JP2007231130A - Colored resin particle, water-based dispersion containing the colored resin particle and ink for inkjet printing or ink for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide colored resin 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 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 particles comprise a resin component, a water-insoluble colorant and water-insoluble inorganic fine particles, wherein the resin component is a composite component of a hydrophilic resin and a hydrophobic resin. A cumulative 90% particle diameter (P90) in a number-accumulated particle size distribution of the colored resin particles as measured, with respect to a dispersed particle diameter thereof upon being dispersed in a water-based dispersion medium, is from 50 to 100 nm. The water-based dispersion containing the colored resin particles and the ink for inkjet printing or 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 particles that are not clogged at the time of printing and excellent in ejection stability, aqueous dispersions containing the colored resin particles, ink for ink jet recording, and ink for color filters.

  Inkjet recording is small and has a low running cost, but enables high-quality color printing, and has rapidly been used in the office and photographic markets. 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 that require preservation, 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 inkjet recording 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 adjuster and preservative and water.

  In a water-insoluble color material, an aqueous dispersion, or an ink prepared therefrom, a high-definition 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. 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. Further, when the water-insoluble colorant is refined, the specific surface area increases and the cohesive force increases, so that it is difficult to stably maintain the dispersion. In addition, when the water-insoluble colorant is extremely refined, the behavior of the dye approaches and the light resistance deteriorates. Therefore, it is necessary to stabilize the dispersion while further miniaturizing and to further prevent the deterioration of light resistance accompanying the miniaturization.

  On the other hand, for the purpose of coloring a recording medium such as recording paper, a resin binder for fixing to the recording medium and giving a glossy feeling to the printed material is essential. Conventionally, a resin or resin emulsion dissolved as a resin binder has been added to a dispersion or ink, but this tends to cause instability of the dispersion state or clogging of the printer head due to an increase in viscosity. .

  Thus, as a means for simultaneously solving the problems of dispersion stabilization and resin binder addition, a microcapsule dispersion and ink in which a resin is coated and dispersed around a pigment have been developed (Patent Documents 1 and 2). Furthermore, for the purpose of reducing the dispersed particle diameter of the microcapsule dispersion and stabilizing the dispersion, a technique for preparing a plasma-treated easy-dispersion pigment, coating the resin and finely dispersing it (Patent Document 3), inorganic A technique for finely dispersing fine composite pigment particles including pigment particles covered with an organic colorant with a resin (Patent Document 4) and a technique for defining and dispersing a zeta potential and a particle size distribution (Patent Document 5) are known. ing.

Japanese Patent Laid-Open No. 9-151342 Japanese Patent Laid-Open No. 10-140065 JP 2002-256166 A JP 2003-268278 A JP 2003-96353 A

  Patent Documents 1 and 2 describe a dispersion and an ink dispersed by coating a resin around a pigment. This dispersion and recording liquid are more transparent than a dye in terms of transparency and color development. It's hard to say.

  Further, Patent Document 3 discloses a dispersion and ink in which a plasma-treated hydrophilic easily disperse pigment is coated with a resin and finely dispersed in order to further refine the dispersed particle size and improve transparency. However, when the pigment is plasma-treated, the pigment becomes hydrophilic, the water resistance of the printed matter is lowered, and it is difficult to say that the plasma treatment is excellent in industrial productivity.

  In addition, Patent Document 4 describes a pigment dispersion in which fine composite pigment particles including inorganic pigment particles covered with an organic color material are coated with a resin and finely dispersed. Since the organic colorant layer has a very small thickness, the light resistance is considered to deteriorate. In addition, since the organic colorant and inorganic pigment particles are combined in substantially the same amount, in order to disperse the organic colorant in the same concentration as the dispersion ink of a normal organic colorant, the double amount of the organic colorant is used. The particles included in the inorganic pigment particles are required, and the solid content increases, making dispersion difficult.

  Further, the technique described in Patent Document 5 is a technique in which pigment particles are pigments whose surfaces are coated with a polymer, and are prepared by defining an average zeta potential and a particle size distribution in an aqueous solvent. It merely describes the general properties of a typical pigment dispersion preparation method.

  Therefore, the present invention provides resin particles and an aqueous dispersion that finely and stably include a water-insoluble colorant, and is excellent in color development, transparency, gloss, water resistance, light resistance, fixability, and the like. It is a technical problem to provide colored resin particles for inkjet recording and color filters that can express images having fastness, and aqueous dispersions and inks containing the colored resin particles.

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

  That is, the present invention is a colored resin particle containing a resin component, a water-insoluble colorant and water-insoluble inorganic fine particles, wherein the resin component is one or more selected from styrene acrylic resin, silicone resin, polyester resin, and urethane resin. This is a composite component of a hydrophilic resin and a hydrophobic resin, and the water-insoluble inorganic fine particles are contained in an amount of 1 to 50% by weight with respect to the water-insoluble colorant. Colored resin particles characterized in that the cumulative 90% particle size (P90) of the distribution is from 50 nm to 100 nm (Invention 1).

