JP5826464B2 - Processed pigment manufacturing method and pigment dispersion manufacturing method - Google Patents

Description

  The present invention particularly relates to a process for producing a processed pigment suitable for use in oily articles, a processed pigment, and a dispersion of the processed pigment. In particular, a technology for providing processed pigments suitable as colorants for paints, gravure inks, offset inks, inkjet inks, stationery inks, wet toners, fiber originals, image display display colors, coating agents, UV coating agents, etc. About.

  Conventionally, the following pigment dispersions have been used as colorants for paints, gravure inks, offset inks, inkjet inks, stationery inks, wet toners, fiber originals, image display colors, coating agents, and UV coating agents. It is used. That is, a pigment dispersion is used in which at least a pigment, a dispersant, and a liquid medium are used and these are dispersed by a disperser, and the pigment is dispersed in fine particles in the liquid medium and stabilized. In the pigment dispersion at that time, it is preferable to disperse the pigment into fine particles up to primary particles, and to prevent aggregation of fine particles in which the pigment is dispersed even over time. For this purpose, pigments are subjected to optimization treatments such as micronization and surface treatment by various methods of pigmentation. In addition, for pigments, pigment derivatives with similar skeletons similar to the skeleton of the pigments are developed and used, and dispersants with various structures are developed and used. The pigment dispersion is obtained by crushing in a medium.

  Further, the pigment dispersion obtained in this way has high color developability and coloring when used in the above-described applications, such as no aggregation of the pigment and the pigment being uniformly applied to the article medium. In some cases, it is required to have high transparency. Furthermore, for the pigment dispersion, in the process of obtaining the article as described above using the pigment dispersion, the influence of heat treatment such as baking and drying, the influence of the treatment due to the force such as stretching and mixing, ultraviolet irradiation and electron Without being affected by light such as radiation, etc., even under these circumstances, the state of fine particles in the used pigment dispersion is maintained, and a clear and highly transparent article is provided. Needed. Recently, in applications such as those listed above, there has been a demand for further improvement in transparency and color development of pigments compared to conventional ones, and further finer pigments have become essential (patents). Reference 1).

JP 2008-111019 A

  However, in order to make the pigment into fine particles to such a high level, a great effort is required to disperse the pigment in the dispersion step. For example, in order to realize such an excellent pigment dispersion, development of various dispersants and pigment derivatives, and a dispersion process using a great deal of energy to obtain the fine particles are essential.

  Furthermore, according to the study by the present inventors, in the case of a pigment dispersion in which a pigment is dispersed in a liquid medium when the particle is fined to an unprecedented high level, an increase in surface energy due to the fine particle makes the liquid of the pigment The stability in the medium is deteriorated, and the following problems are caused due to the formation of fine particles. That is, pigment aggregation or the like occurs during the dispersion process for producing the pigment dispersion, the pigment is difficult to be in the form of fine particles, the fluidity of the pigment dispersion after dispersion is lost, or the fine particle shape is initially maintained. However, the pigments may aggregate over time. Further, in the manufacturing process of an article using the pigment dispersion, for example, the pigment particles can be crystal-grown or aggregated by heat, or conversely melted to maintain the fine particle shape in the pigment dispersion. Things that cannot be done occur. When this happens, there is a problem that the transparency, coloring power and color developability resulting from the finely dispersed performance at a high level of the pigment dispersion cannot be exhibited, and the remarkable product quality improvement effect is not exhibited.

  Therefore, the object of the present invention is that the pigment can be finely dispersed at a higher level than before, and the stability in the liquid medium is high, and the pigment aggregates over time as well as immediately after production. In addition, the present invention is to develop a technology for providing a pigment dispersion that can sufficiently exhibit its high transparency, coloring power, and coloring ability when used as a colorant for a product.

That is, the present invention is to further process the pigment into fine particles in the presence of at least the resin A, when obtaining a processed pigment comprising coated at least the resin A, as the resin A, the amino group alpha has, beta-unsaturated-containing monomer, and, alpha having an acid group, using a anionic cationic polymer as a constituent the beta-unsaturated bond-containing monomer, and a pigment treated fine the water-based paste, the acid groups or amino groups of the resin a in an aqueous solution medium containing the resin a obtained by neutralization, after mixing was stirred and / or to the aqueous dispersion to precipitate the resin a with pigments comprising to provide a method for manufacturing a processed pigment, wherein the benzalkonium that having a step of coating the resin a to the.

The following are mentioned as a preferable form of the manufacturing method of the processed pigment of this invention.
(1) The method for producing a processed pigment as described above, further comprising using a compound a having one or more acid groups and one or more aromatic rings when the pigment is treated.
(2) The processed pigment having the same skeleton as the skeleton of the pigment, the skeleton similar to the skeleton of the pigment, or the same skeleton as any skeleton constituting the pigment. Production method.
(3) Production of the processed pigment described above, which further uses a resin B which is an anionic polymer containing at least an α, β-unsaturated bond-containing monomer having an acid group when the pigment is treated. Method.
(4) The pigment is azo, cyanine, phthalocyanine, quinacridone, indigo, diketopyrrolopyrrole, perylene, perinone, isoindoline, isoindolinone, quinophthalone, antanthrone, dioxazine A process for producing the processed pigment as described above, which is one selected from the group consisting of an indanthrene system, a benzimidazolone system, an azomethine system, an anthraquinone system, and an azo metal complex system.
(5) The process pigment production method described above, wherein each of the acid groups is independently at least one of a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group.

  In another embodiment of the present invention, the pigment contains at least an α, β-unsaturated monomer having an amino group and an α, β-unsaturated bond-containing monomer having an acid group as constituent components. A processed pigment characterized in that it is coated with a material containing resin A, which is an anionic cation polymer, and the ratio of pigment to resin A is 50/50 to 99/1 on a mass basis It is.

  Another embodiment of the present invention is a pigment dispersion obtained by dispersing the processed pigment of the present invention in a liquid medium containing an oily organic solvent as a main component by a pigment dispersant.

The following are mentioned as a preferable form of the pigment dispersion of this invention.
(1) The pigment dispersant is polyacrylic, polystyrene, polystyrene acrylic, polyacryl polyurethane, polyester polyurethane, polyether polyurethane, polyester polyamide, polyester, polyether polyurethane, polyether phosphoric acid The pigment dispersion as described above, which is at least one of an ester series and a polyester phosphate ester series.
(2) The above pigment which is a colorant used in any one of paint, gravure ink, offset ink, inkjet ink, stationery ink, wet toner, fiber original, image display color, coating agent or UV coating agent Dispersion.

  According to the present invention, it is possible to disperse the fine particles of the pigment at a higher level than before, and the stability in an oily liquid medium is high, and the pigment aggregates over time as well as immediately after production. In addition, there is provided a pigment dispersion that, when used as a colorant for a product, exhibits sufficiently high transparency, coloring power and color developability.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the invention. The present invention relates to a pigment dispersion that can be used as a colorant in the production of oil-based articles such as paints and gravure inks, and more particularly to a processed pigment used in the pigment dispersion and a method for producing the processed pigment. It is.

  The processed pigment of the present invention comprises an anion comprising at least an α, β-unsaturated monomer having an amino group and an α, β-unsaturated bond-containing monomer having an acid group as constituents. It is characterized by being coated with a material containing resin A which is a cationic polymer. The processed pigment can be obtained by the method for producing a processed pigment of the present invention. In the method for producing a processed pigment of the present invention, when the pigment is treated in the presence of at least the resin A to obtain a processed pigment coated with at least the resin A, the resin A has an amino group α, Using the anionic cation-type polymer having a β-unsaturation-containing monomer and an α, β-unsaturated bond-containing monomer having an acid group as a constituent component, and using a finer pigment, the resin A After mixing and stirring and / or dispersing in an aqueous liquid medium containing the resin, the resin A is precipitated and the pigment is coated with the resin A, or the pigment is mixed with the resin A with stirring and / or milling and / or Alternatively, it is characterized by having a step of kneading to make the pigment fine and coat the resin A with the pigment. Moreover, when processing a pigment, it is preferable to further use the compound a having one or more acid groups and one or more aromatic rings. The compound a preferably has a basic structure selected from any one of the same skeleton as the pigment to be treated, a skeleton similar to the pigment, and any skeleton constituting the pigment. If necessary, it is preferable to further use resin B, which is an anionic polymer containing at least an α, β-unsaturated bond-containing monomer having an acid group, in combination with resin A. The present inventors consider that the remarkable effects of the present invention were obtained as a result of the above-described components exerting the following actions.

