surfactant are dissolved in an aprotic polar organic solvent in the presence of an alkali, and then poured into water. Technology for obtaining a fine color material (Patent Document 3), a water-insoluble color material and a dispersing agent such as a resin are dissolved in an aprotic polar organic solvent in the presence of an alkali, and then poured into water to obtain a fine color material. After that, acid precipitation and re-dispersion to obtain a fine color material at high concentration (Patent Document 4), a water-insoluble color material is dissolved in an amide organic solvent, and the fine color material is poured into water. The technique to obtain (patent document 5) is known. As a method for adding a resin binder without increasing the viscosity, a microcapsule dispersion and ink in which a resin is coated and dispersed around a water-insoluble colorant have been proposed (Patent Documents 6 and 7). .

Japanese Patent Laid-Open No. 9-221616 JP 11-209641 A JP 2003-26972 A JP 2004-43776 A JP 2004-91560 A Japanese Patent Laid-Open No. 9-151342 Japanese Patent Laid-Open No. 10-140065

  Patent Document 1 describes a dispersion and an ink in which a water-insoluble colorant is dissolved in sulfuric acid and poured into water, and then dispersed by adding a pigment dispersant. The dispersion particle diameter is 100 nm or more. It is difficult to say that sufficient color development and transparency are exhibited.

  In addition, Patent Document 2 describes a fine colorant that is obtained by dissolving a water-insoluble colorant in an aprotic polar organic solvent in the presence of an alkali and then neutralizing with an acid, but has not yet been dispersed. .

  Patent Document 3 describes a technique in which a water-insoluble colorant and a surfactant are dissolved in an aprotic polar organic solvent in the presence of an alkali, and poured into water to obtain a fine colorant dispersion. Yes. However, dispersion stabilization with only a surfactant causes aggregation at the stage of adding an aqueous solvent as an ink for ink jet recording and a color filter ink, and it is difficult to say that excellent characteristics can be exhibited in the above applications. .

  In Patent Document 4, a water-insoluble colorant and a dispersing agent such as a resin are dissolved in an aprotic polar organic solvent in the presence of an alkali and put into water to obtain a fine colorant. And a technique for obtaining a fine color material at a high concentration by performing redispersion. However, since the aggregation of pigment particles cannot be prevented in the acid precipitation step, it can be said that even if neutralization with alkali is performed thereafter, a water-insoluble color material of a nanometer order having a uniform size can be stably obtained. It is difficult.

  Patent Document 5 describes a technique for obtaining a fine color material by dissolving a water-insoluble color material in an amide-based organic solvent and throwing it into water. However, since there is no treatment to stabilize the dispersion in the system, if the operation is performed to remove the amide organic solvent to a concentration that can actually be used as a coloring material, significant aggregation occurs and it cannot be used in practice. Absent.

  Further, Patent Documents 6 to 7 describe dispersions and inks dispersed by coating a resin around a pigment. The dispersion liquid and the recording liquid have a prescription for refining pigment components. Since it is not used, it is difficult to say that transparency and color developability are sufficient.

  Therefore, the present invention prepares an ultrafine water-insoluble colorant, and at the same time, highly disperses and stabilizes with a resin, so that it has excellent color development, transparency, glossiness, water resistance, light resistance, fixability, etc. It is a technical object to provide colored resin fine particles capable of expressing an image with fastness and an aqueous dispersion containing the colored resin fine particles, an ink jet recording ink, or a color filter ink.

  The technical problem can be achieved by the present invention as follows.

  That is, the present invention is a colored resin fine particle containing a water-insoluble colorant and having an average particle diameter of 100 nm or less, and the resin component is composed of a hydrophilic resin and a hydrophobic resin, and the average particle diameter of the water-insoluble colorant is 50 nm. Colored resin fine particles characterized by the following (Invention 1).

  Alternatively, the present invention is the colored resin fine particle according to the first aspect of the present invention, wherein the water-insoluble colorant contained in the colored resin fine particle has an average crystal size of 20 nm or less (Invention 2).

  In the present invention, the hydrophilic resin is a resin selected from a styrene acrylic resin, a silicone resin, a polyester resin, a urethane resin, or a copolymer resin of two or more thereof, and has an acid value of 50 mgKOH / g or more. The colored resin fine particles according to the first or second aspect of the invention, which is an alkali-soluble resin (Invention 3).

  Further, in the present invention, the hydrophobic resin is a resin selected from styrene acrylic resin, silicone resin, polyester resin, urethane resin, or a copolymer resin of two or more thereof, and is an alkali-insoluble resin. The colored resin fine particles according to any one of the present inventions 1 to 3 (present invention 4).

  The present invention also provides the colored resin fine particles according to any one of the first to fourth aspects, wherein the colored resin fine particles contain 10 to 90% by weight of a water-insoluble colorant (Invention 5).

  Further, the present invention is an aqueous dispersion characterized in that the colored resin fine particles according to the first to fifth aspects of the present invention are dispersed in an aqueous dispersion medium (Invention 6).

  Further, the present invention is the aqueous dispersion according to the present invention 6, wherein the dispersed particle size has a cumulative 90% particle size (P90) of the number conversion distribution of 100 nm or less. (Invention 7).

  Further, the present invention is an aqueous dispersion according to the present invention 6 or 7, wherein in the dispersed particle size, the cumulative 90% particle size (P90) of the number conversion distribution and the cumulative 50% particle size (P50) of the number conversion distribution The water-based dispersion is characterized in that the particle size ratio (P90 / P50) is 5 or less (Invention 8).

  Further, the present invention is an ink for ink jet recording using the colored resin fine particles according to any one of the first to fifth aspects or the aqueous dispersion according to any one of the sixth to eighth aspects. (Invention 9)

  Further, the present invention is an ink for a color filter using the colored resin fine particles according to any one of the first to fifth aspects or the aqueous dispersion according to any one of the sixth to eighth aspects (Invention 10).

  The colored resin fine particles according to the present invention are colored resin fine particles containing an ultrafine water-insoluble colorant in the resin fine particles, and exhibit excellent color development and transparency due to the fineness of the water-insoluble colorant. Yes. In addition, by forming resin fine particles by combining a hydrophilic resin and a hydrophobic resin, it is possible to express images with excellent glossiness and fastness such as water resistance, light resistance, and fixability. Since the dispersion stability at the time of preparation is good, it is suitable as a color material to be a precursor of ink for inkjet recording and ink for color filter display.

  Since the aqueous dispersion according to the present invention is composed of colored resin fine particles having the characteristics as described above, the image has excellent color developability, transparency and glossiness, and has fastness such as water resistance, light resistance and fixability. And the dispersion stability at the time of preparing the ink itself is good, and it is suitable as a colorant dispersion that is a precursor of ink for inkjet recording and ink for color filter display.

  The ink for ink jet recording according to the present invention is composed of colored resin fine particles having the characteristics as described above or an aqueous dispersion, so that it has excellent color developability, transparency, glossiness, water resistance, light resistance, fixability and the like. Since an image having fastness can be expressed and the dispersion stability is good, it is suitable as an ink for ink jet recording.

  Since the color filter ink according to the present invention is composed of the colored resin fine particles having the characteristics as described above or an aqueous dispersion, it is excellent in color development, transparency, glossiness, water resistance, light resistance, fixability, etc. An image having fastness can be expressed, and since the dispersion stability is good, it is suitable as an ink for a color filter.

  The configuration of the present invention will be described in more detail as follows.

  First, the colored resin fine particles according to the present invention will be described.

  The colored resin fine particles according to the present invention are resin fine particles composed of two kinds of resins, a hydrophilic resin and a hydrophobic resin containing a water-insoluble colorant prepared in an ultrafine manner, and have an average particle size of 100 nm or less. When the average particle size of the colored resin fine particles exceeds 100 nm, sufficient color developability cannot be exhibited. The average particle size is preferably 95 nm or less, and more preferably the average particle size is 50 to 90 nm.

  The average particle diameter of the water-insoluble colorant in the colored resin fine particles is 50 nm or less. When the average particle diameter of the color material exceeds 50 nm, sufficient transparency cannot be exhibited. The average particle diameter is preferably 45 nm, more preferably the average particle diameter is 10 to 40 nm.

  The average crystal size of the water-insoluble colorant in the colored resin fine particles is preferably 20 nm or less. When the average crystal size exceeds 20 nm, sufficient transparency cannot be exhibited. More preferably, it is 19 nm or less, More preferably, it is 18 nm or less.