  Further, the present invention is the colored resin particle of the present invention 1, wherein the water-insoluble inorganic fine particles are composed of one or more selected from silicon oxide, titanium oxide, and aluminum compound (Invention 2). .

  In addition, the present invention is the colored resin particle according to the first or second aspect of the present invention, wherein the water-insoluble inorganic fine particles are particles that have been subjected to a hydrophobic surface treatment (Invention 3).

  In addition, the present invention is an aqueous dispersion characterized in that the colored resin particles of any one of the present inventions 1 to 3 are dispersed in an aqueous dispersion medium (Invention 4).

  The present invention is the aqueous dispersion according to the present invention 4, wherein the cumulative 90% particle size (P90) of the number conversion distribution is 50 nm or more and 100 nm or less. There is (Invention 5).

  Further, the present invention is the aqueous dispersion of the present invention 4 or 5, 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 6).

  Further, the present invention is an ink for ink jet recording using the colored resin particles according to any one of the first to third aspects or the aqueous dispersion according to any one of the fourth to sixth aspects (Invention 7).

  In addition, the present invention is an ink for a color filter using the colored resin particles according to any one of the first to third aspects or the aqueous dispersion according to any one of the fourth to sixth aspects (Invention 8).

  The colored resin particles according to the present invention are colored resin particles containing a water-insoluble coloring material and surface-treated water-insoluble inorganic fine particles in the resin particles. By including the surface-treated water-insoluble inorganic fine particles, water-insoluble Since the inorganic fine particles function as a surface active powder and dispersibility is improved, excellent color developability and transparency can be exhibited. Furthermore, since the water-insoluble inorganic fine particles absorb light on the short wavelength side after printing, deterioration of the color material due to light is prevented, and light resistance is improved. In addition, by forming resin 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 particles having the characteristics as described above, the image has excellent color developability, transparency, glossiness, and 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 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, etc. Since an image having fastness can be expressed and the dispersion stability is good, it is suitable as an ink for ink jet recording.

  In addition, the color filter ink according to the present invention is composed of the colored resin particles having the characteristics as described above or an aqueous dispersion, so that it is excellent in color development, transparency and gloss, water resistance, light resistance and fixability. Therefore, it is suitable as an ink for a color filter because it can express an image having fastness such as, and has good dispersion stability.

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

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

  The colored resin particles according to the present invention are resin particles composed of two types of resins, a hydrophilic resin and a hydrophobic resin, containing a water-insoluble colorant and surface-treated water-insoluble inorganic fine particles. In the dispersed particle size at the time of dispersion, the cumulative 90% particle size (P90) of the number conversion distribution is 50 nm or more and 100 nm or less. When the cumulative 90% particle size (P90) of the number conversion distribution exceeds 100 nm, sufficient transparency cannot be exhibited. The cumulative 90% particle size (P90) of the number conversion distribution is preferably 50 nm or more and 95 nm or less, more preferably more than 50 nm and 90 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 that does not become hydrophilic even when a basic compound or acidic compound is added to the resin, is insoluble in an aqueous dispersion medium, and is a styrene acrylic resin, silicone resin, polyester resin, urethane resin, or two types Those obtained by copolymerization are preferred. Furthermore, it is preferable that the monomer is polymerized and formed in the vicinity of the hydrophilic resin or the water-insoluble colorant via a surfactant as necessary.

  As monomers, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, divinylbenzene, trivinylbenzene, 4-methoxystyrene, 4 -Styrene monomers such as cyanostyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylphenanthrene, styrene macromer and their derivatives, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic Ethyl hexyl, octyl acrylate, stearyl acrylate, lauryl acrylate, acrylonitrile, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Cyl, ethylhexyl methacrylate, octyl methacrylate, stearyl methacrylate, lauryl methacrylate, glycidyl methacrylate, methacrylonitrile, methacrylamide, itaconic acid, methyl itaconate, ethyl itaconate, fumaric acid, dimethyl fumarate, diethyl fumarate Acrylic acid monomers and derivatives thereof, such as maleic acid, dimethyl maleate, diethyl maleate, crotonic acid, methyl crotonic acid, ethyl crotonic acid, methyl methacrylate macromer, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, Silane monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane and their derivatives, methacryloxypolydimethylsilane One terminal methacrylic modified silicone oil such as hexane, silicone-based monomers and derivatives thereof, such as both ends methacryl-modified silicone oil and the like, may be used in combination of at least these one or two. 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.

  The ratio of the hydrophilic resin to 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 30-300 weight%, More preferably, it is 30-200 weight%.

  The ratio of the resin (total of hydrophilic resin and hydrophobic resin) in the colored resin particles is preferably such that the resin is contained in the colored resin 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.