  Since the resin A used in the present invention has an amino group and an acid group in the structure thereof, the amino group and the acid group are bonded to each other by ionic bonding. Therefore, in the organic solvent which is an oily medium Does not dissolve. For this reason, when the resin mainly composed of the resin A is coated on the pigment and processed, the resin A is not dissolved in the organic solvent that is the oily medium, and the resin A is coated with the pigment in the oily medium. It can exist as it is. Further, in the case of treating a pigment, in addition to the resin A, when the compound a having one or more acid groups and one or more aromatic rings is used, the pigment and the resin are passed through the compound a as follows. It is thought that A can be combined. Since the compound a having the above structure has a high affinity for the pigment due to the aromatic ring in the structure, it is adsorbed on the pigment surface and introduces an acid group on the pigment surface. In particular, when the compound a has a basic structure that is the same as the skeleton of the pigment to be treated, a skeleton similar to the pigment, or any of the structures constituting the pigment, the skeleton is the pigment. Since it is similar to the skeleton, the affinity with the pigment is higher, which is preferable. The acid group introduced into the pigment surface is ionically bonded to the amino group of the resin A existing in the vicinity thereof to form an ionic bond between the acid group of the compound a and the amino group of the resin A on the surface of the pigment. . Furthermore, since an ionic bond between the amino group and acid group of the resin A described above is formed, a pigment coated with the resin A at a higher level (strength) can be obtained. In the present invention, if necessary, resin B which is an anionic polymer is used in the treatment of the pigment. The resin B plays the following role. Resin A and resin B form a composite by the ionic bond between the acid group in resin B and the amino group in resin A. As a result, it is possible to increase the coating amount of the pigment with the resin, or to introduce other functional groups or the like onto the pigment surface.

  In addition, an excess acid group, amino group, or excess acid group of the resin B that has not contributed to the bonding becomes a functional group that does not desorb from the pigment surface, and the pigment is formed on the acidic or basic surface. To do. Then, when the pigment becomes an acidic surface or a basic surface in this manner, adsorption with the dispersant used when obtaining the pigment dispersion is promoted, which is effective in stably dispersing the pigment.

  In the production method of the present invention, when the pigment is treated in the presence of the resin A, the pigment is dispersed, milled or kneaded to use the pigment in the form of fine particles, so the resin is coated with the fine particles. The For this reason, when the obtained processed pigment is dispersed in an oily liquid medium to form a pigment dispersion, the pigment dispersion does not cause aggregation in the dispersion step and can be made into a finely divided pigment dispersion. There is a great advantage that it is possible.

  Further, when the pigment dispersion coated with a resin as described above is used as a colorant for an article, the pigment dispersion is finely divided to a high level without being agglomerated in the dispersion step. Therefore, it is possible to prevent light scattering by the pigment surface in the article, and to prevent pigment aggregation, crystal growth, and heat melting in the article manufacturing process. It becomes an article while maintaining the shape of the fine particles. Therefore, an article using the pigment dispersion of the present invention as a colorant has improved color developability, transparency, sharpness, coloring power, and heat resistance.

  In summary, the processed pigment obtained according to the present invention is preferably used in combination with a resin A having an amino group and an acid group, preferably a compound a, and a resin B having an acid group, if necessary. By doing so, the pigment surface is coated with a resin by a bond via an ionic bond contributed by each functional group, so that a stable fine particle is obtained. And because of the presence of the ionic bond, the resin coated on the pigment surface does not dissolve in the oil-based article or oil-based liquid medium to be used, so it exists in the form of fine particles and as-coated pigment. Since the resin-derived functional group is introduced on the surface of the pigment, adsorption with the dispersant to be used is promoted, and a pigment dispersion that is finely dispersed stably in an oil-based liquid medium can be obtained. In addition, when such a pigment dispersion is used as a colorant for an article, in the production process, aggregation of the pigment and growth or dissolution of the crystals are suppressed, and light scattering is caused by being present in the article in the form of fine particles. Prevented, the resulting article provides high transparency, high color development, and high heat resistance.

Below, each component which comprises this invention is demonstrated in detail.
<Pigment>
First, the pigment used will be described. Conventionally known pigments are used, and organic pigments are particularly preferable.
Organic pigments include soluble azo, insoluble azo, disazo, etc .; cyanine; copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, phthalocyanines such as chlorinated products and brominated products thereof; quinacridone, dimethylquinacridone, dichloroquinacridone, etc. Quinacridone; Indigo; Diketopyrrolopyrrole, Dichlorodiketopyrrolopyrrole, Diketopyrrolopyrrole such as dimethyldiketopyrrolopyrrole; Perylene; Perinone; Isoindoline; Isoindolinone; Quinophthalone; Indanthrene, benzimidazolone, azomethine, anthraquinone, azo metal complexes such as nickel azo, red, blue, yellow, green, purple, orange, black pigments Can be mentioned Moreover, two or more kinds of solid solutions may be used among these pigments, and these various structural crystal bodies can be used. However, the pigments are not particularly limited as long as they have these structures.

Specific examples of pigment numbers in the color index (CI) include the following.
Examples of red pigments include C.I. I. Pigment red, and the following numbers can be used. That is, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like.

  Examples of blue pigments include C.I. I. Pigment blue, and the following numbers can be used. That is, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like.

  Examples of green pigments include C.I. I. Pigment green, and the following numbers can be used. That is, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and the like.

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

  Examples of orange pigments include C.I. I. Pigment orange, and the following numbers can be used. That is, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, and the like.

  Examples of purple pigments include C.I. I. Pigment violet, and the following numbers can be used. That is, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, and the like.

  The black pigment is not particularly limited, and examples thereof include carbon black, carbon nanotube, azomethine azo, and perylene.

  In addition, as the pigment, a pigment that has been subjected to various treatments can be used, and the treatment method is not particularly limited. For example, as the treatment, after pigment synthesis, in a kneader such as a kneader, for example, kneaded with an inert powder such as salt powder or calcium carbonate powder, and the surface is refined, or using a rosin soap or the like Pigments that have been pigmented can be used, such as those that have been surface-treated or crystals that have been prepared using a solvent in water.

<Resin A>
Next, the resin A that coats the pigment will be described. Resin A used in the present invention is an anion cation obtained by using an α, β-unsaturated bond-containing monomer having an amino group and an α, β-unsaturated bond-containing monomer having an acid group as at least components. Type polymer. The resin A covers the surface of a pigment, preferably a finely divided pigment. In this coating, when an amino group and an acid group in the structure of the resin A form an ionic bond and the resins are bonded to each other, and if necessary, a compound a having an acid group described later is used in combination. In addition to the above, since the acid group in the compound a and the amino group in the resin A form an ionic bond, the coated resin A constituting the fine particles is insoluble in the oily liquid medium. become. As a result, by coating the resin A, the pigment has stability, fine particle shape, and thermal stability.

The amino group contained in the structure of the resin A includes a primary amino group that is —NH ₂ , a secondary amino group that is —NRH, a tertiary amino group that is —NR ₂ , and —N ⁺ R ₃ X ^−. A quaternary ammonium base. By using the α, β-unsaturated monomer having these amino groups for the synthesis of Resin A, these amino groups can be introduced into the structure of Resin A. The α, β-unsaturated monomer used in that case is not particularly limited, but examples thereof include those listed below. One or more of these can be used.

  Examples of the α, β-unsaturated monomer having a primary amino group include vinylamine, allylamine, aminostyrene, 2-aminoethyl (meth) acrylate, 2-aminopropyl obtained by hydrolyzing vinylacetamide ( And (meth) acrylamide.

  Examples of the α, β-unsaturated monomer having a secondary amino group include vinylmethylamine, allylmethylamine, methylaminostyrene, t-butylaminoethyl (meth) acrylate, and tetramethylpiperidyl (meth). Examples include acrylate and t-butylaminopropyl (meth) acrylamide.

  Examples of the α, β-unsaturated monomer having a tertiary amino group (tertiary amine) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, N -Ethylmorpholino (meth) acrylate, dimethylpropyl (meth) acrylamide, vinylpyridine, vinylimidazole, vinylbenzotriazole, vinylcarbazole, dimethylaminostyrene, diallylmethylamine and the like.

  Examples of the α, β-unsaturated monomer having a quaternary ammonium base (quaternary ammonium salt) include trimethylammonium styrene chloride, dimethyllaurylaminostyrene chloride, vinylmethylpyridinyl iodide, trimethylamino chloride. Examples include ethyl (meth) acrylate, diethylmethylaminoethyl chloride (meth) acrylate, benzyldimethylaminoethyl (meth) chloride chloride, trimethylaminoethyl (meth) acrylate methyl sulfate, diallyldimethylammonium chloride.

  The acid group constituting the resin A is preferably any of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. By using these α, β-unsaturated monomers having these acid groups for the synthesis of Resin A, these acid groups can be introduced into the structure of Resin A. Although the monomer used in that case is not specifically limited, For example, the following are mentioned. Examples of the monomer having a carboxylic acid group include acrylic acid, methacrylic acid, maleic acid, acrylic acid dimer, itaconic acid, fumaric acid, crotonic acid, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meta ) A monomer obtained by reacting a hydroxyalkyl (meth) acrylate such as acrylate with maleic anhydride, succinic anhydride, or phthalic anhydride. Examples of the monomer having a sulfonic acid group include styrene sulfonic acid, dimethylpropyl sulfonic acid (meth) acrylamide, sulfonic acid ether (meth) acrylate, sulfonic acid ether (meth) acrylamide, and vinyl sulfonic acid. Examples of the monomer having a phosphate group include (di or tri) methacryloyloxyethyl phosphate. One or more of these can be used.