  A hydrophilic resin is a resin in which acidic groups are neutralized and hydrophilic when a basic compound is added to the resin. Styrene acrylic resin, silicone resin, polyester resin, urethane resin, or two or more types are copolymerized Those are preferred. For example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, divinylbenzene, trivinylbenzene, 4-methoxystyrene, 4-cyano Polymers of monomers selected from styrene monomers such as styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylphenanthrene, styrene macromer and derivatives thereof, or acrylic acid, methyl acrylate, ethyl acrylate, acrylic Propyl acrylate, butyl acrylate, ethyl hexyl acrylate, octyl acrylate, stearyl acrylate, lauryl acrylate, acrylonitrile, acrylamide, dimethylaminoethyl acrylate, methacrylic acid, methyl methacrylate , Ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl hexyl methacrylate, octyl methacrylate, stearyl methacrylate, lauryl methacrylate, glycidyl methacrylate, methacrylonitrile, methacrylamide, dimethylaminoethyl methacrylate, itaconic acid, itacone Acrylic monomers such as methyl acrylate, ethyl itaconate, fumaric acid, dimethyl fumarate, diethyl fumarate, maleic acid, dimethyl maleate, diethyl maleate, crotonic acid, methyl crotonic acid, ethyl crotonic acid, methyl methacrylate macromer And a monomer polymer selected from the group consisting of styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, Tylene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl acid copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-maleic acid copolymer, styrene-maleic acid half ester copolymer, styrene-maleic acid diester copolymer Polymer, acrylic acid-methacrylic acid copolymer, acrylic acid-methacrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-methyl methacrylate-acrylic acid copolymer, styrene-methacrylic acid Two types such as acid-acrylic acid copolymer Styrene acrylic resins such as block copolymers, random copolymers, or graft copolymers polymerized from these monomers, and side-chain, single-end, double-end, and side-chain double-end modifications Silicone resins such as silicone oil, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, sodium sulfoisophthalate, succinic acid, adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, A divalent carboxylic acid such as dimer acid, a polyvalent carboxylic acid such as trivalent or higher carboxylic acid such as trimellitic acid, pyromellitic acid, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 2,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polytetraethylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, etc. Polymers of polyhydric alcohols such as trihydric alcohols such as polyhydric alcohols, trimethylolpropane and pentaerythritol, or polyester resins such as block copolymers, random copolymers, graft copolymers thereof, , Polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), poly (tetramethylene adipate) G), poly (hexamethylene adipate), poly-ε-caprolactone, poly (hexamethylene carbonate), silicone polyol and the like, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene Polymers with urethane bonds of isocyanates such as diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, or block copolymers, random copolymers, graft copolymers thereof. Urethane resin such as polymer, or styrene acrylic resin-polyester resin copolymer, styrene acrylic resin-urethane Examples include an interpolymer resin such as a resin copolymer, an anion resin having an acid group such as a carboxyl group, a sulfonic acid group, a sulfate ester group, or a phosphate ester group in the resin. Is preferably 50 mgKOH / g or more. More preferably, it is 50-300 mgKOH / g, More preferably, it is 100-250 mgKOH / g. The weight average molecular weight is preferably 1,000 to 25,000. More preferably, it is 1,500-20,000, More preferably, it is 2,000-18,000.

  Hydrophobic resin is a resin component that is insoluble in an aqueous dispersion medium without being neutralized even if a basic compound or an acidic compound is added to the resin (alkali insoluble). Styrene acrylic resin, silicone resin, polyester resin , Urethane resins, or those obtained by copolymerization of two or more types are preferred. Furthermore, when the hydrophobic resin component is formed by further polymerizing on the surface and inside of the resin fine particles, the monomer is polymerized in the vicinity of the hydrophilic resin or the water-insoluble colorant via a surfactant, if necessary. It is preferable that

  When a hydrophobic resin is formed by a polymerization reaction, the monomers used are styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, α-methylstyrene, chlorostyrene, bromo Styrene monomers such as styrene, divinylbenzene, trivinylbenzene, 4-methoxystyrene, 4-cyanostyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylphenanthrene, styrene macromer, and derivatives thereof, acrylic acid, acrylic acid Methyl, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl hexyl acrylate, octyl acrylate, stearyl acrylate, lauryl acrylate, acrylonitrile, acrylamide, methacrylic acid, methyl methacrylate, Ethyl crylate, propyl methacrylate, butyl methacrylate, ethyl hexyl methacrylate, octyl methacrylate, stearyl methacrylate, lauryl methacrylate, glycidyl methacrylate, methacrylonitrile, methacrylamide, itaconic acid, methyl itaconate, ethyl itaconate, Acrylic monomers and their derivatives such as fumaric acid, dimethyl fumarate, diethyl fumarate, maleic acid, dimethyl maleate, diethyl maleate, crotonic acid, methyl crotonic acid, ethyl crotonic acid, methyl methacrylate macromer, vinyltrichlorosilane Silanes such as vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane Mer and derivatives thereof, methacryloxypolydimethylsiloxane and other one-end methacryl-modified silicone oils, both-end methacryl-modified silicone oils and other silicone-based monomers and their derivatives, and these can be used alone or in combination of two or more. . At the same time, alkyl vinyl monomers such as isoprene, chloroprene, isobutene and 3-methyl-1-butene, vinyl ether monomers such as butyl vinyl ether and isobutyl vinyl ether, vinyl carboxylates such as vinyl formate, vinyl acetate and vinyl propionate, vinyl chloride In addition, a different monomer such as a vinyl halide monomer such as vinylidene chloride or vinylidene fluoride may be contained. In addition, a polyfunctional monomer, or a macromer such as a polyoxyethylene macromer or a polyoxazoline macromer can also be included.

  As the surfactant, either one having no reactive group or one having a reactive group may be used, but if it has no reactive group, alkylbenzene sulfonic acid and its salt, alkyl naphthalene sulfonic acid and its salt, dialkyl sulfosuccinic acid And salts thereof, alkyl diphenyl ether disulfonic acid and salts thereof, fatty acids and salts thereof such as stearic acid and oleic acid, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Oxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Over DOO, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitol, glycerol monostearate, glycerol mono-Ore benzoate and the like. If it has a reactive group, vinylsulfonic acid, allylsulfonic acid, 3-acryloyloxypropanesulfonic acid, 2-methylallylsulfonic acid, 2-acryloyloxyethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid And sulfuric acid ester of allyl alcohol, alkylallylsulfosuccinic acid and its salt, methacryloyloxypolyoxyalkylene sulfate and its salt, and the like. These can be used alone or in combination of two or more.

  As a ratio of the hydrophilic resin and the hydrophobic resin, the hydrophobic resin is preferably 20 to 500% by weight with respect to the hydrophilic resin. When the amount is less than 20% by weight, the hydrophilic resin diffuses into the aqueous dispersion medium when dispersed in the aqueous dispersion medium, and the dispersion tends to become unstable. Furthermore, there is a concern about deterioration of water resistance. On the other hand, if it exceeds 500% by weight, the hydrophobicity becomes too strong and the function of dispersing in an aqueous dispersion medium is lowered, making it difficult to use as an ink. More preferably, it is 30 to 300% by weight.

  The proportion of the resin (total of hydrophilic resin and hydrophobic resin) in the colored resin fine particles is preferably such that the resin is contained in the colored resin fine particles in an amount of 10 to 90% by weight. When the amount is less than 10% by weight, when dispersed in an aqueous dispersion medium, the surface property of the water-insoluble colorant becomes dominant with respect to the dispersion, the dispersion stability is lowered, and it becomes difficult to use as an ink. On the other hand, if it exceeds 90% by weight, the resin content is too much with respect to the water-insoluble colorant, and when trying to be dispersed in an aqueous dispersion medium at an appropriate color density, the viscosity tends to increase and it is difficult to use. . More preferably, it is 20 to 80% by weight.

  As the water-insoluble colorant of the colored resin fine particles according to the present invention, any material can be used as long as it is insoluble in the aqueous dispersion medium and can achieve the present invention. More preferably, the water-insoluble colorant that does not change in quality during the micronization operation is preferable. Specifically, organic pigments, oil-soluble dyes, disperse dyes, vat dyes, and the like that are used as colorants for printing inks, paints, and resin compositions can be used.

  The water-insoluble colorant may be used at the same time depending on the required hue. Further, two or more kinds of similar colors may be used depending on the required hue and characteristics.

  Examples of the organic pigment include Pigment-Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 19, 21, 22, 23, 31, 32, 37, 38, 41. 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52, 52: 1, 52: 2, 53, 53: 1, 53 : 2, 53: 3, 57, 57: 1, 58: 4, 60, 63: 1, 63: 2, 64: 1, 68, 81, 81: 1, 81: 2, 81: 3, 81: 4 83, 88, 90: 1, 97, 112, 114, 122, 123, 144, 146, 147, 149, 150, 151, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176 177, 178, 179, 180, 181, 184, 185, 187, 88, 190, 191, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 215, 216, 217, 219, 220, 221, 223, 224, 226, 227, 228, 238, 240, 242, 243, 245, 247, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 267, 268, 269, 270, 272, 273, 274, 279, Pigment-Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 18, 19, 22, 24, 25, 27, 56, 56: 1, 57, 60, 61, 61: 1, 62, 63, 64, 66, 80, 88, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 88, 93, 94, 95, 97, 98, 99, 100, 101, 102, 104, 105, 108, 109, 110, 111, 115, 116, 117, 120, 123, 125, 126, 127, 128, 129, 130, 133, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 185, 188, 191, 192, 193, 194, 196, 198, 199, 202 , 203, 213, 214, Pigment-Black 1, 20, 31, 32, Pigment-Green 1, 7, 8, 10, 36, Pigment-Orange 1, 2, 5, 13, 16, 17, 22, 24, 34, 36 38, 43, 48, 49, 51, 55, 59, 61, 62, 64, 66, 67, 69, 70, 71, 72, 73, 74, 77, Pigment-Violet 3, 19, 23, 25, 29 30, 31, 32, 37, 39, 40, 42, 50, Pigment-Brown 1, 23, 25, 27, organic fluorescent pigment (fluorescent dye / synthetic resin solid solution), and the like.