  Any water-insoluble colorant for the colored resin particles according to the present invention can be used as long as it is insoluble in an aqueous dispersion medium and can achieve the present invention. More preferably, those that do not deteriorate by reacting with water-insoluble inorganic fine particles are preferred. Specifically, organic pigments, inorganic pigments, oil-soluble dyes, disperse dyes, vat dyes, and the like that are used as colorants for printing inks, paints, resin compositions, and the like can be used.

  The water-insoluble colorant may be mixed and used according to 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 inorganic pigment, Pigment-Red 101, 102, 104, 105, 106, 107, 108, 108: 1, 113, 230, 231, 232, 233, 235, 236, 275, Pigment-Blue 28, 29, 33, 35 36, 71, 72, 73, 74, Pigment-Yellow 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 118 119, 157, 158, 159, 160, 161, 162, 163, 164, 184, 189, Pigment-Black 6, 7, 8, 9, 10, 11, 12, 13, 14, 19, 22, 23, 24 , 25, 26, 27, 28, 29, 30, 34, Pigment-Green 15, 17, 18, 19, 2 , 23, 26, 50, Pigment-Orange 20, 21, 23, 75, 78, Pigment-Violet 14, 15, 16, 47, 49, Pigment-Brown 6, 7, 11, 24, 29, 31, 33, 34, 35 , 37, 39, 40, 43, 44, 45, Pigment-White 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 18, 19, 20, 21, 22, 23, 24, 25 26, 27, 28, 32, 33, Pigment-Metal 1, 2, 3, 4, 5, 6, pearl pigment, inorganic fluorescent pigment, 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 particles is preferably such that the water-insoluble colorant is contained in the colored resin particles in an amount of 10 to 90% by weight. When the amount is less than 10% by weight, the resin content is too much with respect to the water-insoluble color material, and when dispersed in an aqueous dispersion medium with an appropriate color density, the viscosity is likely to increase, making it difficult to use. When it exceeds 90% 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. More preferably, it is 15-80 weight%, More preferably, it is 20-60 weight%.

  The colored resin particles according to the present invention contain water-insoluble inorganic fine particles together with a water-insoluble colorant. Water-insoluble inorganic fine particles act as a surface active powder, and finely stabilize the dispersion of resin 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 ratio of the water-insoluble inorganic fine particles is 1 to 50% by weight with respect to the water-insoluble colorant. If it is less than 1% by weight, the effect of stabilizing the dispersion and the effect of improving light resistance are reduced, which is not preferable. If it exceeds 50% by weight, the content of the water-insoluble colorant is undesirably reduced. Preferably it is 1-30 weight%.

The water-insoluble inorganic fine particles according to the present invention include Mg, Ca, Ba, Ti, Zr, Ta, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Au, Zn, and Al. , Ga, Si, and Ge are selected from compounds of oxides, hydroxides, carbonates, and sulfates of one or more elements, 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, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and the like. 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 agent is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, based on 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 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 And sulfur-containing compounds such as sulfolane and dimethyl sulfoxide. One or a combination of two or more of these can be used.

  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, and more preferably 20 to 68 nm. The cumulative 90% particle size (P90) of the number conversion distribution is preferably 50 nm or more and 100 nm or less. When the cumulative 90% particle size (P90) of the particle size distribution exceeds 100 nm, sufficient transparency cannot be exhibited. More preferably, the cumulative 90% particle size (P90) of the particle size distribution is 50 nm or more and 95 nm or less, and more preferably more than 50 nm and 90 nm or less.

  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 (P50) 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 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 colored resin particles and an aqueous dispersion according to the present invention will be described.

  As a method for producing resin particles and a water-based dispersion containing a water-insoluble colorant, an interface deposition method and an interface polymerization method are generally known. Among them, the phase inversion emulsification method and the acid precipitation method in the interfacial deposition method are used for inkjet. However, these interfacial deposition methods only bind to the color material surface only by adsorption, so that adsorption / desorption occurs and dispersion tends to become unstable. Further, it is difficult to increase the density of the resin on the color material surface. Therefore, in the present invention, the dispersion is stabilized and the binder resin is designed by combining the interfacial deposition method and the interfacial polymerization method and coating with a double layer resin. In addition, the surface-treated water-insoluble inorganic fine particles are added to this system and included in the resin together with the water-insoluble colorant, whereby the dispersion stability and light resistance superior to those of the conventional ones are obtained.

  The colored resin particles and the aqueous dispersion of the present invention can be obtained through each step of a pre-dispersion step, a polymerization step, an acid precipitation step, a water washing step, a redispersion step, and a post-treatment step.