  In addition, when synthesizing the resin A used in the present invention, an α, β-unsaturated bond-containing monomer having an amino group and an α, β-unsaturated bond having an acid group are enumerated as described above. In addition to the monomers, other α, β-unsaturated bond-containing monomers that can be copolymerized therewith may also be copolymerized. The α, β-unsaturated bond-containing monomer used at that time is not particularly limited, and any of conventionally known monomers listed below can be used.

  For example, styrene, vinyl toluene, vinyl hydroxybenzene, chloromethyl styrene, vinyl naphthalene, vinyl biphenyl, vinyl ethyl benzene, vinyl dimethyl benzene, α-methyl styrene, ethylene, propylene, isoprene, butene, butadiene, 1-hexene, cyclohexene, cyclodecene Vinyl such as dichloroethylene, chloroethylene, fluoroethylene, tetrafluoroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl ethyl ketone, isocyanatodimethylmethane isopropenylbenzene, phenylmaleimide, cyclohexylmaleimide, hydroxymethylstyrene It is a system monomer.

  Also, methyl (meth) acrylate, ether (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-methylpropane (meth) acrylate, t-butyl (meth) acrylate, pentyl (Meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) a Relate, t-butylcyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclodecylmethyl (meth) acrylate, benzyl (meth) acrylate, t-butylbenzotriazole Aliphatic, alicyclic, and aromatic alkyl (meth) acrylates such as phenylethyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and allyl (meth) acrylate.

  Moreover, as a monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy Of alkylene glycols such as hexyl (meth) acrylate, 5-hydroxy-3-methylpentyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, cyclohexanediol mono (meth) acrylate, etc. Mono (meth) acrylic acid ester and the like.

  Also, poly (n = 2 or more) ethylene glycol mono (meth) acrylate, poly (n = 2 or more) prolene glycol mono (meth) acrylate, poly (n = 2 or more) tetramethylene glycol mono (meth) acrylate, mono Or poly (n = 2 or more) ethylene glycol mono or poly (n = 2 or more) pro (glycol) random copolymer mono (meth) acrylate, mono or poly (n = 2 or more) ethylene glycol mono or poly (n = 2 or more) ) Mono (meth) acrylates of polyalkylene glycols such as mono (meth) acrylates of prolene glycol block copolymers.

  In addition, lactones such as ε-caprolactone and γ-butyrolactone using the (poly) alkylene glycol mono (meth) acrylic acid ester such as (meth) acryloyloxyethyl mono or poly (n = 2 or more) caprolactone as an initiator. Polyester-based mono (meth) acrylic acid ester obtained by ring-opening polymerization of a polymer.

  In addition, the above-mentioned (poly) alkylene glycol mono (meth) acrylic acid such as 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate and 2- (meth) acryloyloxyethyl-2-hydroxyethyl succinate An ester-based (meth) acrylate obtained by reacting a dibasic acid with an ester to form a half ester and then reacting the other carboxylic acid with an alkylene glycol.

  Also, mono (meth) acrylates of polyfunctional hydroxyl compounds having three or more hydroxyl groups such as glycerol mono (meth) acrylate and dimethylolpropane mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, etc. Α-hydroxyl-substituted methyl acrylates such as halogen-containing (meth) acrylates and ether-α-hydroxymethyl acrylate.

  Also, (poly) ethylene glycol monomethyl ether (meth) acrylate, (poly) ethylene glycol monooctyl ether (meth) acrylate, (poly) ethylene glycol monolauryl ether (meth) acrylate, (poly) ethylene glycol monostearyl ether (meta) ) Acrylate, (poly) ethylene glycol monooleyl ether (meth) acrylate, (poly) ethylene glycol monostearate (meth) acrylate, (poly) ethylene glycol monononylphenyl ether (meth) acrylate, (poly) propylene glycol monomethyl Ether (meth) acrylate, (poly) propylene glycol monoethyl ether (meth) acrylate, (poly) propylene glycol monooctyl (Polyalkylene) glycol monoalkyl, alkylene, alkyne ether, such as ether (meth) acrylate, (poly) propylene glycol monolauryl ether (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol monomethyl ether (meth) acrylate, or And mono (meth) acrylates of esters.

  In addition, oxygen atom-containing cyclic alcohols such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, oxetanylmethyl (meth) acrylate, morpholino (meth) acrylate, methylmorpholino (meth) acrylate, methylmorpholinoethyl (meth) acrylate, etc. (Meth) acrylate and the like.

  Also, nitrogen atom-containing monomers such as (meth) acryloyloxyethyl isocyanate and ethyleneiminoethyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) Amide monomers such as acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.

  Also, fluorine or silicon group-containing (meth) acrylates such as octafluorooctyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, and tetramethylsilaneethyl (meth) acrylate. And 1 type or more selected suitably from what was enumerated above can be used.

  Moreover, when manufacturing resin A, it obtains using macromonomers obtained by introduce | transducing an unsaturated bond into the one terminal of the oligomer obtained by superposing | polymerizing these monomers, cobalt compounds, such as cobalt porphyrin, etc. In addition, a macromonomer having an unsaturated bond at its terminal can be used.

  Resin A obtained by using the monomers listed above as a constituent component is converted by the amount of potassium hydroxide whose amine value is equivalent to the amount of hydrogen chloride capable of neutralizing the amino group in the structure of resin A. 10 to 300 mgKOH / g, more preferably 20 to 100 mgKOH / g. This is because if the amine value is less than 10 mgKOH / g, the amount of ionic bonds between the amino group of resin A and the acid group of resin A, and further the acid group of resin B and the acid group of compound a is reduced. This is because the coated resin may be dissolved in the oily solvent. On the other hand, if the amine value exceeds 300 mgKOH / g, the amount of acid groups that can be introduced into the structure of the resin A when introducing the corresponding acid groups is reduced, resulting in fewer ionic bonds to be formed between the resins. This is not preferable because there is a possibility that the bonding of the resin becomes insufficient. Further, if the amine value is too high, the affinity for water is high, so that it may be dissolved in water or the water resistance may be deteriorated.

  The acid value of the resin A is 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, in terms of the amount of potassium hydroxide that can neutralize it. This is because if the acid value is less than 10 mgKOH / g, the resin A has too few acid groups, there are few ionic bonds with the amino groups in the resin A, and the resin between the resins is not sufficiently bonded to each other. This is because it may be dissolved in a solvent. On the other hand, if the acid value exceeds 300 mgKOH / g, the amount of amino groups that can be introduced when introducing the corresponding amino group into the structure of the resin A is reduced, resulting in fewer ionic bonds to be formed. There is a risk that the coupling of will be insufficient. Moreover, when an acid value exceeds 300 mgKOH / g, since affinity with water is high and water resistance may worsen, it is not preferable.

  The molecular weight of the resin A is preferably 1,000 to 100,000 as the number average molecular weight (Mn) in terms of styrene in the gel perchromatograph. More preferably, Mn is 3,000 to 50,000, and more preferably Mn 5,000 to 30,000. Further, the dispersity (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight, is preferably 1 to 3, and more preferably 1.1 to 2.5.

  The method for obtaining the resin A is not particularly limited. For example, it can be obtained by conventionally known bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or dispersion polymerization. Preferably, it can be obtained by solution polymerization. In particular, since there is an ionic bond between molecules, solution polymerization performed in a solvent that dissociates ions is preferable.

  Examples of solvents that can be used for ion dissociation include water, lower alcohols such as ethanol and isopropanol, polar solvents such as dimethyl sulfoxide, dimethylformamide, and dimethylacetamide, ethylene glycol, propylene glycol, and their (mono or di) alkyls. The glycol solvent which is ether and its multimer is mentioned, 1 type or those mixtures are used. Moreover, a conventionally well-known organic solvent can also be used as needed, However, In that case, it is preferable to use together the solvent which promotes the above-mentioned ion dissociation.

  Further, when the resin A is obtained by suspension polymerization or emulsion polymerization, it can be taken out by filtering as it is, or salted out and salted out. If necessary, it can be dissolved in a solvent or neutralized to form an aqueous solution. The resin solution obtained by solution polymerization can be used as it is. However, if necessary, the resin solution is precipitated in a solvent having a low polarity such as hexane, methanol, toluene, etc. Can be taken out as a solid and used.

  Further, since the resin A has an acid group and an amino group, the acid group or amino group can be neutralized to be water-soluble. When the acid group is neutralized to be water-soluble, it is neutralized with an alkaline substance such as ammonia, diethanolamine, triethanolamine, morpholine, triethylamine, sodium hydroxide, potassium hydroxide or the like. When the amine group is neutralized to form an aqueous solution, it is neutralized with an acid substance such as hydrochloric acid, sulfuric acid, nitric acid, or acetic acid.

  When the resin A is neutralized to form an aqueous solution, the alkaline substance that neutralizes the acid group is particularly preferably a weak base having a small pKa such as ammonia, diethanolamine, triethanolamine, or morpholine. In addition, as the acidic substance that neutralizes the amino group, a weak acid such as acetic acid or propionic acid is particularly preferable.