  As the oil-soluble dye, Solvent-Red 1, 2, 3, 4, 8, 13, 18, 23, 24, 25, 26, 27, 30, 32, 43, 44, 45, 49, 51, 52, 60, 72, 73, 79, 89, 91, 92, 109, 111, 122, 124, 127, 132, 135, 146, 168, 179, 195, 197, 218, 242, Solvent-Blue 2, 4, 5, 6, 8, 11, 13, 23, 24, 35, 36, 38, 44, 45, 59, 70, 74, 78, 104, 122, 124, Solvent-Yellow 2, 5, 6, 7, 14, 15, 16, 18, 19, 21, 29, 33, 44, 51, 56, 62, 72, 79, 82, 83, 83: 1, 93, 98, 114, 116, 133, 145, 163, 167, 17 Solvent-Black 3, 5, 7, 27, 29, 34, 45, Solvent-Green 1, 3, 5, 7, 28, Solvent-Orange 2, 60, 63, 41, 45, 54, 60, 62, 63, 86 Solvent-Violet 3, 8, 9, 11, 13, 31, 37, 49, 56, 59, Solvent-Brown 1, 41, 43, 53, and the like.

  Disperse dyes include Disperse-Red 1, 4, 11, 13, 50, 54, 58, 60, 72, 73, 74, 82, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135. , 143, 145, 146, 152, 153, 154, 159, 164, 167, 167: 1, 177, 179, 181, 191, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283 311, 323, 343, 348, 356, 362, 364, Disperse-Blue 3, 7, 14, 35, 56, 60, 72, 73, 77, 79, 87, 106, 113, 128, 143, 148, 154 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 2 4, 225, 257, 266, 267, 284, 287, 291, 301, 354, 358, 359, 365, 366, 367, 368, Disperse Yellow 3, 5, 23, 42, 54, 64, 79, 82, 83, 93, 99, 100, 114, 119, 121, 122, 124, 126, 134, 160, 184, 184: 1, 186, 198, 199, 204, 224, 237, 211, 241, Disperse-Green 6: 1, 9, Disperse-Orange 1, 3, 11, 25, 29, 30, 31, 31: 1, 33, 44, 49, 54, 66, 73, 118, 119, 163, Disperse-Violet 1, 26, 33, 35, 63, 77, 93, 96, Disperse-Brown 1, 19 And the like.

  As vat dyes, Vat-Red 1, 10, 13, 14, 15, 23, 29, 31, 41, Vat-Blue 1, 4, 6, 20, 43, Vat-Yellow 1, 2, 4, 10, 12, 27, 29, 33, Vat-Black 16, 25, 27, 29, Vat-Green 1, 3, 8, 9, Vat-Orange 1, 2, 3, 4, 7, 9, 11, 15, 16, Vat-Violet 1, 9, Vat-Brown 1, 3, 5, 57, and the like.

  The ratio of the water-insoluble colorant in the colored resin fine particles is preferably 10 to 90% by weight of the water-insoluble colorant in the colored resin fine particles. When the amount is less than 10% by weight, the resin content is too much with respect to the water-insoluble colorant, and when it is used by being dispersed in an aqueous dispersion medium with an appropriate color density, the viscosity tends to increase and it is difficult to use. In the case of 90% by weight or more, when dispersed in an aqueous dispersion medium, the surface property of the water-insoluble colorant becomes dominant with respect to the dispersion, the dispersion stability is lowered, and it becomes difficult to use as an ink. More preferably, it is 20 to 80% by weight.

  The colored resin fine particles according to the present invention may contain water-insoluble inorganic fine particles together with the water-insoluble colorant. The water-insoluble inorganic fine particles function as a surface active powder and have a function of finely stabilizing the dispersion of resin fine particles as a whole system. In addition, since this water-insoluble inorganic fine particle has an absorption band on the short wavelength side in the ultraviolet-visible region of light, it absorbs the short-wavelength side in the ultraviolet-visible region of light such as sunlight and fluorescent lamps, and the color material deteriorates due to light And the light resistance of the printed matter can be improved.

  The content of the water-insoluble inorganic fine particles is preferably 1 to 50% by weight with respect to the water-insoluble colorant. If it exceeds 50% by weight, the content of the water-insoluble colorant is undesirably reduced. More preferably, it is 1 to 30% by weight.

As water-insoluble inorganic fine particles, Mg, Ca, Ba, Ti, Zr, Ta, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Au, Zn, Al, Ga, Si , A compound composed of an oxide, hydroxide, carbonate, sulfate of one or more elements selected from Ge, and those not directly related to coloring are preferable. For example, silicon oxide fine particles such as silica, titanium oxide fine particles such as rutile and anatase, aluminum compound fine particles such as alumina and boehmite, magnesium compound fine particles such as calcium carbonate fine particles, magnesia and hydrotalcite, zinc oxide fine particles, barium sulfate fine particles, Iron oxide fine particles such as hematite, magnetite, and goethite, preferably silicon oxide fine particles, titanium oxide fine particles, and aluminum compound fine particles.
In addition, when the water-insoluble inorganic fine particles themselves are colored, for example, when carbon black is used as a color material, the same color system such as black magnetite can be used, and the hue is slightly different However, any colorant that does not hinder the hue of the colorant used as the water-insoluble colorant can be used.

  The particle shape of the water-insoluble inorganic fine particles may be any shape such as spherical, granular, polyhedral, needle-shaped, spindle-shaped, rice-grained, flake-shaped, flake-shaped and plate-shaped. In view of dispersion and dispersion, spherical, granular, and polyhedral shapes are preferred.

The average particle size of the water-insoluble inorganic fine particles is preferably 1 to 50 nm, more preferably 10 to 45 nm. The BET specific surface area is preferably 1 to 300 m ² / g.

  The water-insoluble inorganic fine particles are preferably subjected to a hydrophobic surface treatment for the purpose of preventing aggregation due to surface hydroxyl groups and for the purpose of improving the surface activity and the adsorptivity with the resin. Hydrophobic surface treatment agents include silane-based surface treatment agents, titanium-based surface treatment agents, organic compounds that bind to the surface of water-insoluble inorganic fine particles through organic reactions, or hydrophobic properties such as surfactants and hydrophobic resins. These materials can be used, and one kind or a mixture of two or more kinds can be used.

Silane surface treatment agents include methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, trimethyltrimethoxysilane, triethylethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane , Trimethylchlorosilane, hexamethyldisilazane, hexaphenyldisilazane, trimethylsilane, allyldimethylchloro , Allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl Examples include acrylate, vinyldimethylacetoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and 1,3-diphenyltetramethyldisiloxane.
Titanium surface treatment agents include isopropoxy titanium / triisostearate, isopropoxy titanium / dimethacrylate / isostearate, isopropoxy titanium / tridodecylbenzene sulfonate, isopropoxy titanium / trisdioctyl phosphate, isopropoxy titanium / tris N-ethylaminoethylaminato, titanium bisdioctyl pyrophosphate oxyacetate, bisdioctyl phosphate ethylene dioctyl phosphite, di-n-butoxy bistriethanolaminato titanium and the like.

  Organic compounds that bind to the surface of water-insoluble inorganic fine particles through organic reactions include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, beef tallow fatty acid, castor cured Fatty acids such as fatty acids, soybean fatty acids, palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid and their salts or their esters or their acid chlorides, lauryl alcohol, myristyl alcohol, cetyl alcohol, octyl alcohol, decyl Higher alcohols such as alcohol, cetostearyl alcohol, stearyl alcohol, 2-octyldodecanol and behenyl alcohol, hydrophobic amino such as glycine, alanine, phenylalanine, leucine, isoleucine and valine Thiols such as acids, peptides and proteins rich in hydrophobic amino acids, thiophenol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, decylcyol, dodecylthiol, ethyl chloride, butyl chloride, pentyl chloride, hexyl chloride And alkyl halides such as benzyl chloride, acid chlorides such as benzoyl chloride and hexyl carboxychloride.

  As the surfactant, glyceryl monostearate, glyceryl monooleate, glyceryl monocaprylate, propylene glycol monostearate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan dioleate, Examples include sorbitan trioleate, sorbitan sesquioleate, coconut fatty acid sorbitan, sorbitan monopalmitate, isostearyl glyceryl ether, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, and stearyltrimethylammonium chloride. Examples of hydrophobic resins include homopolymers of styrene such as polystyrene and polyvinyltoluene, and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate. Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene- Vinyl methyl ketone , Styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, and other styrene copolymers; polymethyl methacrylate, polybutyl methacrylate, polyacetic acid Vinyl, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic Examples include petroleum resin, paraffin wax, and carnauba wax.

  The treatment amount of the hydrophobic surface treatment is preferably 1 to 50% by weight, more preferably 1 to 30% by weight with respect to the water-insoluble inorganic fine particles.

  Next, the aqueous dispersion according to the present invention will be described.

  The aqueous dispersion according to the present invention is one in which the colored resin fine particles are dispersed in an aqueous dispersion medium.