  In the pre-dispersion step, a hydrophilic resin is dissolved in an aqueous dispersion medium, and then a water-insoluble colorant, surface-treated water-insoluble inorganic fine particles, and, if necessary, a monomer, a surfactant, a polymerization initiator, and a polymerization chain. In the process of adding a transfer agent, etc., pre-dispersing the water-insoluble colorant with a high-speed stirrer such as a homomixer or homogenizer, a kneading and dispersing machine such as a bead mill or roll mill, or a dispersing machine such as an ultrasonic dispersing machine such as an ultrasonic homogenizer. is there.

  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, urethane resin, inorganic salts such as sodium hydroxide, potassium hydroxide, 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.

  The polymerization step is a step of stably preparing colored resin particles in water by adding a monomer, a surfactant, a polymerization initiator, a polymerization chain transfer agent, etc., as necessary, and conducting an emulsion polymerization reaction. . You may disperse | distribute with the above-mentioned disperser etc. 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 pre-dispersion. If it is a water-soluble polymerization initiator, it may be added immediately before the polymerization reaction.

  As the polymerization initiator, oil-soluble ones such as 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl) are used. Valeronitrile), azo polymerization initiators such as 2,2-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 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 and redox initiator. One or a combination of two or more of these can be used.

  Polymerization chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, xanthogen disulfides such as dimethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethyltylium Tyrium sulfides such as disulfide, tetrabutyltyramium disulfide, halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide, hydrocarbons such as pentaphenylethane, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthio Examples thereof include unsaturated hydrocarbons such as glycolate. These can be used alone or in combination of two or more.

  In the acid precipitation step, colored resin particles contained in the system are precipitated by adding acid to the colored resin particles obtained in the polymerization step to oxidize acidic groups in the hydrophilic resin portion to precipitate the colored resin particles in the aqueous dispersion medium. This is a step of separating particles and impurities such as unreacted monomers and salts. At the same time, since the resin appears on the water-insoluble colorant particles, the resin and the water-insoluble colorant are more strongly bound. Examples of the acid to be added include inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as formic acid, acetic acid, citric acid and oxalic acid. The pH after aciding out is preferably in the range of 2 to 4.

  The water washing step is performed by separating the precipitate of the colored resin particles obtained in the acid precipitation step from the aqueous dispersion medium by a filtration step such as centrifugal separation, suction filtration, and pressure filtration, and further washing by the same operation. In this process, impurities such as acid, unreacted monomer and salt are removed.

  In the redispersion step, a basic substance is added to the precipitate of the colored resin particles purified in the previous step, and part of the hydrophilic resin is made hydrophilic again and dispersed in water to obtain an aqueous dispersion of colored resin particles. It is a process. 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, triethanolamine, etc. The pH after redispersion is preferably in the range of 7-11.

  The post-treatment step removes coarse particles and impurities contained in the obtained aqueous dispersion by filtering and centrifuging, and further diluting by adding ion exchange water or ultrafiltration, membrane filtration, vacuum distillation, etc. This is a step of performing concentration and adjusting the concentration.

  In the present invention, when it is necessary to take out as colored resin particles, the aqueous dispersion that has undergone the post-treatment process may be filtered and dried by a conventional method.

  Since the colored resin 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 inkjet recording according to the present invention contains 1 to 30%, preferably 2 to 20%, of the colored resin particles as the concentration of the water-insoluble colorant by diluting the colored resin particles or the aqueous dispersion according to the present invention. .

  The ink for inkjet recording according to the present invention comprises the colored resin particles or the aqueous dispersion according to the present invention and water, and if necessary, additives such as surfactants, water-soluble organic compounds, pH adjusters, preservatives, etc. It 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, dodecyl benzene 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.), and one kind or a mixture of two or more kinds 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. Polyhydric alcohols such as 1,6-hexanediol and glycerol, 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 monoethyl Ether, triethylene glycol monobutyl ether, Polyhydric alcohol alkyl ethers such as traethylene 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, γ -Nitrogen-containing heterocyclic compounds such as butyrolaclone, amides such as N, N-dimethylformamide and urea, amines such as monoethanolamine, diethanolamine and triethanolamine, sulfur-containing compounds such as thiodiethanol, sulfolane and dimethylsulfoxide, glucose , Mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, cellulose, dextrin, cyclo Examples thereof include saccharides such as dextrin, 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, chlorxylenol 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 ink jet 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, and more preferably 20 to 68 nm. The cumulative 90% particle size (P90) of the number conversion distribution is preferably 50 nm or more and 100 nm or less. When it exceeds 100 nm, sufficient transparency cannot be exhibited. More preferably, the cumulative 90% particle size (P90) of the number conversion distribution is 50 nm or more and 95 nm or less, and more preferably more than 50 nm and 90 nm or less.