  In the production method of the present invention, when resin B, which is an anionic polymer having an acid group described later, is used together with resin A, resin A is preferably an aqueous solution obtained by neutralizing an acid.

Here, the relationship between the acid-basicity necessary for forming an ionic bond between the resin A and the resin B and further with the compound a to be described later used as necessary will be described. The strength is not particularly limited, but is preferably as follows.
The acidity of the acid group of the resin A, the acid group of the resin B, or the compound a is represented by pKa (A acid), pKa (B acid), pKa (a acid), the amino group of the resin A, the resin A or the resin B, respectively. When the basicity of the alkaline substance that neutralizes the acid group is pKa (A amino) and pKa (neutralized alkali), respectively, it is preferable that the following relationship holds.
pKa (a acid) <pKa (A acid) = pKa (B acid)
pKa (A amino)> pKa (neutralized alkali)

  In the case of having the above relationship, the present inventors consider that the reason why it is more preferable is as follows. For example, the acid group of the resin A is neutralized with a weak base (alkaline substance), and the pigment is added in the presence of a compound a that is stronger than the acid group of the resin A and has a high affinity for the pigment. When added, since the amino group of the resin A is a stronger base than the neutralized alkali substance, the acid group of the compound a existing on the pigment surface and the amino group of the resin A are ions rather than the alkali substance. Make a bond. As a result, it is considered that the resin A was able to coat the pigment in a more preferable state via the acid group of the compound a. In contrast, when the acid group of resin A is neutralized with a stronger base (alkaline substance) than the amino group of resin A, and the pigment is added in the presence of compound a having a high affinity for the pigment Since the alkaline substance neutralized with the resin A is a stronger base than the amino group of the resin A, the acid group of the compound a is neutralized with the neutralized alkaline substance. As a result, the ionic bond between the compound a and the resin A is hardly formed, and the resin A covers the pigment without bonding with the pigment. The embodiment of the present invention also includes this case, but particularly preferably, it is configured as described above, and by incorporating the compound a, there is a bond between the resin A and the pigment via the acid group of the compound a. More preferably.

  As a polymerization method of the resin A, it is preferable to obtain the resin A by a conventionally known radical polymerization method. The initiator that can be used in this case is not particularly limited as long as radical polymerization can be initiated, and commonly used organic peroxides and azo compounds can be used. Specific examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butylperoxy-2-ethylhexanoate. , Tert-hexylperoxy-2-ethylhexanoate, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (tert-butyl) Peroxy) hexyl-3,3-isopropyl hydroperoxide, tert-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, isobuty Peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) ) 3,3,5-trimethylcyclohexane, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-) 2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyrate) and the like.

  A radical polymerization initiator having an appropriate half-life is selected according to the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-30 mass parts with respect to a total of 100 mass parts of the monomer used for a copolymerization reaction, Preferably it is 1-10 mass parts.

  In the present invention, a chain transfer agent may be used for the purpose of controlling the molecular weight and molecular weight distribution. Specific examples include mercaptans such as dodecyl mercaptan, octyl mercaptan and mercaptoacetic acid; sulfides such as dibutyl sulfide and dibutyl disulfide; halogens such as carbon tetrachloride, chloroform, carbon tetrabromide and butyl bromide. . The usage-amount of a chain transfer agent is 0.1-30 mass parts with respect to a total of 100 mass parts of the monomer used for a copolymerization reaction, Preferably it is 0.5-10 mass parts.

  Similarly, addition-cleavage type chain transfer polymerization can also be used as chain transfer polymerization, and chain transfer agents used at that time include α-bromomethyl acrylate esters, α-iodomethyl acrylate esters, Examples include α-substituted methyl acrylates such as α-alkylthiomethyl acrylates; cobalt compounds such as cobalt porphyrin and cobalt phthalocyanine; iodine transfer polymerization using iodine compounds such as trifluoromethane iodide, and the like.

Moreover, you may obtain using the conventionally well-known control radical polymerization method. Thereby, a block copolymer and a structure can be obtained. By doing this, we obtain various higher-order structures such as block copolymers with a narrow molecular weight distribution, acid groups and amino groups, gradient copolymers with a monomer concentration gradient, graft copolymers, and star polymers. This is preferable. The method includes an atom transfer radical polymerization method using a complex such as an amino compound of a heavy metal such as copper, iron, ruthenium, or the like using an organic halide as a starting compound, or a nitroxide method using a tetramethylpiperidinyl oxide radical. , Reversible addition-fragmentation chain transfer polymerization using dithiocarboxylic acid ester compounds and xanthate compounds, transfer exchange polymerization using alkyl metal compounds such as germanium, bismuth and tellurium, phosphorus and nitrogen that inhibit polymerization And a reversible chain transfer catalytic polymerization method using an oxygen-containing compound, and is not particularly limited.
The resin A used for this invention is obtained as mentioned above.

<Compound a>
Subsequently, the compound a used in the present invention will be described. In the production method of the present invention, when a processed pigment is obtained using the pigment and the resin A, it is preferable to use a compound a having at least one acid group and one aromatic ring as the other compound. This compound a is one that remarkably adsorbs to the pigment by the aromatic ring in its structure to make the pigment surface acidic, and introduces an acid group to the pigment surface by the acid group in its structure. The acid group on the surface of the pigment introduced by the compound a works to ionically bond with the amino group of the resin A. Further, as described above, the amino group and the acid group in the resin A are ion-bonded to bond the resins to each other, and the acid group on the pigment surface introduced by the compound a and the amino group in the resin A , The resin A can form a coating with the pigment more firmly.

  It is essential that the compound a has one or more acid groups, and this acid group is any of the acid groups as described above, that is, any one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. preferable. Particularly preferred is a sulfonic acid group which is a strong acid group.

  Further, it is essential that the compound a contains at least one aromatic ring in order to increase the affinity with the pigment. Due to the presence of this aromatic ring, it can be adsorbed to the pigment surface by a π-π bond.

  The compound a used in the present invention is not particularly limited as long as it satisfies the above-mentioned conditions, and various examples can be given. For example, low molecular weight compounds such as benzene sulfonic acid, naphthalene sulfonic acid, dodecyl benzene sulfonic acid, benzoic acid, rosin acid, diphenyl phosphite, and other dye structures. Particularly preferably, the compound a has the same skeleton as that of the pigment used in the present invention, or a part of the structure constituting the pigment and the same skeleton, or a structure similar to the skeleton of the pigment used. Those having the same skeleton or those having a polycyclic pigment-like structure are preferred. Furthermore, it is more preferable to have one or more acid groups, particularly preferably a sulfonic acid group, in a part of each skeleton selected from these in order to increase the affinity of the pigment.

In particular, the compound a is not limited, but preferred examples used in the present invention include the following. Specifically, the aforementioned C.I. I. In the numbered pigment structure, a sulfonic acid group, a carboxylic acid group, or a phosphoric acid group is introduced. Particularly preferred is a sulfonic acid group introduced.
For example, monosulfonated copper phthalocyanine, tetrasulfonated copper phthalocyanine, sulfonated dimethyl diketopyrrolopyrrole, sulfonated diketopyrrolopyrrole, sulfonated dimethylquinacridone, sulfonated dimethylquinacridone, sulfonated dichloroquinacridone, sulfonated brominated copper phthalocyanine Sulfonated chlorinated copper phthalocyanine, sulfonated azo compounds and the like. Examples of the pigment-like structure include JP-A-2001-271004, JP-A-2005-097562, JP-A-2006-232867, JP-A-2006-265528, JP-A-2006-299050, and JP-A-2006-299050. Examples of the sulfonated compounds described in JP-A-2006-321979, JP-A-2007-023266, JP-A-2004-91497, and the like; These can be obtained by using a material having a sulfonic acid group as a raw material, or dissolving the obtained pigment in sulfuric acid for sulfonation, or sulfonation with sulfurous acid gas.

  The usage-amount of the above-mentioned compound a is 0.5 mass part-50 mass parts with respect to 100 mass parts of pigments, Preferably it is 1 mass part-20 mass parts. If the amount is less than 0.5 parts by mass, the performance due to the use of Compound a is not sufficiently exhibited. On the other hand, if it exceeds 50 parts by mass, the color is too much different from the original pigment color. This is not preferable because the property of the compound a is greatly increased and other problems such as hindering the inherent properties of the pigment may occur.

<Resin B>
Next, in the present invention, the resin B used as necessary in the treatment of the pigment will be described. The resin B is another resin added together with the resin A essential in the present invention, and is an anionic polymer having an acid group, and one or more types can be used. This is added for the purpose of causing the resin B to act as a cushioning agent when the resin A alone has many ionic bonds and the film of the bonded resin A becomes too hard. Furthermore, for the purpose of lowering the pigment content by introducing the surface of other functional groups or increasing the amount of resin used when the amount of the film consisting only of resin A is small, the resin-derived functional group is also added to the pigment surface. It is added for the purpose of imparting a group.