  The aqueous dispersion according to the present invention can contain water and, if necessary, a water-soluble organic solvent as an aqueous dispersion medium. The ratio of the water-soluble organic solvent in the aqueous dispersion is preferably 1 to 50% by weight, more preferably 1 to 30% by weight.

  Examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1 , 3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, and other polyhydric alcohols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol monomethyl ether, triethylene glycol Polyethyl alcohol alkyl ethers such as noethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, polyhydric alcohol allyl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, Nitrogen-containing heterocyclic compounds such as 1,3-dimethylimidazolidinone and γ-butyrolaclone, amides such as N, N-dimethylformamide and urea, amines such as monoethanolamine, diethanolamine and triethanolamine, thiodiethanol , Sulfolane, dimethyl sulfoxide and other sulfur-containing compounds are used, and these may be used alone or in combination.

  As for the dispersed particle diameter of the aqueous dispersion according to the present invention, the cumulative 10% particle diameter (P10) of the number conversion distribution is preferably 10 nm or more, more preferably 20 to 60 nm. The cumulative 50% particle size (P50) of the number conversion distribution is preferably 70 nm or less, more preferably 20 to 68 nm. The cumulative 90% particle size (P90) of the number conversion distribution is preferably 100 nm or less, more preferably 95 nm or less, still more preferably 30 to 90 nm.

  In the dispersed particle size of the aqueous dispersion according to the present invention, the particle size ratio (P90 / P50) between the cumulative 90% particle size (P90) of the number conversion distribution and the cumulative 50% particle size (P90) of the number conversion distribution is 5 or less is preferable. When the particle size ratio exceeds 5, scattered light may be generated and transparency may be lowered. More preferably, it is 3 or less, and still more preferably 2 or less.

  The viscosity of the aqueous dispersion according to the present invention is preferably 20.0 mPa · s or less. When the viscosity exceeds 20.0 mPa · s, the viscosity of the ink-jet ink prepared using this is unfavorable. More preferably, it is 16.0 mPa · s or less. The lower limit is about 1.0 mPa · s.

  The content of the colored resin fine particles in the aqueous dispersion according to the present invention is preferably 1 to 40% as the concentration of the water-insoluble colorant. If it is less than 1%, the color density is dilute and it is difficult to use it as an ink in various applications. When it exceeds 40%, it becomes difficult to sufficiently disperse. More preferably, it is 2 to 30%.

  Next, a method for producing the colored resin fine particles and the aqueous dispersion according to the present invention will be described.

  In the present invention, first, a water-insoluble colorant is dissolved in an aprotic organic solvent and precipitated in an aqueous dispersion medium to obtain a slurry in which the water-insoluble colorant is finely divided. The slurry is concentrated, and a hydrophilic resin is added thereto to sufficiently disperse the finely divided water-insoluble colorant. At this stage, the hydrophilic resin tends to diffuse into water, and dispersion tends to become unstable over time. Therefore, in the present invention, the resin fine particles formed by the hydrophilic resin by adding a hydrophobic resin or adding a surfactant and a monomer as necessary and performing seed polymerization by emulsion polymerization in or near the hydrophilic resin. A network structure of a hydrophobic resin is formed in the inner layer or in the vicinity thereof to form a crosslinking point with the hydrophilic resin to obtain colored resin fine particles and an aqueous dispersion.

  The colored resin fine particles and the aqueous dispersion according to the present invention are obtained through each step of a dissolution step, a precipitation step, a concentration step, a dispersion step, a hydrophobic resin addition or polymerization step, a water washing step, a redispersion step, and a post-treatment step. Can do.

  The dissolution step is a step of dissolving the water-insoluble colorant in an aprotic organic solvent or an aprotic organic solvent in the presence of a basic substance.

  Examples of aprotic organic solvents include 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, nitrogen-containing heterocyclic compounds such as γ-butyrolacron, N, N-dimethylformamide, tetramethylurea, hexamethylphospho Amides such as amide, hexamethylphosphorotriamide, cyclic amines such as pyridine and 2-methylpyridine, ketones such as acetone, 2-butanone and cyclohexanone, ethers such as diethyl ether, tetrahydrofuran and dioxane, dimethyl sulfoxide and sulfolane Examples thereof include sulfur-containing compounds, nitriles such as acetonitrile, benzonitrile, and propionitrile.

  Basic substances include inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, N-methyldiethylamine, morpholine, N, N-dimethylaminoethanol, N, Organic amines such as N-diethylaminoethanol, 2-amino-2-methyl-1-propanol, monoethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, diisopropanolamine, diethanolamine and triethanolamine can be used. .

  In the precipitation step, if necessary, the solution prepared in the dissolution step is quickly added to an aqueous dispersion medium containing a surfactant and an aqueous organic solvent, and the ultrafine water-insoluble colorant is re-introduced into the aqueous dispersion medium. It is a step of precipitation or recrystallization.

  When a water-insoluble colorant solution is added to an aqueous dispersion medium to form an ultrafine water-insoluble colorant, high pressure is applied to the precipitation process in order to increase the crystallization speed and make finer and more uniform precipitates or crystals. Dispersers such as a homogenizer, an ultrasonic homogenizer, an internal circulation type stirrer, an external circulation type stirrer, and a thin film swirl type high speed stirrer can be used.

  The concentration step is a step of increasing the concentration of the ultrafine water-insoluble colorant prepared in the precipitation step and adjusting the slurry to a concentration suitable for the dispersion step.

  When concentrating, use distillation with an evaporator, distillation tower, etc., filtration with a filter, crossflow membrane, ultrafiltration membrane, reverse osmosis membrane, etc., centrifugation with a centrifuge, freeze drying, chromatography, etc. Can do.

  In the dispersing step, the hydrophilic hydrophilic resin is dissolved in the concentrated liquid, and if necessary, a monomer, a surfactant, a polymerization initiator, a polymerization chain transfer agent, etc. are added, and a high-pressure disperser such as a high-pressure homogenizer, a homogenizer, In this step, an ultrafine water-insoluble colorant is dispersed in an aqueous dispersion medium by a dispersing machine such as a high-speed stirrer such as a homomixer, a kneading and dispersing machine such as a bead mill or a roll mill, or an ultrasonic dispersing machine such as an ultrasonic homogenizer.

  A hydrophilic resin can be obtained by adding a basic compound to a hydrophilic resin to neutralize acidic groups. Specifically, for resins such as styrene acrylic resin, silicone resin, polyester resin and urethane resin, inorganic salts such as sodium hydroxide, potassium hydroxide and lithium hydroxide, or ammonia, trimethylamine, ethylamine, diethylamine, triethylamine N-methyldiethylamine, morpholine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, 2-amino-2-methyl-1-propanol, monoethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, di It can be obtained by adding a basic compound such as organic amines such as isopropanolamine, diethanolamine and triethanolamine.

  Hydrophobic resin addition or polymerization step is performed by adding a hydrophobic resin or, if necessary, adding a monomer, a surfactant, a polymerization initiator, a polymerization chain transfer agent, and conducting an emulsion polymerization reaction. This is a step of stably preparing colored resin fine particles in water. You may disperse | distribute with the above-mentioned disperser etc. as needed.

  When preparing hydrophobic resin by superposition | polymerization, a polymerization initiator can be used as needed. The polymerization initiator may be either oil-soluble or water-soluble, but if it is an oil-soluble polymerization initiator, it may be added before the start of dispersion. If it is a water-soluble polymerization initiator, it may be added immediately before the polymerization reaction.

  As the polymerization initiator, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero) are those that are oil-soluble. Nitriles) and 2,2-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and other azo polymerization initiators, and peroxide polymerization initiators such as benzoyl peroxide and lauryl peroxide. Examples of water-soluble compounds include persulfates such as sodium persulfate and potassium persulfate, peroxides such as hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4 -Cyanovaleric acid), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) ) Propane] dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamide] hydrate and other azo polymerization initiators, a combination of ammonium persulfate and sodium bisulfite, ammonium persulfate And a combination of aminoethanol, redox initiator and the like. One or a combination of two or more of these can be used.

  When preparing hydrophobic resin by superposition | polymerization, a polymerization chain transfer agent can be used as needed. Specific examples of the polymerization chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, xanthogen disulfides such as dimethyl xanthogen disulfide, diisopropyl xanthogen disulfide, tetra Thiraum sulfides such as methyltyramium disulfide and tetrabutyltalladium disulfide, halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide, hydrocarbons such as pentaphenylethane, acrolein, methacrolein, allyl alcohol, 2 -Unsaturated hydrocarbons such as ethylhexyl thioglycolate. These can be used alone or in combination of two or more.

  In the water washing step, the colored resin fine particles obtained in the addition of the hydrophobic resin or the polymerization step are washed by centrifugation, suction filtration, pressure filtration, ultrafiltration, reverse osmosis membrane filtration, etc. This is a step of removing impurities such as existing salts and unreacted monomers.

  The redispersion step is a step in which a slight amount of a basic substance is added to the obtained colored resin fine particles as necessary to make the resin surface hydrophilic again and dispersed in an aqueous dispersion medium to obtain an aqueous dispersion. Examples of basic substances to be added include inorganic salts such as sodium hydroxide, potassium hydroxide and lithium hydroxide, or ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, N-methyldiethylamine, morpholine, N, N-dimethylaminoethanol, Organic amines such as N, N-diethylaminoethanol, 2-amino-2-methyl-1-propanol, monoethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, diisopropanolamine, diethanolamine and triethanolamine The pH after redispersion is preferably in the range of 7-11. In the redispersion step, it is preferable to use the same disperser as used in the dispersion step.