  In the dispersed particle size of the ink for inkjet 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 (P50) 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 particles or aqueous dispersion according to the present invention, ion-exchanged water, if necessary, a surfactant, a water-soluble organic compound, a pH adjuster, a preservative, etc. It is obtained by mixing additives 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 1 to 30%, preferably 2 to 20%, of the colored resin particles as the concentration of the water-insoluble colorant by diluting the colored resin particles or the aqueous dispersion according to the present invention. .

  The color filter ink according to the present invention comprises the colored resin 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 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 can be obtained by mixing additives such as preservatives, preservatives, etc., and then filtering or centrifuging using a membrane filter or both.

<Action>
The colored resin particles according to the present invention are colored resin particles in which a water-insoluble colorant and water-insoluble inorganic fine particles are included in two types of resins, hydrophilic and hydrophobic. The hydrophilic resins of these two types of resin composition help to disperse in the aqueous dispersion medium, prevent the hydrophobic resin from being entangled with the hydrophilic resin and preventing the hydrophilic resin from diffusing into the aqueous dispersion medium. Dispersion stability at the time of manufacturing or ink preparation, and high ink discharge performance in an ink jet system. Furthermore, this resin composition exhibits high gloss, high fixability and high water resistance of the printed matter. In addition, since the surface-treated water-insoluble inorganic fine particles are included, the water-insoluble inorganic fine particles function as a surface active powder and the dispersibility is improved, so that high color development and high transparency can be exhibited. Furthermore, since the water-insoluble inorganic fine particles absorb light on the short wavelength side after printing, the inventor presumes that the color material is prevented from being deteriorated by light and the light resistance is improved.

  Since the aqueous dispersion according to the present invention is composed of colored resin 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. High light resistance and high fixability.

  The ink for ink jet recording according to the present invention is composed of the colored resin particles having the characteristics as described above, or an aqueous dispersion, so that it exhibits high dispersion stability, high ink discharge performance in the ink jet system, and high print quality. Exhibits color development, high gloss, 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 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. However, 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 with a diameter (D50).
The BET specific surface area was measured by Monosorb MS-21 manufactured by Yuasa Ionics.
The carbon content was measured by Horiba carbon / sulfur analyzer EMIA-820W.
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.

(Surface treatment example 1)
100 parts by weight of silica particles (average particle size 20 nm, BET specific surface area 200 m ² / g, carbon content 0.0% by weight) manufactured by Nippon Silica Industry were suspended in 300 parts by weight of toluene and 8 parts by weight of diethylamine. To this suspension, 12 parts by weight of methyltriethoxysilane was added, stirred with a stirring blade for 30 minutes, then heated to 60 ° C. and stirred for 2 hours. The suspension was allowed to cool, then filtered, washed with toluene, and dried with a vacuum dryer (60 ° C., 20 mmHg) to obtain a white solid. This solid content was identified by silica having a surface-treated methylsilane by infrared absorption spectrum. The obtained methylsilane surface-treated silica (surface-treated silica 1) had an average particle diameter of 20 nm, a BET specific surface area of 147 m ² / g, and a carbon content of 1.5% by weight.

(Surface treatment example 2)
Trimethylsilane surface-treated silica (surface-treated silica 2) was obtained in the same manner as in Surface Treatment Example 1 except that methyltriethoxysilane was changed to hexamethyldisilazane. This surface-treated silica had an average particle diameter of 20 nm, a BET specific surface area of 99 m ² / g, and a carbon content of 2.5% by weight.

(Surface treatment example 3)
A phenylsilane surface-treated silica (surface-treated silica 3) was obtained in the same manner as in Surface Treatment Example 1 except that methyltriethoxysilane was changed to phenyltriethoxysilane. This surface-treated silica had an average particle diameter of 17 nm, a BET specific surface area of 142 m ² / g, and a carbon content of 1.8% by weight.

(Surface treatment example 4)
Methylsilane surface-treated titanium oxide (surface-treated titanium oxide 1) was prepared in the same manner as in Surface Treatment Example 1 except that the silica particles were changed to Teica titanium oxide (rutile type, average particle size 15 nm, BET specific surface area 100 m ² / g). Obtained. This surface-treated titanium oxide had an average particle size of 17 nm, a BET specific surface area of 75 m ² / g, and a carbon content of 0.5% by weight.

(Surface treatment example 5)
Methylsilane surface-treated alumina (surface-treated alumina 1) was obtained in the same manner as in Surface Treatment Example 1 except that the silica particles were changed to Nippon Aerosil made alumina (average particle size 13 nm, BET specific surface area 100 m ² / g). This surface-treated alumina had an average particle diameter of 16 nm, a BET specific surface area of 68 m ² / g, and a carbon content of 0.5% by weight.