  As this resin B, the aforementioned α, β-unsaturated bond-containing monomer having an acid group, and more preferably the aforementioned α, β-unsaturated bond-containing monomer that can be copolymerized with the monomer having the acid group is used. A resin obtained by copolymerizing the monomer with a chain transfer agent or the like, if necessary, can be used.

  Examples of the acid group in the structure of the resin B include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, as described above. Particularly preferred is a weak acid group such as a carboxylic acid group. This is because when the acid group of the resin B is a strong acid, even if an ionic bond between the resin A and the compound a is formed, if the added resin B is a stronger acid, the amino group of the resin A This is because the ionic bond with the acid group of the resin B is changed, and the ionic bond between the pigment formed through the acid group of the compound a adsorbed on the pigment surface and the resin A may be cut.

  The resin B used in the present invention can be polymerized by the same method as the resin A described above, and further taken out or processed by the method described above.

  The molecular weight of the resin B is 1,000 to 50,000, preferably 3,000 to 30,000 as the molecular weight in terms of styrene in GPC. Moreover, as the acid value to contain, it is 10-300 mgKOH / g, Preferably it is 20-150 mg / KOH.

The usage-amount with respect to the pigment of resin A and B in the manufacturing method of the processed pigment of this invention is demonstrated. The total amount of the resin A and the resin B to be added as necessary is 1 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the pigment. This is because if the amount is less than 1 part by mass, the amount of the resin covering the pigment is insufficient, and the effects of the present invention may not be sufficiently obtained. On the other hand, when the total resin amount exceeds 100 parts by mass, the ratio of the pigment becomes too low, and when it is used as a dispersion having a required pigment concentration, the content ratio of the resin becomes too high and the desired performance is obtained. This is because there is a possibility that the color developability may be inferior when there is a risk of affecting the resin or when the resin content is greater than the pigment content.
The ratio of the resin A and the resin B is not particularly limited, and cannot be generally specified by the amount of acid groups and amino groups in the structure, but when the total resin amount is 100, on a mass basis, for example, A: B = 100: 0 to 1:99, preferably A: B = 100: 0 to 40:60.

  As described above, the processed pigment of the present invention is obtained by adding the target pigment, using the compound a as necessary, and adding the resin A and the resin B as necessary. This is a processed pigment in which the pigment is coated with the resin A through ionic bonds. This is because the pigment is coated with a resin in a solvent that does not cause ion dissociation due to ionic bonding, and the fine particles are allowed to exist as they are.

Next, the method for obtaining the processed pigment of the present invention will be described in detail.
Examples of the method for obtaining the processed pigment of the present invention include the following two methods.
(1) An aqueous solution of a resin A obtained by neutralizing an acid group or an amino group of a refined pigment, or a water paste thereof, and a pigment or a water paste to which compound a is added if necessary, If necessary, the pigment is aqueous-dispersed using an aqueous resin B obtained by neutralizing the acid group. Then, when the acid group of the resin is neutralized with an alkaline substance, the acid substance is added. When the amino group of the resin A is neutralized with an acidic substance, an alkaline substance is added to change the pH. A method of depositing a resin and coating the pigment with the resin.

(2) In the process of milling or kneading the pigment using an inert salt or the like, if necessary, compound a is added as necessary at the time of the miniaturization, and at the same time or to some extent fine Then, the powder and solution of resin A, a neutralized aqueous solution, and if necessary, the powder and solution of resin B and a neutralized aqueous solution are added to carry out a pigment micronization step. Subsequently, the refined pigment is precipitated in water or an acidic aqueous solution, and the salt is removed. At the same time, when the resin is insoluble in water, the resin is simply deposited in water, or when the resin is neutralized, the resin is deposited by changing the pH to coat the pigment.

The above method will be described individually.
As the pigment used in the above method (1), a refined pigment is used, but the refinement method (a refinement step) is not particularly limited. For example, the mixture is kneaded at room temperature or heated for 30 minutes to 60 hours, preferably 1 hour to 12 hours, using a known kneader such as a kneader, an extruder, or a ball mill. Also, if necessary, use a carbonate or chloride salt as a fine medium to make the system finer, and use a viscous solvent such as glycerin, ethylene glycol, or diethylene glycol for lubrication. It is preferable to carry out in combination. The salt is used in an amount of 1 to 30 times, preferably 2 to 20 times that of the pigment. The pigment water paste can be obtained by precipitating the obtained complex of pigment and salt in water and sufficiently removing the salt.

  At this time, it is preferable to add the compound a of the present invention during the milling of the pigment. This is because in the kneading step of the pigment and the compound a, the pigment and the compound a are bonded by a strong force called π-π bond, the compound a is uniformly adsorbed on the pigment surface, and the surface of the pigment is This is because it can be covered with an acid group. However, the invention is not limited thereto, and the finely divided pigment may be peptized in water, neutralized compound a may be added and stirred well, and then neutralized and precipitated to adsorb compound a onto the pigment surface.

The pigment refined as described above may be used as a water paste, or may be dried and used as a powder pigment. Preferably, a water paste is preferred to prevent secondary aggregation due to drying.
The single micronized pigment obtained as described above may be miniaturized in combination with the main pigment and one or two or more complementary color pigments in accordance with the target chromaticity. The individual pigments may be desalted simultaneously to form a mixture paste.

  The refined pigment obtained by the above-mentioned refinement is added to water, resin A, resin B if necessary, further an organic solvent, and if necessary, additives such as an antifoaming agent. By dispersing by this method, an aqueous dispersion of the pigment used in the above method (1) can be obtained.

  The organic solvent used in the dispersion step has an affinity for the resin when the resin is difficult to dissolve in water, and the resin has an affinity for water, or the initial wettability of the pigment. It is used for improvement. As this solvent, a conventionally known organic solvent can be used. In this case, a water-soluble solvent is particularly preferable. For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, ketone solvents such as acetone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc., and glycol systems such as mono- or dialkyl ethers thereof One or more solvents, ether solvents such as diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, pyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, dimethylethyleneurea, ethylene carbonate, propylene carbonate and the like are used. The amount of the organic solvent added in the dispersing step is not particularly limited, but is preferably 1 to 200%, more preferably 10 to 100% with respect to the pigment.

  The pigment concentration in the dispersion medium (water, organic solvent) in the dispersion step is 1 to 50%, preferably 5 to 30%. If it is less than 1%, the viscosity becomes too low due to the low concentration, so that the dispersion energy is not transmitted and the dispersion is difficult to proceed. On the other hand, if the pigment concentration exceeds 50%, the fluidity of the liquid deteriorates, which is not preferable.

  Moreover, when disperse | distributing a fine pigment, water, resin A, an organic solvent, an additive, etc., a conventionally well-known stirring apparatus, a dispersion apparatus, and a dispersion method can be taken and it does not specifically limit. Examples of the stirrer include a dissolver and a homogenizer. Examples of the dispersion method include bead mill dispersion, ultrasonic dispersion, and dispersion using an emulsifier. In the present invention, examples of a disperser that can be suitably used include a kneader, an attritor, a ball mill, a sand mill using glass or zircon, a horizontal media disperser, a colloid mill, and an ultrasonic disperser.

  Particularly preferable dispersion methods in the present invention are bead dispersion and ultrasonic dispersion. A dispersion method using very fine beads or a high output ultrasonic dispersion is preferable. The confirmation of the dispersion is confirmed by a conventionally known method, for example, by observing with a microscope or measuring the particle diameter with a particle size distribution meter. The average particle size at this time is not particularly limited, but is preferably 300 nm or less, more preferably 150 nm or less, and further preferably 80 nm or less.

  In addition, coarse particles may be removed by centrifugal filtration or filter filtration. As described above, an aqueous dispersion of the micronized pigment can be obtained.

  Next, the treatment of the aqueous pigment dispersion obtained as described above, which is performed by the above-described method for producing a processed pigment (1), will be described. That is, after stirring and / or dispersing for a predetermined time as described above, acidic water, that is, an acidic substance is added with stirring to precipitate the resin A and the resin B, and the fine pigment is coated with the resin.

  In this case, the aqueous pigment dispersion obtained above may be diluted, and the pigment concentration is preferably about 5 to 10% by mass. This is because when it is precipitated with an acid, the viscosity is remarkably increased, so that stirring is smoothly performed. As the acidic substance, conventionally known substances are used and are not particularly limited. For example, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as acetic acid, propionic acid and lactic acid can be used. Use a weak acid such as acetic acid. That is, if it is a strong acid, the ionic bond between the amino group and the acid group of the resin A or the ionic bond between the compound a and the resin A is cleaved, making it difficult to obtain the target coated pigment in the present invention. The acidic substance is preferably added as it is, preferably diluted to 1 to 10% by mass and gradually added. Moreover, although it precipitates when an acidic substance is added, it is good to make pH to 1, preferably to 3, and more preferably to 4.5. This is because if it is too acidic, the amino group of the resin A is neutralized, which may lead to solubility in water and breakage of ionic bonds.

  Moreover, when it filters after depositing, since it takes time for filtration when a particle diameter is small, in order to agglomerate a particle | grain or to make resin A and resin B adsorb | suck to a pigment surface strongly, it is 50-80 degreeC, for example. You may heat.