  In the post-treatment step, coarse particles and impurities contained in the obtained aqueous dispersion are removed by filtering and centrifuging, and further dilution or ultrafiltration by adding ion exchange water, reverse osmosis membrane filtration, and vacuum distillation And the like, and the concentration of the colored resin fine particles is adjusted.

  In the present invention, when it is necessary to take out the colored resin fine particles, the dispersion after the post-treatment step may be taken out by a conventional method such as ultrafiltration, reverse osmosis membrane filtration, centrifugation, spray drying, freeze drying and the like. .

  Since the colored resin fine particles according to the present invention are prepared in an aqueous dispersion medium, the aqueous dispersion after the post-treatment step can be directly used as the aqueous dispersion according to the present invention.

  Next, the ink for ink jet recording according to the present invention will be described.

  The ink for ink-jet recording according to the present invention contains 1 to 30%, preferably 2 to 20%, of the concentration of the water-insoluble coloring material by diluting the colored resin fine particles or the aqueous dispersion according to the present invention. .

  The ink for inkjet recording according to the present invention comprises the colored resin fine particles or the aqueous dispersion according to the present invention and water, and if necessary, additives such as a surfactant, a water-soluble organic compound, a pH adjuster and a preservative. You may contain.

  As the surfactant, an anionic surfactant or a nonionic surfactant can be used. Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, dodecylbenzene sulfonate, and laurate. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylamide, 2,4,7,9-tetramethyl. Acetylene glycols such as -5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol (for example, manufactured by Air Products) Surfinol 104, 420, 440, 465, 485, etc.) can be used, and one or a mixture of two or more can be used.

  Examples of water-soluble organic compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,3-butanediol, and 1,5-pentanediol. , 1,6-hexanediol, glycerol, and other polyhydric alcohols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Ethyl ether, triethylene glycol monobutyl ether Polyhydric alcohol alkyl ethers such as tetraethylene glycol monomethyl ether, polyhydric alcohol allyl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, Nitrogen-containing heterocyclic compounds such as γ-butyrolaclone, N, N-dimethylformamide, amides such as urea, amines such as monoethanolamine, diethanolamine and triethanolamine, sulfur-containing compounds such as thiodiethanol, sulfolane and dimethylsulfoxide Compound, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, cellulose, Examples thereof include saccharides such as dextrin and cyclodextrin, and one kind or a mixture of two or more kinds can be used.

  Examples of pH adjusters include inorganic salts such as sodium hydroxide, potassium hydroxide and lithium hydroxide, or ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, N-methyldiethylamine, morpholine, N, N-dimethylaminoethanol, N , N-diethylaminoethanol, 2-amino-2-methyl-1-propanol, monoethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, diisopropanolamine, diethanolamine, triethanolamine and other organic amines , One or a mixture of two or more can be used.

  Examples of the preservative include alkyl isothiazolone, chloroalkyl isothiazolone, benzisothiazolone, bromonitroalcohol, oxazolidine, chloroxylenol and the like, and one or a mixture of two or more can be used.

  As for the dispersed particle diameter of the ink for inkjet recording according to the present invention, the cumulative 10% particle diameter (P10) of the number conversion distribution is preferably 10 nm or more, more preferably 20 to 60 nm. The cumulative 50% particle size (P50) of the number conversion distribution is preferably 70 nm or less, more preferably 20 to 68 nm. The cumulative 90% particle size (P90) of the number conversion distribution is preferably 100 nm or less, more preferably 95 nm or less, still more preferably 30 to 90 nm.

  In the dispersed particle size of the ink for ink jet recording according to the present invention, the particle size ratio (P90 / P50) between the cumulative 90% particle size (P90) of the number conversion distribution and the cumulative 50% particle size (P90) of the number conversion distribution. Is preferably 5 or less. When the particle size ratio exceeds 5, scattered light may be generated and transparency may be lowered. More preferably, it is 3 or less, and still more preferably 2 or less.

  The viscosity of the ink for inkjet recording according to the present invention is preferably 10.0 mPa · s or less, and when the viscosity exceeds 10.0 mPa · s, a printed image exhibiting a clear hue cannot be obtained. More preferably, it is 8.0 mPa * s or less, and a lower limit is about 1.0 mPa * s.

  The storage stability of the ink for ink jet recording according to the present invention is preferably 7% or less, more preferably 6% or less, still more preferably 5% or less, in terms of the change in the dispersed particle diameter after one week. Further, the viscosity change rate after one week is preferably 10% or less, more preferably 8% or less, and still more preferably 6% or less.

  Next, a method for producing the ink for ink jet recording according to the present invention will be described.

  The ink for inkjet recording according to the present invention comprises a predetermined amount of the colored resin fine particles or the aqueous dispersion according to the present invention, ion-exchanged water, and additives such as a water-soluble organic compound, a pH adjuster, and a preservative as necessary. It is obtained by mixing and then filtering and / or centrifuging using a membrane filter.

  Next, the color filter ink according to the present invention will be described.

  The color filter ink according to the present invention contains the colored resin fine particles or the aqueous dispersion according to the present invention in a concentration of 1 to 30%, preferably 2 to 20%, as the concentration of the water-insoluble colorant. .

  The color filter ink according to the present invention comprises the colored resin fine particles or the aqueous dispersion according to the present invention and water, and if necessary, has the same surface activity as described in the resin aqueous solution, resin emulsion, and ink jet recording ink. You may contain additives, such as an agent, a water-soluble organic compound, a pH adjuster, and antiseptic | preservative.

  Examples of the resin aqueous solution and resin emulsion resin include polyvinyl alcohol, polyacrylamide, acrylic polymer, polyester, urethane, fluororesin, and melamine resin, and one or a mixture of two or more can be used.

  Next, a method for producing the color filter ink according to the present invention will be described.

  The color filter ink according to the present invention comprises a predetermined amount of the colored resin fine particles or aqueous dispersion according to the present invention, ion-exchanged water, if necessary, a resin aqueous solution, a resin emulsion, a surfactant, a water-soluble organic compound, pH adjustment. It is obtained by mixing additives such as preservatives and preservatives, and then filtering and / or centrifuging using a membrane filter.

<Action>
The colored resin fine particles according to the present invention are colored resin fine particles in which an ultrafine water-insoluble colorant is included with two types of resins, hydrophilic and hydrophobic. The ultrafine water-insoluble colorant component exhibits excellent transparency and color development. Of these two resin compositions, the hydrophilic resin functions to disperse the colored resin fine particles containing the water-insoluble colorant in the aqueous dispersion medium, and the hydrophobic resin is entangled with the hydrophilic resin. Is prevented from diffusing into the aqueous dispersion medium, and exhibits dispersion stability and ink ejection stability during preparation of the aqueous dispersion or ink. Further, it is presumed that this resin composition exhibits gloss, fixability, light resistance and water resistance during printing.

  Since the aqueous dispersion according to the present invention is composed of the colored resin fine particles having the characteristics as described above, it exhibits a high degree of dispersion stability, and also has high color development, high glossiness, high transparency, and high water resistance of the printed matter. High light resistance and high fixability.

  The ink for ink jet recording according to the present invention is composed of colored resin fine particles having the characteristics as described above or an aqueous dispersion, so that it exhibits high dispersion stability and high ink ejection stability in an ink jet system, and also a printed matter. High color development, high glossiness, high transparency, high water resistance, high light resistance and high fixability.

  The color filter ink according to the present invention is composed of the colored resin fine particles having the characteristics as described above or an aqueous dispersion, so that it exhibits a high degree of dispersion stability and also exhibits high color development and high transparency of the color filter. To do.

  Next, the present invention will be described in more detail with reference to examples. In the text, “parts” and “%” are based on mass. The present invention is not limited to the following examples.

The infrared absorption spectrum was measured by Shimadzu Fourier transform infrared spectrophotometer FTIR-8700.
The average particle diameter is based on a transmission image of particles photographed by a transmission electron microscope JEM1200EX02 manufactured by JASCO Corporation. Cumulative 50% of the number conversion distribution calculated by image analysis software made by Soft Imaging System, Analysis Pro It was displayed in diameter (D50).
The average crystal size of the water-insoluble colorant was estimated by the Scherrer method based on the X-ray diffraction spectrum measured by the RINT2500 X-ray diffractometer manufactured by Rigaku Corporation.
The dispersed particle size was measured by a concentrated particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd., and the cumulative 10% particle size (P10), 50% cumulative particle size (P50), and 90% cumulative particle size ( P90).
The viscosity was measured with an E-type viscometer TV-30 manufactured by Toki Sangyo.
The concentration of the water-insoluble colorant was calculated by measuring the extinction coefficient at the maximum wavelength of the ultraviolet / visible absorption spectrum with a Shimadzu spectrophotometer UV-2100 and comparing it with the extinction coefficient of each water-insoluble colorant.