[Example 1] (CI-Pigment-Red122 colored resin particle aqueous dispersion)
<Pre-dispersion step> 10 parts by weight of a hydrophilic resin styrene-α-methylstyrene-acrylic acid copolymer (weight average molecular weight 12,000, acid value 200 mg KOH / g) is 1 mol / kg sodium hydroxide aqueous solution 20 Dissolved in parts by weight, C.I. I. 10 parts by weight of Pigment-Red 122, 1 part by weight of surface-treated silica 1, 2 parts by weight of sodium alkylallylsulfosuccinate, 4 parts by weight of styrene, 2 parts by weight of methyl methacrylate, and 70 parts by weight of ion-exchanged water were mixed to obtain 0.1 mm zirconia. Using a bead mill filled with beads, dispersion was performed at 2000 rpm for 30 minutes, and a dispersion having a cumulative 50% particle size (P50) of 50 nm as a number conversion distribution was obtained.
<Polymerization step> 0.1 part by weight of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamide] hydrate is added to the obtained dispersion, and a thermometer and a nitrogen gas introduction tube are added. The mixture was placed in a four-necked flask equipped with a stirrer and a reflux condenser, allowed to react at 80 ° C. for 3 hours under a nitrogen atmosphere, and allowed to cool.
<Acid precipitation step> 1 mol / kg hydrochloric acid was added to the obtained dispersion to adjust the pH to 3 or less, thereby causing precipitation.
<Water Washing Step> The obtained precipitate was filtered by suction filtration using a 0.8 μm membrane filter, and washed with 500 ml of ion exchange water to obtain a wet cake having a pH of 5.5. To this was added a 1 mol / kg sodium hydroxide aqueous solution as a basic compound, and the pH was adjusted to 8.
<Redispersion step> The dispersion was again performed at 2000 rpm for 30 minutes using a bead mill filled with 0.1 mm zirconia beads.
<Post-treatment step> The obtained dispersion is filtered through a 0.8 μm Millipore filter to remove coarse particles, and a small amount of ion-exchanged water is added to adjust the concentration of the water-insoluble colorant to 10%. An aqueous dispersion of colored resin particles was obtained.
The dispersed particle size of the obtained aqueous dispersion was a number conversion distribution. The cumulative 10% particle size (P10) was 43 nm, the cumulative 50% particle size (P50) was 53 nm, and the cumulative 90% particle size (P90) was 77 nm. It was. The viscosity was 7 mPa · s.

Moreover, in order to analyze the composition of the colored resin particles, composition analysis was performed as follows.
1 mol / kg hydrochloric acid was added to a part of the obtained aqueous dispersion of colored resin particles to condense the colored resin particles, followed by filtration, washing with water and drying. Next, 1.00 parts by weight of the colored resin particles were collected and subjected to Soxhlet extraction with toluene to extract and separate the resin component into toluene. The remaining insoluble component was 0.36 parts by weight. When the infrared absorption spectrum of this insoluble component was measured, it was identified to be quinacridone pigment which is a water-insoluble colorant and surface-treated silica 1 which is water-insoluble inorganic fine particles. When a mixed solvent of 3 parts by weight of dimethyl sulfoxide and 1 part by weight of 10% potassium hydroxide methanol solution was added to this insoluble component to dissolve quinacridone as a water-insoluble colorant, surface treated silica 1 as remaining water-insoluble inorganic fine particles was obtained. Was 0.03 part by weight. From this, the water-insoluble colorant was 0.33 parts by weight.
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 0.29 parts by weight, and the hydrophilic resin was 0.35 parts by weight.
From these results, the water-insoluble colorant contained in the colored resin particles is 33% by weight, the water-insoluble inorganic fine particles are 3% by weight, and the water-insoluble inorganic fine particles are contained in 10% by weight with respect to the water-insoluble colorant. It was. Further, the hydrophobic resin contained in the colored resin particles was 29% by weight, the hydrophilic resin was 35% by weight, the total resin was 64% by weight, and the hydrophobic resin was 83% by weight with respect to the hydrophilic resin. It was.

[Example 2] (CI-Pigment-Red122 colored resin particle aqueous dispersion)
The surface-treated silica 1 is changed to the surface-treated silica 2, and the hydrophilic resin is 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). A water-based dispersion was obtained in the same manner as in Example 1 except that the above was changed. The dispersion diameter of the obtained aqueous dispersion was a number conversion distribution. The cumulative 10% particle size (P10) was 31 nm, the cumulative 50% particle size (P50) was 39 nm, and the cumulative 90% particle size (P90) was 58 nm. It was. The viscosity was 7 mPa · s.