  When the precipitation treatment is performed, a salt is generated. Therefore, it is preferable to sufficiently remove the salt, and then filtration and washing are preferably performed. The obtained pigment paste is dried to form a chip, which is further pulverized into powder to be used as a processed pigment. As described above, the processed pigment can be obtained using the method (1).

Next, the method (2) described above will be described in detail. This is a method for coating a resin by adding resin A or, if necessary, resin B powder, solvent solution or aqueous solution to the pigment to be refined in the above-described pigment refinement step. And kneading in the same manner.
These additions are made in advance when the pigment is refined, or after the pigment is refined to some extent, or after the pigment is refined in a state where only the resin A is added, the resin B is added and further kneaded. The method can be taken. Then, after making into the shape of the desired fine particles, the salt is removed by putting out into water, or the salt is removed while putting out into acidic water or alkaline water to precipitate the resin. As a more preferable method, it is better to add the pigment and the compound a and knead, and after the pigment is refined to some extent, add the resin A and knead, and further add the resin B and knead. This is because after the compound a is adsorbed to the pigment, the resin A is ion-bonded to the pigment via the acid group of the compound a and is further treated with the resin B. In this manner, then, as described above, filtered, washed, can be dried to obtain the processed pigment.
The processed pigment of the present invention can be obtained by the above two methods.

  Next, the pigment dispersion obtained by using the processed pigment of the present invention obtained by the above method will be described.

The pigment dispersion of the present invention comprises at least the processed pigment of the present invention, a dispersant, and a liquid medium.
Dispersants used at this time are polyacrylic, polystyrene, polystyrene acrylic, polyacryl polyurethane, polyester polyurethane, polyether polyurethane, polyester polyamide, polyester, polyether phosphate ester, polyester A phosphate ester type can be used and is not particularly limited as long as the structure thereof is used.

  Specifically, examples of the polyacrylic and polystyreneacrylic dispersants include dispersants obtained by polymerizing the aforementioned monomers. Moreover, in this polymer such as polyacrylic or polystyreneacrylic, a monomer containing a hydroxyl group is copolymerized as one component of the constituent monomer, and a diisocyanate such as isophorone diisocyanate or toluene diisocyanate is used. A polyacryl polyurethane-based dispersant, which is a reaction product with an isocyanate compound, obtained by reacting one isocyanate of a compound with a tertiary amino group-containing alkyl alcohol or amine such as dimethylaminoethanol, diethylaminoethylamine, and hydroxyethylimidazole. It is done. In addition, polyisocyanates such as diisocyanates described above at the terminal hydroxyl groups of polycaprolactone and poly12-hydroxystearic acid, or multimers thereof such as allophanates and uretdiones, or polyisocyanates such as reactants of diisocyanate in trimethylolpropane, and the above-described amino group containing Examples thereof include polyester polyurethane-based dispersants reacted with alkylamines and alcohols.

A polyether polyurethane dispersant obtained by reacting a polyether such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol in place of the polyester polyurethane polyester can be used. Moreover, the polyester polyamide type dispersing agent which made polyamines, such as polyethylenimine and polyallylamine, react with polyesters, such as polycaprolactone, poly 12-hydroxystearic acid, and polyricinoleic acid. Moreover, the polyester-type dispersing agent which is a reaction product of secondary amine compounds, such as the above-mentioned polyester, the above-mentioned alkylamine which has an amino group, and a dibutylamine, and a compound which has an epoxy group is mentioned. In addition, polyether phosphate ester-based dispersants and polyester phosphate ester-based dispersants, which are reaction products of the above-described polyesters and polyethers with phosphorus-based compounds such as phosphorus trichloride, can be mentioned. Among these, a dispersant having an amino group is preferable in order to promote adsorption with the acid group of the resin A or the resin B.

  Next, the liquid medium used for the pigment dispersion of the present invention contains an organic solvent as a main component. The processed pigment of the present invention is a processed pigment in which a pigment and a resin or a resin are bonded via an ionic bond to coat the pigment. Therefore, it is not preferable to use a solvent that breaks ionic bonds. That is, media such as polar solvents such as water and dimethyl sulfoxide are unsuitable, and furthermore, low-molecular acidic substances and basic substances that break their ionic bonds in the system, especially hydrochloric acid, sulfuric acid, paratoluene. It is also not preferred to add a strong acid such as sulfonic acid or a strong base such as sodium hydroxide or potassium hydroxide.

  Examples of the organic solvent that can be used in the pigment dispersion of the present invention include the following low-polar solvents. For example, hydrocarbon solvents such as hexane, toluene, xylene, ethylbenzene, isodecane, ketones having a large carbon number such as methyl isobutyl ketone, diethyl ketone, cyclohexanone, alcohols having a large carbon number such as butanol, hexanol, lauryl alcohol, Examples thereof include esters such as ether acetate, butyl acetate and dioctyl phthalate, glycol-based alkyl ether alkyl esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and the above-described monomers. However, even if it is the said solvent which breaks an ionic bond, when using this low polar solvent together, it can be used.

  In addition to the processed pigment, dispersant, and liquid medium of the present invention, various additives can be added to the pigment dispersion of the present invention. For example, durability improvers such as UV absorbers and antioxidants; anti-settling materials; release agents or release improvers; aromatics, antibacterial agents, antifungal agents; plasticizers, anti-drying agents, etc. Furthermore, if necessary, compound a, a dispersion aid, a dye and the like can be added.

  The dispersion method for obtaining the pigment dispersion of the present invention can be obtained by dispersing by the liquid medium method described above as (1) of the process pigment production method. The average particle size at this time is not particularly limited, but is preferably 300 nm or less, more preferably 150 nm or less, and further preferably 80 nm or less. This can be the same as the particle size of the finely divided pigment, and is more preferable.

  As described above, a processed pigment and a pigment dispersion using the processed pigment can be obtained, and the pigment dispersion is suitably used for conventionally known oil-based articles. For example, ink, paint, coating agent, IT Can be used for colorants such as related coatings and inks. More specifically, paints for automobile painting, metal painting, building material painting, etc .; inks such as gravure ink, offset ink, flexo ink, UV ink; oil-based inkjet ink, UV inkjet ink, color for image display, IT-related coating agents and inks such as wet toner; coating agents such as plastic surface coating agents and UV coating agents; oil-based stationery pen inks; Used in. And, these articles are given high transparency and high color developability from their very high level and stabilized fine particles. By coating the pigment with a resin, the aggregation of the pigment due to heat during the manufacture of the article It prevents melting and improves heat resistance.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these examples. In the text, “part” or “%” is based on mass.

<Synthesis of Resin A>
[Synthesis Example 1]
100 parts of propylene glycol monomethyl ether and 100 parts of industrial ethanol were added to a reaction apparatus equipped with a stirrer, a reverse flow condenser, a thermometer, a nitrogen introduction tube, and a dropping device, and heated to 80 ° C. in a hot water bath. In a separate container, 50 parts of styrene (hereinafter abbreviated as St), 70 parts of butyl acrylate, 40 parts of methacrylic acid (hereinafter abbreviated as MAA), 40 parts of dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA), as an initiator 2.8 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was charged to dissolve the initiator in the monomer.

  Next, 1/2 of the monomer mixture was added, and the remaining monomer mixture solution was added dropwise to the reaction system over 1.5 hours. The hot water bath was adjusted to 80 ° C., 1 hour after the completion of the dropwise addition, 1 part of AIBN was added, and then polymerization was carried out at that temperature for 5 hours.

After the completion of the polymerization, the mixture was cooled to 50 ° C., and a mixture obtained by adding 29.6 parts of 28% ammonia aqueous solution to 70.4 g of water was added to another container for neutralization. A resin solution which is a resin A of the present invention having a pale yellow transparent viscosity was obtained. When measured with an infrared moisture meter, the solid content was 41.3% and the polymerization rate was almost 100%.
When the resin solution before neutralization was sampled and the molecular weight was measured by GPC, the number average molecular weight was 8,300. The theoretical acid value in this resin is 127.3 mgKOH / g, and the theoretical amine value is 71.4 mgKOH / g. This is anion cation type polymer-1 (corresponding to resin A).

[Synthesis Examples 2 to 4]
In the same manner as in Synthesis Example 1 with the monomer composition shown in Table 1, anion cation type polymers -2 to -4 as Resin A were obtained. Table 1 shows the composition and properties of the obtained resin.

[Synthesis Example 5]
In a reaction vessel equipped with a stirrer, a backflow condenser, a thermometer and a nitrogen introduction tube, 200 parts of diethylene glycol dimethyl ether (hereinafter abbreviated as DMDG), 5.0 parts of iodine, 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile) (hereinafter abbreviated as V-70) 24.2 parts, BzMA 120 parts, methyl methacrylate (hereinafter abbreviated as MMA) 30 parts and N-iodosuccinimide (hereinafter abbreviated as NIS) 0.1 The first block portion was synthesized by charging the portion and polymerizing at 45 ° C. for 4 hours with nitrogen bubbling. Sampling and measuring the solid content, the polymerization conversion rate converted from the non-volatile content was 100%. In the visible light detector (hereinafter abbreviated as RI) in GPC, Mn was 7,400 and PDI was 1.22.