Example 1 (CI Pigment-Red 122 Colored Resin Fine Particles and Aqueous Dispersion)
<Dissolution step> C.I. I. Pigment-Red122, 10 parts by weight was suspended in 80 parts by weight of dimethyl sulfoxide. To this solution was added 30 parts by weight of a methanol solution in which 10 parts of potassium hydroxide was dissolved, and C.I. I. A dark blue solution in which Pigment-Red 122 was dissolved was obtained.
<Precipitation process> In 2000 parts by weight of ion-exchanged water, 1 part by weight of ammonium salt of polyoxyethylene distyrenated phenyl ether sulfate is dissolved and used as an aqueous dispersion medium. The aqueous dispersion medium was stirred at 8000 rpm with a stirring blade, and the solution prepared in the dissolution step was poured into the aqueous dispersion medium from a 0.2 mm needle at 3 ml / min. I. A slurry containing Pigment-Red 122 was obtained.
<Concentration step> The slurry is filtered by suction using a 0.5 μm membrane filter, concentrated and washed with water, and the organic solvent such as dimethyl sulfoxide and methanol, and inorganic salts such as potassium hydroxide are removed to obtain a total solution. The amount of slurry was 100 parts by weight.
<Dispersing Step> 5 parts by weight of 1 mol / kg of styrene-α-methylstyrene-acrylic acid copolymer (weight average molecular weight 12,000, acid value 200 mgKOH / g) which is a hydrophilic resin is added to 100 parts of the obtained slurry. A solution dissolved in 10 parts by weight of sodium hydroxide and 1 part by weight of ammonium salt of polyoxyethylene distyrenated phenyl ether sulfate were added and dispersed using an ultrasonic homogenizer to prepare a pre-dispersion.
<Addition of hydrophobic resin or polymerization step> To the obtained pre-dispersion, 1 part by weight of sodium alkylallylsulfosuccinate and 0.1 part by weight of potassium persulfate are added, and a dropping funnel, a nitrogen gas inlet tube, a stirrer, reflux cooling The mixture was placed in a four-necked flask equipped with a tube, and stirred and purged with nitrogen. This solution was heated to 80 ° C. with an oil bath, and then 2 parts by weight of styrene and 1 part by weight of methyl methacrylate were dropped from the dropping funnel, and the mixture was heated and stirred for 3 hours to polymerize, allowed to cool, and a crude aqueous system. A dispersion was obtained.
<Washing step and redispersion step> The obtained crude aqueous dispersion is transferred to an ultrafiltration device (fraction molecular weight 20,000), concentrated and dialyzed, and the electric conductivity of the filtrate becomes 100 μS / cm or less. Until washed. Furthermore, after adding 1 mol / kg potassium hydroxide aqueous solution so that pH might be set to about 8.0, it re-dispersed using the ultrasonic homogenizer.
<Post-treatment step> Thereafter, coarse particles are removed by filtration through a 0.8 μm Millipore filter, and ion-exchanged water is added to adjust the concentration of the water-insoluble colorant to 10%. An aqueous dispersion was obtained.
The dispersion diameter of the obtained aqueous dispersion was 52 nm for the cumulative 10% particle size (P10), 68 nm for the cumulative 50% particle size (P50), and 82 nm for the cumulative 90% particle size (P90) in the number conversion distribution. It was. The viscosity was 5 mPa · s. Moreover, the average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 65 nm based on the analysis using the transmission electron microscope.

Further, in order to analyze the composition of the colored resin fine particles, the composition analysis was performed as follows.
1 mol / kg hydrochloric acid was added to a part of the obtained aqueous dispersion to agglomerate the colored resin fine particles, followed by filtration, washing with water and drying. Next, 1.00 parts by weight of the colored resin fine particles were collected and subjected to Soxhlet extraction using toluene, and the resin component in the colored resin fine particles was extracted and separated in toluene. The remaining insoluble component was 0.53 parts by weight. When the infrared absorption spectrum of this insoluble component was measured, it was identified that this insoluble component was a quinacridone pigment which is a water-insoluble colorant. The average particle diameter of the isolated water-insoluble colorant is 30 nm based on the analysis using the transmission electron microscope, and the average crystal size is 6 nm based on the analysis using the X-ray diffraction spectrum. Estimated.
Next, the toluene solution from which the resin component was extracted was placed in a separatory funnel, and an extraction operation was performed by adding a 1 mol / kg sodium hydroxide aqueous solution. It is clear that the resin remaining in the toluene phase is a hydrophobic resin and the resin extracted into the aqueous phase is a hydrophilic resin. After this extraction operation, the toluene phase and the aqueous phase were separated and concentrated, and hexane was added to the toluene phase and 1 mol / kg hydrochloric acid was added to the aqueous phase to precipitate the resin component, which was dried and recovered. The recovered hydrophobic resin was 0.21 part by weight and the hydrophilic resin was 0.26 part by weight.
From these results, the water-insoluble colorant contained in the colored resin fine particles is 53% by weight, the hydrophobic resin is 21% by weight, the hydrophilic resin is 26% by weight, and the total resin component is 47% by weight. The resin was 81% by weight based on the hydrophilic resin.

Example 2 (CI Pigment-Violet 19 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Violet 19 was used except that the monomer was changed from 2 parts by weight of styrene, 1 part by weight of methyl methacrylate to 1 part by weight of styrene, 0.5 part by weight of methyl methacrylate, and 0.5 part by weight of methacryloxypolydimethylsiloxane. An aqueous dispersion was obtained in the same manner as in Example 1.
The dispersion diameter of the obtained aqueous dispersion was 48 nm for the cumulative 10% particle size (P10), 52 nm for the cumulative 50% particle size (P50), and 70 nm for the cumulative 90% particle size (P90) in terms of number distribution. It was. The viscosity was 4 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 45 nm.
Further, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 25 nm, and the average crystal size was 6 nm. The water-insoluble colorant contained in the colored resin fine particles is 55% by weight, the hydrophobic resin is 17% by weight, the hydrophilic resin is 28% by weight, the total resin component is 45% by weight, and the hydrophobic resin is hydrophilic. 61% by weight based on the conductive resin.

[Example 3] (CI Pigment-Red254 colored resin fine particles and aqueous dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. An aqueous dispersion was obtained in the same manner as in Example 1, except that the monomer was changed from Pigment-Red 254 to 2 parts by weight of styrene and 1 part by weight of methyl methacrylate to 4 parts by weight of styrene and 2 parts by weight of methyl methacrylate.
The dispersion diameter of the obtained aqueous dispersion was 52 nm for the cumulative 10% particle size (P10), 72 nm for the cumulative 50% particle size (P50), and 85 nm for the cumulative 90% particle size (P90) in terms of number distribution. It was. The viscosity was 7 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 70 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 30 nm, and the average crystal size was 7 nm. The water-insoluble colorant contained in the colored resin fine particles is 45% by weight, the hydrophobic resin is 32% by weight, the hydrophilic resin is 23% by weight, the total resin component is 55% by weight, and the hydrophobic resin is hydrophilic. It was 139 weight% with respect to conductive resin.

Example 4 (CI Pigment-Red 269 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Red 269 was the same as Example 1 except that the monomer was changed from 2 parts by weight of styrene, 1 part by weight of methyl methacrylate to 5 parts by weight of styrene, 2 parts by weight of methyl methacrylate, and 2 parts by weight of methacryloxypolydimethylsiloxane. Thus, an aqueous dispersion was obtained.
The dispersion diameter of the aqueous dispersion obtained was 44 nm for the cumulative 10% particle size (P10), 63 nm for the cumulative 50% particle size (P50), and 79 nm for the cumulative 90% particle size (P90) in terms of number distribution. It was. The viscosity was 7 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 70 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 20 nm, and the average crystal size was 5 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 40% by weight, the hydrophobic resin is 40% by weight, the hydrophilic resin is 20% by weight, the total resin component is 60% by weight, and the hydrophobic resin is hydrophilic. The content was 200% by weight based on the conductive resin.

Example 5 (CI Solvent-Red 49 colored resin fine particles and aqueous dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Solvent-Red49, except that the hydrophilic resin was changed from a styrene-α-methylstyrene-acrylic acid copolymer to a styrene-maleic acid half ester copolymer (weight average molecular weight 8,000, acid value 200 mgKOH / g). Obtained an aqueous dispersion in the same manner as in Example 1.
The dispersed particle size of the obtained aqueous dispersion was a number conversion distribution with a cumulative 10% particle size (P10) of 39 nm, a cumulative 50% particle size (P50) of 45 nm, and a cumulative 90% particle size (P90) of 69 nm. It was. The viscosity was 5 mPa · s. The average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 45 nm.
As a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 25 nm and the average crystal size was 5 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 53% by weight, the hydrophobic resin is 21% by weight, the hydrophilic resin is 26% by weight, the total resin component is 47% by weight, and the hydrophobic resin is hydrophilic. The content was 81% by weight based on the conductive resin.

Example 6 (CI Solvent-Red 52 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Solvent-Red 52, 5 parts by weight of styrene-α-methylstyrene-acrylic acid copolymer of hydrophilic resin, 3 parts by weight of monomer, 2 parts by weight of styrene, 1 part by weight of methyl methacrylate, 1.5 parts by weight of styrene An aqueous dispersion was obtained in the same manner as in Example 1 except that the amount was changed.
The dispersion diameter of the obtained aqueous dispersion was 45 nm for the cumulative 10% particle size (P10), 54 nm for the cumulative 50% particle size (P50), and 77 nm for the cumulative 90% particle size (P90). It was. The viscosity was 5 mPa · s. Moreover, the average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 52 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 20 nm, and the average crystal size was 7 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 65% by weight, the hydrophobic resin is 16% by weight, the hydrophilic resin is 19% by weight, the total resin component is 35% by weight, and the hydrophobic resin is hydrophilic. The content was 84% by weight based on the conductive resin.