[Example 3] (CI-Pigment-Red122 colored resin particle aqueous dispersion)
1 part by weight of surface-treated silica 1 is 0.5 part by weight of surface-treated silica 3 and 4 parts by weight of styrene, 2 parts by weight of methyl methacrylate, 4 parts by weight of styrene, 2 parts by weight of methyl methacrylate, methacryloxypolydimethyl An aqueous dispersion was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts by weight of siloxane. The dispersed particle size of the obtained aqueous dispersion was a number-converted distribution with a cumulative 10% particle size (P10) of 49 nm, a cumulative 50% particle size (P50) of 62 nm, and a cumulative 90% particle size (P90) of 87 nm. It was. The viscosity was 7 mPa · s.
As a result of analyzing the composition of the colored resin particles in the same manner as in Example 1, the water-insoluble colorant contained in the colored resin particles was 33% by weight, the water-insoluble inorganic fine particles were 2% by weight, and the water-insoluble inorganic fine particles were The amount was 5% by weight based on the water-insoluble colorant. Further, the hydrophobic resin contained in the colored resin particles was 32% by weight, the hydrophilic resin was 33% by weight, the total resin was 65% by weight, and the hydrophobic resin was 97% by weight with respect to the hydrophilic resin. It was.

[Example 4] (CI-Pigment-Blue 15: 3 aqueous dispersion of colored resin particles)
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 Pigment-Blue 15: 3 was changed from 4 parts by weight of styrene and 2 parts by weight of methyl methacrylate to 4 parts by weight of styrene and 2 parts by weight of butyl methacrylate. It was. The dispersed particle size of the obtained water-based dispersion was a number conversion distribution, the cumulative 10% particle size (P10) was 46 nm, the cumulative 50% particle size (P50) was 56 nm, and the cumulative 90% particle size (P90) was 79 nm. It was. The viscosity was 7 mPa · s.

[Example 5] (CI-Pigment-Blue 15: 3 aqueous dispersion of colored resin particles)
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 surface-treated silica 1 was changed to Pigment-Blue 15: 3 and the surface-treated titanium oxide 1. The dispersed particle size of the obtained aqueous dispersion was a number-converted distribution with a cumulative 10% particle size (P10) of 48 nm, a cumulative 50% particle size (P50) of 62 nm, and a cumulative 90% particle size (P90) of 88 nm. It was. The viscosity was 7 mPa · s.

[Example 6] (CI-Pigment-Yellow 74 aqueous dispersion of colored resin particles)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Yellow 74, 1 part by weight of surface-treated silica 1 to 2 parts by weight of surface-treated titanium oxide 1, 4 parts by weight of styrene, 2 parts by weight of methyl methacrylate, 4 parts by weight of styrene, 2 parts by weight of methyl methacrylate, An aqueous dispersion was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts by weight of methacryloxypolydimethylsiloxane. The dispersed particle size of the obtained aqueous dispersion was a number-converted distribution with a cumulative 10% particle size (P10) of 45 nm, a cumulative 50% particle size (P50) of 58 nm, and a cumulative 90% particle size (P90) of 82 nm. It was. The viscosity was 8 mPa · s.
As a result of analyzing the composition of the colored resin particles in the same manner as in Example 1, the water-insoluble colorant contained in the colored resin particles was 31% by weight, the water-insoluble inorganic fine particles were 6% by weight, and the water-insoluble inorganic fine particles were The content was 19% by weight based on the water-insoluble colorant. Further, the hydrophobic resin contained in the colored resin particles was 32% by weight, the hydrophilic resin was 31% by weight, the total resin was 63% by weight, and the hydrophobic resin was 103% by weight with respect to the hydrophilic resin. It was.

[Example 7] (CI-Pigment-Yellow128 aqueous dispersion of colored resin particles)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Yellow128, surface-treated silica 1 to surface-treated alumina 1, and hydrophilic resin from styrene-α-methylstyrene-acrylic acid copolymer to styrene-maleic acid half ester copolymer (weight average molecular weight 8,000, Example 1 except that the monomer was changed from 4 parts by weight of styrene and 2 parts by weight of methyl methacrylate to 4 parts by weight of styrene, 2 parts by weight of methyl methacrylate, and 2 parts by weight of methacryloxypolydimethylsiloxane, with an acid value of 200 mgKOH / g) In the same manner as in Example 1, an aqueous dispersion was obtained. The dispersed particle size of the obtained aqueous dispersion was a number conversion distribution. The cumulative 10% particle size (P10) was 24 nm, the cumulative 50% particle size (P50) was 26 nm, and the cumulative 90% particle size (P90) was 56 nm. It was. The viscosity was 7 mPa · s.

[Example 8] (CI-Pigment-Black7 colored resin particle aqueous dispersion)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Black 7 (carbon black), except that surface-treated silica 1 was changed to surface-treated silica 3 and the monomer was changed from 4 parts by weight of styrene and 2 parts by weight of methyl methacrylate to 4 parts by weight of styrene and 2 parts by weight of ethylhexyl methacrylate. Obtained an aqueous dispersion in the same manner as in Example 1. The dispersed particle size of the obtained aqueous dispersion was a number-converted distribution with a cumulative 10% particle size (P10) of 45 nm, a cumulative 50% particle size (P50) of 54 nm, and a cumulative 90% particle size (P90) of 77 nm. It was. The viscosity was 7 mPa · s.