  Next, 30 parts of MAA and 20 parts of DMAEMA were successively added, and further polymerized at the same temperature for 4 hours to synthesize a second block part. Sampling and measuring solid content, the polymerization conversion rate converted from the non volatile matter was 99%. At this time, Mn in GPC RI was 8,200, and PDI was 1.35. Since the molecular weight is increased from the first block portion, the obtained polymer is considered to be a diblock polymer.

After the completion of the polymerization, a mixture obtained by adding 23.3 parts of 28% aqueous ammonia to 76.7 g of water was added to another container for neutralization to obtain a light blue transparent resin solution. Since the obtained polymer is a block structure, the water-insoluble part is aggregated and partly emulsified, so it is considered that the polymer has a light blue color. When measured with an infrared moisture meter, the solid content was 41.0%.
The theoretical acid value in this resin is 97.8 mgKOH / g, and the theoretical amine value is 35.7 mgKOH / g. This is designated as anion-cationic polymer-5 (corresponding to resin A).

  For each anionic cation type polymer, the resin solution after polymerization is precipitated in methanol, filtered, washed with methanol, dried and pulverized to obtain a solid resin, which is toluene, ether acetate, butyl acetate, propylene glycol monomethyl. When added to ether (hereinafter abbreviated as PGMAc) and stirred, it was confirmed that it did not dissolve.

<Synthesis of Resin B>
[Synthesis Examples 6 to 8]
In the same manner as in Synthesis Example 1, anionic polymers -1- to -3 as Resin B were obtained. Table 2 shows the composition and properties of the obtained resin.

[Synthesis Example 9]
Charge 200 parts DMDG, 5.0 parts iodine, 24.2 parts V-70, 130 parts BzMA, 30 parts MMA, 0.1 parts NIS and 0.1 parts nitrogen bubbling in the same reactor as in Synthesis Example 5. The first block portion was synthesized by polymerization at 45 ° C. for 4 hours. Sampling and measuring the solid content, the polymerization conversion rate converted from the non-volatile content was 100%. Moreover, Mn in RI by GPC was 7,300, and PDI was 1.24.

  Next, 40 parts of MAA was added and further polymerized at the same temperature for 4 hours to synthesize a second block part. Sampling and measuring the solid content, the polymerization conversion rate converted from the non-volatile content was 100%. At this time, Mn in GPC RI was 8,000, and PDI was 1.34. Since the molecular weight is larger than that of the first block portion, the obtained polymer is considered to be a diblock polymer.

After completion of the polymerization, a mixture obtained by adding 31.0 parts of a 28% aqueous ammonia solution to 69.0 g of water in a separate container was neutralized to obtain a light blue transparent resin solution. When measured with an infrared moisture meter, the solid content was 41.5%.
Moreover, the theoretical acid value in this solid content (resin) is 130.4 mgKOH / g. This is designated as Anionic Polymer-4 (corresponding to Resin B).

<Manufacture of pigment kneaded material>
[Formulation Example 1]
100 parts of a commercially available diketopyrrolopyrrole red pigment (CIPR 254), 200 parts of diethylene glycol, and 700 parts of salt are put into a 3 L kneader and adjusted so that the temperature is maintained at 80 to 100 ° C. And milled for 8 hours to obtain a kneaded product R-1. 800 parts of the obtained kneaded product R-1 was put into 2,000 parts of water and stirred at high speed for 4 hours. Next, filtration and washing were performed to obtain a mixed pigment water paste (pigment purity 29.3%). This is referred to as kneaded product R-1.

[Formulation Example 2]
5 parts of monosulfonated diketopyrrolopyrrole (average amount of sulfonic acid group: 0.5 / 1 molecule) was further added to Formulation Example 1, and kneaded product R-2 was obtained in the same manner. The solid content was 23.5% in terms of pure pigment content.

[Composition Example 3]
100 parts of a commercially available nickel azo-based yellow pigment (C.I.P.Y.150), 200 parts of diethylene glycol, and 700 parts of sodium chloride are put into a 3 L kneader and adjusted so that the temperature is kept at 80 to 100 ° C. After kneading for a time, a kneaded material Y-1 was obtained. A water paste was obtained in the same manner as in Formulation Example 1 using this kneaded product Y-1. The solid content was 30.2% in terms of pure pigment content.

[Formulation Example 4]
100 parts of a commercially available brominated phthalocyanine green pigment (CIPG 36), 6 parts of an anthraquinone compound (Chemical Formula 1) described in the synthesis example of JP-A No. 2001-271004 as a dispersant, diethylene glycol 200 parts and 700 parts of sodium chloride were put into a 3 L kneader, adjusted so that the temperature was kept at 100 ° C. to 120 ° C., and ground for 8 hours to obtain a kneaded product G-1. And it post-processed like the compounding example 1. The solid content was 37.2% in terms of pure pigment content.

[Formulation Example 5]
100 parts of commercially available ε-type phthalocyanine-based blue pigment (CIPB.15: 6), 5 parts of monosulfonated copper phthalocyanine, 200 parts of diethylene glycol, and 700 parts of sodium chloride were put into a 3 L kneader and the temperature was 100. The mixture was adjusted so as to maintain a temperature of from 120 ° C. to 120 ° C. and ground for 8 hours to obtain a kneaded product B-1. Then, post-treatment was performed in the same manner as in Formulation Example 1. The solid content was 24.1% as pure pigment.

[Composition Example 6]
100 parts of a commercially available dioxazine-based purple pigment (C.I.P.V.23), 200 parts of diethylene glycol, and 700 parts of sodium chloride are put into a 3 L kneader and adjusted so that the temperature is maintained at 60 to 80 ° C. After kneading for a time, a kneaded material V-1 was obtained. It processed like the compounding example 1, and obtained the water paste whose solid content is 32.6% with a pure pigment content.

[Comparative Examples 1-6]
The water pastes of Formulation Examples 1 to 6 were dried and pulverized as they were to prepare comparative pigments without resin treatment.

[Example 1]
Add 100 parts of the kneaded product R-1 obtained in Formulation Example 1, 7.1 parts of the anionic cationic polymer-1 (Resin A) obtained in Synthesis Example 1, and 39.4 parts of water, and mix with a disper. Stir. Next, 500 parts of zirconia beads having a bead diameter of 0.5 mm were filled in a glass bottle and dispersed for 5 hours with a paint conditioner to finely disperse the pigment. This was filtered with a membrane filter to remove coarse particles to obtain a pre-aqueous pigment dispersion. At this time, the average particle diameter of the primary particles by TEM observation was about 46 nm.

  Next, the pre-aqueous pigment dispersion is diluted with ion-exchanged water into a 3 liter beaker to make the pigment content about 5%, and a 5% aqueous acetic acid solution prepared in advance is added with stirring. A was deposited and coated with the pigment. The final pH of the pigment treatment solution was 4.9. Further, this pigment treatment liquid was heated to 50 ° C. in a water bath and stirred for 1 hour, so that the resin was adsorbed to the pigment well. Next, this treatment liquid was filtered, washed thoroughly with ion-exchanged water, dried and pulverized. This was designated as processed pigment R-1 of this example.

[Example 2]
100 parts of the PR-254 kneaded product obtained in Formulation Example 2, 5.6 parts of anionic cation type polymer-2 (Resin A) obtained in Synthesis Example 2 and 11.9 parts of water were added, Dispersed for 3 hours in the same manner as in Example 1. Next, 5.74 parts of anionic polymer-1 (resin B) obtained in Synthesis Example 6 was added and dispersed for another 2 hours. Next, a pre-aqueous pigment dispersion was obtained in the same manner as in Example 1. The average particle size at this time was 45 nm. This was precipitated in the same manner as in Example 1, heated and stirred, dried and pulverized to obtain processed pigment R-2 of this example.

[Examples 3 to 8]
In the same manner as in Example 1 or 2, processed pigments having the structures shown in Table 3 below were obtained.

[ Reference Example 9]
100 parts of a commercially available anthraquinonyl red pigment (CIPR 177), 200 parts of diethylene glycol and 700 parts of sodium chloride are put into a 3 L kneader, preliminarily mixed and stirred, and then anion cation type 23.8 parts of polymer-2 (resin A) was added, adjusted so that the temperature was maintained at 80 ° C. to 100 ° C., and ground for 8 hours. Next, the kneaded material was gradually added to a bath in which 6 parts of acetic acid was dissolved in 2,000 parts of water while stirring at high speed to precipitate the resin. Next, the mixture was filtered, washed thoroughly with ion exchange water, dried and pulverized. The average particle size was 32 nm. This is designated as processed pigment R-5.

<Creation of pigment dispersion>
[Example 10]
50 parts of acrylic resin varnish is blended with 15 parts of the processed pigment R-1 obtained earlier, 10 parts of polyester polyamide dispersant and 25 parts of PGMAc, and after premixing, is dispersed in a horizontal bead mill. A pigment dispersion was obtained. The acrylic resin varnish was obtained by polymerization at a molar ratio of benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate = 70/15/15, and had a molecular weight of 12,000 and an acid value of 97. A PGMAc solution having a solid content of 40% was used. Moreover, the reaction product (solid content 46%) of polycaprolactone and polyethyleneimine which uses 12-hydroxystearic acid as an initiator was used as the polyester polyamide-based dispersant.