Example 7 (CI Pigment-Blue 15: 3 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Blue 15: 3, monomer changed from 2 parts by weight of styrene, 1 part of methyl methacrylate to 2 parts by weight of styrene, 1 part by weight of butyl methacrylate, 1 part by weight of methacryloxypolydimethylsiloxane and 0.1 part by weight of divinylbenzene An aqueous dispersion was obtained in the same manner as in Example 1 except that.
The dispersion diameter of the obtained aqueous dispersion was 28 nm for the cumulative 10% particle size (P10), 33 nm for the cumulative 50% particle size (P50), and 56 nm for the cumulative 90% particle size (P90) in terms of the number distribution. It was. The viscosity was 6 mPa · s. The average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 32 nm.
Further, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 28 nm and the average crystal size was 8 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 50% by weight, the hydrophobic resin is 25% by weight, the hydrophilic resin is 25% by weight, the total resin component is 50% by weight, and the hydrophobic resin is hydrophilic. 100% by weight with respect to the conductive resin.

Example 8 (CI Pigment-Blue 16 colored resin fine particles and aqueous dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Changed to Pigment-Blue 16, 5 parts by weight of a styrene-α-methylstyrene-acrylic acid copolymer of hydrophilic resin, 10 parts by weight of monomer, 2 parts by weight of styrene, 1 part by weight of methyl methacrylate to 4 parts by weight of styrene An aqueous dispersion was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts by weight, 2 parts by weight of ethylhexyl methacrylate, and 2 parts by weight of methacryloxypolydimethylsiloxane.
The dispersion diameter of the obtained aqueous dispersion was 45 nm for the cumulative 10% particle size (P10), 62 nm for the cumulative 50% particle size (P50), and 82 nm for the cumulative 90% particle size (P90). It was. The viscosity was 7 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 70 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 20 nm, and the average crystal size was 5 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 34% by weight, the hydrophobic resin is 32% by weight, the hydrophilic resin is 34% by weight, the total resin component is 66% by weight, and the hydrophobic resin is hydrophilic. The amount was 94% by weight based on the conductive resin.

Example 9 (CI Solvent-Blue 5 colored resin fine particles and aqueous dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Solvent-Blue 5, 3 parts by weight of a copolymer of styrene-α-methylstyrene-acrylic acid as a hydrophilic resin, 3 parts by weight of a monomer, 2 parts by weight of styrene, 4 parts by weight of styrene An aqueous dispersion was obtained in the same manner as in Example 1 except for changing to 2 parts by weight of methyl methacrylate and 2 parts by weight of methacryloxypolydimethylsiloxane.
The dispersion diameter of the obtained aqueous dispersion was 48 nm for the cumulative 10% particle size (P10), 62 nm for the cumulative 50% particle size (P50), and 88 nm for the cumulative 90% particle size (P90) in terms of number distribution. It was. The viscosity was 5 mPa · s. Moreover, the average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 50 nm.
Further, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 17 nm, and the average crystal size was 4 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 45% by weight, the hydrophobic resin is 41% by weight, the hydrophilic resin is 14% by weight, the total resin component is 55% by weight, and the hydrophobic resin is hydrophilic. The content was 293 wt% with respect to the conductive resin.

[Example 10] (CI Disperse-Blue 72 colored resin fine particles and aqueous dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. It changed to Disperse-Blue72, did not perform a polymerization reaction, and the same manner as in Example 1 except that 10 parts by weight of an ethyl acetate solution in which 5 parts by weight of polystyrene (weight average molecular weight 220,000) was dissolved was added. An aqueous dispersion was obtained.
The dispersion diameter of the obtained aqueous dispersion was 46 nm for the cumulative 10% particle size (P10), 56 nm for the cumulative 50% particle size (P50), and 79 nm for the cumulative 90% particle size (P90). It was. The viscosity was 6 mPa · s. Moreover, the average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 60 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 20 nm, and the average crystal size was 8 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 48% by weight, the hydrophobic resin is 28% by weight, the hydrophilic resin is 24% by weight, the total resin component is 52% by weight, and the hydrophobic resin is hydrophilic. The content was 117% by weight based on the conductive resin.

Example 11 (CI Pigment-Yellow 74 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Yellow 74 was added, and 1 part by weight of titanium oxide fine particles (rutile type, average particle size of 15 nm: aluminum laurate surface treatment), which is water-insoluble inorganic fine particles simultaneously with the water-insoluble colorant, was added, and the monomer was 2 parts by weight of styrene An aqueous dispersion was obtained in the same manner as in Example 1, except that 1 part by weight of methyl methacrylate was changed to 2 parts by weight of styrene, 1 part by weight of methyl methacrylate, and 1 part by weight of methacryloxypolydimethylsiloxane.
The dispersion diameter of the aqueous dispersion obtained was 49 nm for the cumulative 10% particle size (P10), 62 nm for the cumulative 50% particle size (P50), and 87 nm for the cumulative 90% particle size (P90). It was. The viscosity was 5 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 48 nm.
Further, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 23 nm and the average crystal size was 10 nm. The water-insoluble coloring material contained in the colored resin fine particles is 47% by weight, the hydrophobic resin is 24% by weight, the hydrophilic resin is 24% by weight, and the total resin component is 48% by weight. The hydrophobic resin is hydrophilic. 100% by weight with respect to the conductive resin.

Example 12 (CI Pigment-Yellow128 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Yellow128, hydrophilic resin from styrene-α-methylstyrene-acrylic acid copolymer to styrene-maleic acid half ester copolymer (weight average molecular weight 8,000, acid value 200 mgKOH / g), monomer as styrene 2 parts by weight, 1 part by weight of methyl methacrylate, 2 parts by weight of styrene, 1 part by weight of methyl methacrylate, 1 part by weight of methacryloxypolydimethylsiloxane, 0.1 part by weight of divinylbenzene An aqueous dispersion was obtained.
The dispersed particle size of the obtained aqueous dispersion was a number converted distribution with a cumulative 10% particle size (P10) of 31 nm, a cumulative 50% particle size (P50) of 39 nm, and a cumulative 90% particle size (P90) of 58 nm. It was. The viscosity was 5 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 29 nm.
Further, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 17 nm and the average crystal size was 8 nm.

Example 13 (CI Pigment-Green 36 Colored Resin Fine Particles and Aqueous Dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. An aqueous dispersion was obtained in the same manner as in Example 1 except that the pigment was changed to Pigment-Green 36.
The dispersed particle size of the obtained aqueous dispersion is a number conversion distribution with a cumulative 10% particle size (P10) of 43 nm, a cumulative 50% particle size (P50) of 53 nm, and a cumulative 90% particle size (P90) of 79 nm. there were. The viscosity was 6 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 48 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 19 nm and the average crystal size was 8 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 53% by weight, the hydrophobic resin is 21% by weight, the hydrophilic resin is 26% by weight, the total resin component is 47% by weight, and the hydrophobic resin is hydrophilic. The content was 81% by weight based on the conductive resin.

[Example 14] (Colored resin fine particles and aqueous dispersion of CI Solvent-Green 5)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. An aqueous dispersion was obtained in the same manner as in Example 1 except that Solvent-Green 5 was used.
The dispersion diameter of the obtained aqueous dispersion was 45 nm for the cumulative 10% particle size (P10), 62 nm for the cumulative 50% particle size (P50), and 88 nm for the cumulative 90% particle size (P90) in terms of the number distribution. It was. The viscosity was 5 mPa · s. Moreover, the average particle diameter of the colored resin fine particles contained in the aqueous dispersion was 53 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 20 nm, and the average crystal size was 9 nm. Further, the water-insoluble colorant contained in the colored resin fine particles is 53% by weight, the hydrophobic resin is 21% by weight, the hydrophilic resin is 26% by weight, the total resin component is 47% by weight, and the hydrophobic resin is hydrophilic. The content was 81% by weight based on the conductive resin.

[Comparative Example 1] (When prepared without refining water-insoluble colorant)
(C.I. Pigment-Red122 colored resin fine particles and aqueous dispersion)
The dissolution process, the precipitation process, and the concentration process are omitted, and C.I. I. An aqueous dispersion was obtained in the same manner as in Example 1 except that Pigment-Red 122 was suspended in ion-exchanged water to form a slurry.
The dispersed particle size of the obtained aqueous dispersion was a number conversion distribution with a cumulative 10% particle size (P10) of 100 nm, a cumulative 50% particle size (P50) of 168 nm, and a cumulative 90% particle size (P90) of 252 nm. It was. The viscosity was 8 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 130 nm.
Furthermore, as a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the average particle size of the water-insoluble colorant contained was 80 nm and the average crystal size was 23 nm.
In this system, since the water-insoluble colorant is not miniaturized, sufficient transparency and color developability cannot be exhibited.