[Example 9] (CI-Pigment-Green 36 colored resin particle 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 surface-treated silica 1 was changed to Pigment-Green 36 and the surface-treated silica 3 was changed. The dispersion diameter of the obtained aqueous dispersion is 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. there were. The viscosity was 8 mPa · s.

[Example 10] (CI-Pigment-Red269 colored resin particle 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 surface-treated silica 1 was changed to Pigment-Red 269 and the surface-treated titanium oxide 1. The dispersed particle size of the obtained aqueous dispersion is a number conversion distribution, the cumulative 10% particle size (P10) is 44 nm, the cumulative 50% particle size (P50) is 55 nm, and the cumulative 90% particle size (P90) is 79 nm. there were. The viscosity was 8 mPa · s.

[Comparative Example 1] (When the resin component is only a hydrophilic resin and does not contain water-insoluble inorganic fine particles)
(CI-Pigment-Red122 colored resin particle aqueous dispersion)
A water-based dispersion was obtained in the same manner as in Example 1 except that the water-insoluble inorganic fine particles were not contained, the surfactant and the monomer were not contained, and the polymerization step was omitted. The dispersed particle size of the obtained aqueous dispersion was a number conversion distribution with a cumulative 10% particle size (P10) of 52 nm, a cumulative 50% particle size (P50) of 69 nm, and a cumulative 90% particle size (P90) of 112 nm. there were. The viscosity was 10 mPa · s.

[Comparative Example 2] (When the resin component is only a hydrophilic resin and does not contain water-insoluble inorganic fine particles)
(C.I. Pigment-Yellow74 aqueous dispersion of colored resin particles)
A water-insoluble coloring material is C.I. I. Pigment-Red 122 to C.I. I. Pigment-Yellow 74 was changed to Pigment-Yellow 74, and the aqueous dispersion was obtained in the same manner as in Example 1 except that the preparation was carried out without the water-insoluble inorganic fine particles, the surfactant and the monomer, and omitting the polymerization step. The dispersed particle size of the obtained aqueous dispersion is a number conversion distribution, the cumulative 10% particle size (P10) is 18 nm, the cumulative 50% particle size (P50) is 27 nm, and the cumulative 90% particle size (P90) is 38 nm. there were. The viscosity was 10 mPa · s.

[Comparative Example 3] (When prepared without containing water-insoluble inorganic fine particles)
(CI-Pigment-Red122 colored resin particle aqueous dispersion)
An aqueous dispersion was obtained in the same manner as in Example 1 except that the preparation was carried out without including the surface-treated silica 1. The dispersed particle size of the obtained aqueous dispersion is a number conversion distribution, the cumulative 10% particle size (P10) is 59 nm, the cumulative 50% particle size (P50) is 72 nm, and the cumulative 90% particle size (P90) is 121 nm. there were. The viscosity was 13 mPa · s.

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

  As shown in Table 2, it is clear that the colored resin particles and the aqueous dispersion according to the present invention are prepared and dispersed extremely finely.

[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 14, 19, and 20 were used as they were), and the color developability of the solid OHP sheet MJ0PS1N made by Epson as described above (good color developability is visually ◯, obvious) 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 particles according to the present invention are excellent in color developability, transparency and gloss, 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 (8)

Colored resin particles containing a resin component, a water-insoluble colorant and water-insoluble inorganic fine particles, wherein the resin component is one or more hydrophilic resins selected from styrene acrylic resin, silicone resin, polyester resin, and urethane resin and hydrophobic 90 to 50% of the number conversion distribution in the dispersed particle size when dispersed in the aqueous dispersion medium, wherein the water-insoluble inorganic fine particles are contained in an amount of 1 to 50% by weight with respect to the water-insoluble colorant. A colored resin particle having a diameter (P90) of 50 nm or more and 100 nm or less. The colored resin particles according to claim 1, wherein the water-insoluble inorganic fine particles comprise one or more selected from silicon oxide, titanium oxide, and aluminum compounds. The colored resin particles according to claim 1 or 2, wherein the water-insoluble inorganic fine particles are particles subjected to a hydrophobic surface treatment. An aqueous dispersion in which the colored resin particles according to any one of claims 1 to 3 are dispersed in an aqueous dispersion medium. 5. The aqueous dispersion according to claim 4, wherein in the dispersed particle diameter, the cumulative 90% particle diameter (P90) of the number conversion distribution is 50 nm or more and 100 nm or less. 6. The aqueous dispersion according to claim 4, wherein in the dispersed particle size, a particle size ratio of a cumulative 90% particle size (P90) of the number conversion distribution to a 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 particles according to any one of claims 1 to 3 or the aqueous dispersion according to any one of claims 4 to 6. An ink for a color filter using the colored resin particles according to any one of claims 1 to 3 or the aqueous dispersion according to any one of claims 4 to 6.