[Examples 11 to 13 , 15 to 18 , Reference Example 14 ]
In place of the processed pigment of Example 1, processed pigments R-2, R-3, R-4, R-5, Y-1, G-1, B-1, and V-1 were used, respectively. In the same manner as in Example 10, pigment dispersions of respective colors of Examples 11 to 13 , 15 to 18 and Reference Example 14 were obtained.

[Evaluation of pigment dispersions of Examples 10 to 13 , 15 to 18 and Reference Example 14 ]
When the average particle diameter of the pigment dispersions of the pigment dispersions of the respective colors of Examples and Reference Examples obtained as described above was measured, the average particle diameter was about 40 to 55 nm, which was an intermediate stage for obtaining a processed pigment. It was confirmed that the particles were finely dispersed until the particle diameter was equal to that in the pre-aqueous pigment dispersion. Further, the viscosity of each pigment dispersion was measured. The particle diameter and viscosity of the pigment dispersion are summarized in Table 4.

[Comparative Examples 7-12]
Comparative pigment dispersions were respectively obtained in the same manner as in Example 10 except that the non-resin-treated pigments obtained in Comparative Examples 1 to 6 were used. When the average particle diameter of the pigment of the obtained pigment dispersion of each color was measured, the average particle diameter was about 30 to 50 nm, and it was a finely dispersed pigment dispersion that gave a fine particle diameter after kneading. It was confirmed. Also, the viscosity was low.

[Example 19]
In Example 10, processed pigment B-1 was used instead of processed pigment R-1 as the pigment, butyl carbitol acetate was used instead of PGMAc as the solvent, and the dispersant was a polyurethane-based dispersant (polyethylene A pigment dispersion B-2 was obtained in the same manner as in Example 10 except that the reaction product was a reaction product of caprolactone, dimethylaminoethylamine, toluene diisocyanate, and trimethylolpropane. The obtained pigment dispersion had an average particle diameter of 52 nm and a viscosity of 26.0 mPa · s.

[Example 20]
In Example 19, except that the solvent was changed to butyl acetate and butanol (91/10 mass ratio) and the dispersant was changed to BYK-2001 (acrylic block copolymer having an amine value), Example 19 and Example 19 Similarly, pigment dispersion B-3 was obtained. The obtained pigment dispersion had an average particle size of 48 nm and a viscosity of 20.3 mPa · s.

[Application Example 1]
Using the pigment dispersions of the present invention obtained in Examples 10 to 19 as display display colors (colorants), RGB color filters were respectively prepared. The resulting color filter has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, excellent properties such as contrast and light transmission, and excellent properties for image display. It was. In particular, when this color filter plate was heated at 270 ° C. for 10 minutes, in all pigment dispersions, the contrast retention before and after the heating was all 80%, and excellent heat resistance was obtained. A fine particle state that can withstand heat was obtained.

  Using the pigment dispersions of Comparative Examples 7 to 12, color filter plates were prepared in the same manner as described above. As a result, like the pigment dispersion of the example of the present invention, it has excellent spectral curve characteristics, excellent fastness such as light resistance, and excellent properties such as contrast and light transmittance, and image display. As an excellent property. However, when heating was performed at 270 ° C. for 10 minutes, the contrast retention before and after heating all decreased to 40% or less.

  That is, the processed pigment of the example of the present invention is coated with a specific resin A that does not dissolve in an organic solvent that is an oily medium, and in a more preferable form, the processed pigment is formed through an acid group introduced on the pigment surface. Is ion-bonded to the pigment surface and is difficult to peel off from the pigment. As a result, when used as a colorant for a product, there is no melting, aggregation, or crystallization of the pigment due to heat in the production process of the product, and the dispersed fine particle shape is not destroyed by the heat. It is considered that the color filter plate using the processed pigment of Example 1 has improved heat resistance and improved contrast retention. On the other hand, when the pigment of the comparative example which is not resin-treated is used, it is considered that the pigment aggregates due to heat and the contrast when the color filter plate is formed is lowered.

[Application Example 2]
Ink was prepared by mixing and stirring 250 parts of pigment dispersion B-3 of Example 20, 250 parts of an acrylic resin solution, 286 parts of ethanol, and 60 parts of methylcyclohexane. As the acrylic resin solution, a solution prepared by dissolving methyl methacrylate / 2-hydroxyethyl methacrylate / acryloyloxyethyl phthalate / lauryl methacrylate copolymer in an ethanol / cyclohexane mixed solvent (solid content 40%) was used. . The viscosity of the obtained ink was 5.9 mPa · s. Even when stored at 50 ° C. for 1 week, the change in viscosity was as low as 4.3%, and no precipitation of the pigment was observed. Next, when this ink was packed in a pen body having a fiber bundle core and written on a polyethylene film, it was successfully written.

[Application Example 3]
Ink was prepared by mixing and stirring 100 parts of Pigment Dispersion B-2 of Example 19, 250 parts of the acrylic resin solvent used in Application Example 2, and 346 parts by changing the additive solvent to butoxycarbitol acetate. Next, 100 parts of this were converted into an ink by adding 20 parts of ethoxypropanol and 5 parts of benzyl alcohol, and printed with an ink jet printer. As a result, a good printed matter was obtained.

  The pigment dispersion obtained by dispersing the processed pigment of the present invention is stably finely divided at a high level, and when used as a coloring material for various products, in the production process of the product, the pigment dispersion by heat is also applied. There is no melting, aggregation, or crystallization, and the shape of fine particles dispersed by heat is not lost.Especially in image display devices such as color displays, high image quality and high color development can be given, and beautiful images can be obtained. Moreover, high designability can be given in the coating of general articles.

Claims (9)

An organic pigment that has been micronized by a kneader such as a kneader, an extruder, or a ball mill to form fine particles is further treated with at least the resin A and the compound a to be coated with at least the resin A and the compound a. When obtaining processed pigments,
As the resin A, an α-, β-unsaturated monomer having an amino group, and an anionic cation-type polymer having an α, β-unsaturated bond-containing monomer having an acid group as constituent components are used.
As the compound a, a compound having one or more acid groups of carboxylic acid group, sulfonic acid group or phosphoric acid group and one or more aromatic rings (provided that a polymer of a monomer having an acid group, or The resin A and the organic compound via the acid group of the compound a introduced to the surface of the organic pigment, except for a polymer obtained by polymerizing a monomer having no acid group with a polymerization initiator having an acid group) In order for the pigment to bind and the organic pigment to be coated with resin A and compound a,
As the finely divided organic pigment, an organic pigment obtained by adsorbing the compound a on the pigment surface at the time of the miniaturization treatment is used, and a water paste containing the organic pigment, or the finely divided organic pigment, Either of the water paste to which the compound a is added,
In the aqueous liquid medium containing the resin A obtained by neutralizing the acid group or amino group of the resin A, after mixing and stirring and / or aqueous dispersion, the resin A is precipitated, and the resin A and the compound a A process for producing a processed pigment, comprising the step of coating an organic pigment with   Compound a is C.I. I. The method for producing a processed pigment according to claim 1, wherein a sulfonic acid group, a carboxylic acid group or a phosphoric acid group is introduced into the numbered pigment structure.   The method for producing a processed pigment according to claim 1 or 2, wherein the acid group of the compound a is a sulfonic acid group.   The resin B, which is an anionic polymer containing at least an α, β-unsaturated bond-containing monomer having an acid group as a constituent, is further added to the aqueous liquid medium containing the resin A. The manufacturing method of the processed pigment of any one of these.   The organic pigment is azo, cyanine, phthalocyanine, quinacridone, indigo, diketopyrrolopyrrole, perylene, perinone, isoindoline, isoindolinone, quinophthalone, antanthrone, dioxazine, The method for producing a processed pigment according to any one of claims 1 to 4, wherein the processed pigment is one selected from the group consisting of indanthrene, benzimidazolone, azomethine, anthraquinone, and azo metal complex.   The acid group of the resin A is at least one of a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group, and the acid group of the compound a is a stronger acid group than the acid group of the resin A. The manufacturing method of the processed pigment of any one of -5. The method for producing a processed pigment according to any one of claims 1 to 6, wherein a ratio between the organic pigment and the resin A is 50/50 to 99/1 on a mass basis. After obtaining the processed pigment by the method for producing a processed pigment according to any one of claims 1 to 7, the obtained processed pigment is put into a liquid medium containing an oily organic solvent as a main component by a pigment dispersant. method for manufacturing a pigment dispersion characterized that you distributed. The pigment dispersant is polyacrylic, polystyrene, polystyrene acrylic, polyacryl polyurethane, polyester polyurethane, polyether polyurethane, polyester polyamide, polyester, polyether polyurethane, polyether phosphate ester and The method for producing a pigment dispersion according to claim 8, which is at least one of polyester phosphate esters.