[Comparative Example 2] (When prepared without refining water-insoluble colorant)
(C.I. Solvent-Red49 colored resin fine particles and aqueous dispersion)
The dissolution process, the precipitation process, and the concentration process are omitted, and C.I. I. An aqueous dispersion was obtained in the same manner as in Example 5 except that Solvent-Red49 was suspended in ion-exchanged water to form a slurry.
However, since the water-insoluble colorant is not miniaturized in this system, most physical properties cannot be measured.
Further, the average particle size of the colored resin fine particles contained in the obtained aqueous dispersion settled at 10 μm or more, and could not be used as an aqueous dispersion or ink at all.

[Comparative Example 3] (When dispersed without performing the polymerization step)
(C. I. Pigment-Red254 colored resin fine particles and aqueous dispersion)
An aqueous dispersion was obtained in the same manner as in Example 3 except that the polymerization step was omitted.
The dispersion diameter of the obtained aqueous dispersion was 28 nm for the cumulative 10% particle size (P10), 45 nm for the cumulative 50% particle size (P50), and 57 nm for the cumulative 90% particle size (P90) in terms of number distribution. It was. The viscosity was 4 mPa · s. The average particle size of the colored resin fine particles contained in the aqueous dispersion was 45 nm.
As a result of analyzing the composition of the colored resin fine particles in the same manner as in Example 1, the water-insoluble colorant contained had an average particle size of 30 nm, and the water-insoluble colorant had an average crystal size of 7 nm.
In this system, colored resin fine particles and an aqueous dispersion having low viscosity and sufficient transparency were obtained, but the dispersion stability was not sufficient, and gelation occurred in several days.

  The production conditions at this time are shown in Table 1, and the characteristics of the obtained colored resin fine particles and the aqueous dispersion are shown in Table 2.

  As shown in Table 2, it is clear that the colored resin fine particles according to the present invention have extremely small average particle diameter and crystal size, and the aqueous dispersion is very finely dispersed.

[Ink for inkjet recording]
Each raw material was mixed at the following blending ratio to prepare a water-insoluble colorant concentration of 5%, and passed through a 0.8 μm Millipore filter to obtain an ink for inkjet recording according to the present invention. And it evaluated by the following method.

Aqueous dispersion 50 parts Glycerin 10 parts Diethylene glycol 5 parts Surfinol 465 (manufactured by Air Products) 1 part Ion-exchanged water 34 parts

(1) Dispersed particle size and viscosity The dispersed particle size is measured by a concentrated particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd., and a cumulative 10% particle size (P10), 50% cumulative particle size (P50) of the number conversion distribution, The cumulative 90 particle size (P90) was displayed. The viscosity was measured with an E-type viscometer TV-30 manufactured by Toki Sangyo.

(2) Storage stability The storage stability was left for 3 weeks after the preparation, and the dispersion particle size was measured again in the same manner as described above. ○, those in which a change of 10 to 50% occurred Δ, and those in which a change exceeding 50% occurred were evaluated as ×.

(3) Ink ejectability The ink ejectability was obtained by filling the Epson inkjet printer PX-V600 with the ink for ink jet recording according to the present invention, performing solid printing on Nippon Paper A4PPC paper clean, and not fading more than 50 sheets. ◯, 10 or less and less than 50 sheets faded, Δ or 10 or less.

(4) Plain paper colorability In the same way as described above, the color density of plain paper is the same as described above. The optical density (OD value) of a clean, solidly printed A4PPC paper is X-Rite reflective color spectrocolorimeter X- It was measured by Rite 939, and it was evaluated as ◯ when the OD value was 1.10 or more, Δ when it was 0.95 or more and less than 1.10, and × when it was less than 0.95.

(5) Glossy paper glossiness Glossy paper glossiness is the gloss at 20 ° between Epson A4 photographic paper <Glossy> KA420PSK and solid photographic paper parts, as described above. The degree difference is measured with a digital variable angle photometer UGV-5D manufactured by Suga Test Instruments Co., Ltd., when the difference in glossiness is +5 or more, ○ when the difference in glossiness is 0 or more and less than +5, and when the difference in glossiness is less than 0 Things were marked as x.

(6) Transparency Transparency is the same as described above, with the haze value when solid printing was performed on an exclusive OHP sheet MJ0PS1N made by Epson, the haze value of the printed part was less than 10 by a Toyo Seiki haze meter, A value of 10 or more and less than 20 was evaluated as Δ, and a value of 20 or more was evaluated as ×.

(7) Light resistance In the same manner as described above, the light resistance was set by printing a solid on Epson A4 photographic paper <glossy> KA420PSK on an Isuperi UV tester SUV-W13 manufactured by Iwasaki Electric Co., Ltd., temperature 50 ° C., humidity 60 Irradiating with ultraviolet rays (limited wavelength 295 nm to 450 nm) at an intensity of 100 mW / cm ² , and measuring the OD value before and 50 hours after the ultraviolet irradiation, the residual optical density (OD after 50 hours of ultraviolet irradiation) Value / OD value before ultraviolet irradiation × 100 (%)), the optical density residual ratio is 70% or more, ○ is less than 70%, 30% or more is Δ, and less than 30% is ×.

(8) Water resistance In the same manner as described above, the water resistance was A4PPC paper made by Nippon Paper Industries, which was solid-printed, dipped in water and then watered.

(9) Fixing property Fixing property was evaluated by a peel test using a cellophane tape after solid printing on Epson A4 photographic paper <Glossy> KA420PSK, as described above. The case where there was no detachment ○ and the case where there was detachment were rated as x.

  The evaluation results at this time are shown in Table 3.

  As shown in Table 3, the ink for ink jet recording according to the present invention is clearly excellent in various ink characteristics.

[Color filter ink]
The color filter ink according to the present invention was obtained by the same production method and composition as the ink jet recording ink according to the present invention. Although it is clear from Table 3 that these ink characteristics are excellent, R (red), G (green), and B (blue), which are the three primary colors of the color filter, are evaluated for the performance evaluation of the color filter. (The ink jet recording inks obtained in Examples 17, 21, and 27 were used as they were), and the color developability of the solid OHP sheet MJ0PS1N made by Epson in the same manner as described above. And those having poor color developability were evaluated as “x”) and transparency (transmittance at a maximum wavelength was measured using Shimadzu's spectrophotometer UV-2100. Less than% was marked as x.).

  The evaluation results at this time are shown in Table 4.

As shown in Tables 3 and 4, it is clear that the color filter ink according to the present invention is excellent in various ink characteristics, color developability and transparency.

  The colored resin fine particles according to the present invention are excellent in color developability, transparency and glossiness, light resistance, water resistance and fixability, and good dispersion stability during aqueous dispersion preparation and ink preparation. Therefore, it is suitable as a precursor for ink for inkjet recording and ink for color filter.

  The aqueous dispersion according to the present invention is excellent in color developability, transparency and glossiness, has good light resistance, water resistance and fixability, and itself has good dispersion stability at the time of ink preparation. It is suitable as a precursor for recording ink and color filter ink.

  The ink for ink-jet recording according to the present invention is suitable as an ink for ink-jet recording because it has excellent color development, transparency, and gloss, light resistance, water resistance, fixability, and good dispersion stability. is there.

The color filter ink according to the present invention is suitable as a color filter ink because it is excellent in color development and transparency, has good light resistance, water resistance and fixability, and has good dispersion stability.

Claims (10)

Colored resin fine particles containing a water-insoluble colorant and having an average particle diameter of 100 nm or less, the resin component is composed of a hydrophilic resin and a hydrophobic resin, and the average particle diameter of the water-insoluble colorant is 50 nm or less. Characteristic colored resin fine particles. The colored resin fine particles according to claim 1, wherein the water-insoluble colorant contained in the colored resin fine particles has an average crystal size of 20 nm or less. The hydrophilic resin is a resin selected from a styrene acrylic resin, a silicone resin, a polyester resin, a urethane resin, or a copolymer resin of two or more thereof, and has an acid value of 50 mgKOH / g or more and an alkali-soluble resin. The colored resin fine particles according to claim 1, wherein the colored resin fine particles are. The hydrophobic resin is a resin selected from a styrene acrylic resin, a silicone resin, a polyester resin, a urethane resin, or a copolymer resin of two or more thereof, and is an alkali-insoluble resin. 4. The colored resin fine particles according to any one of 3. The colored resin fine particles according to any one of claims 1 to 4, wherein the colored resin fine particles contain 10 to 90% by weight of a water-insoluble colorant. An aqueous dispersion in which the colored resin fine particles according to any one of claims 1 to 5 are dispersed in an aqueous dispersion medium. The aqueous dispersion according to claim 6, wherein in the dispersed particle size, the cumulative 90% particle size (P90) of the number conversion distribution is 100 nm or less. The water-based dispersion according to claim 6 or 7, wherein in the dispersed particle size, the particle size ratio of the cumulative 90% particle size (P90) of the number conversion distribution to the cumulative 50% particle size (P50) of the number conversion distribution ( An aqueous dispersion characterized in that P90 / P50) is 5 or less. An ink for ink jet recording using the colored resin fine particles according to any one of claims 1 to 5 or the aqueous dispersion according to any one of claims 6 to 8. An ink for a color filter using the colored resin fine particles according to any one of claims 1 to 5 or the aqueous dispersion according to any one of claims 6 to 8.