JP2019163387A - Coating pigment, and pigment aqueous dispersion, and use therefor, and method for producing the same - Google Patents

Abstract

To provide a fine coating pigment that suppresses coarse particles and can be easily dispersed.SOLUTION: A coating pigment has its surface coated with a resin, the resin being an α-olefin copolymer having an acidic group, and the amount of the resin coating on the coating pigment is 10 pts.mass or more and 50 pts.mass or less when the amount of the pigment (X) before coating is 100 pts.mass. Preferably, the resin is an α-olefin copolymer having a side chain and an acidic group. Further preferably, the resin is at least one selected from the group consisting of a styrene-(meth) acrylic resin, a styrene-(anhydride) maleic acid resin, and a (meth) acrylic resin.SELECTED DRAWING: None

Description

  The present invention relates to a resin-coated pigment.

  BACKGROUND ART Pigment compositions using organic pigments are used in various applications in the paint field such as automobiles and building materials, the printing ink field, etc., both indoors and outdoors. Among them, fine pigments with less coarse particles than other applications are required in fields requiring high functions such as the paint field, inkjet recording field, color filter color resist field, toner field, and stationery field.

  Examples of a method for obtaining a fine organic pigment include salt milling. Salt milling is a process of mechanically kneading the pigment with a water-insoluble synthetic resin, a water-soluble inorganic salt such as salt, and a water-soluble organic solvent and a kneader, and then washing with water to wash the water-soluble inorganic salt and the water-soluble organic. Remove the solvent. However, in salt milling, since the pigment is fine, aggregation between the pigments is extremely strong, and it is difficult to disperse the pigment to the primary particles in the subsequent process of obtaining the pigment dispersion, and a great deal of energy is input. A dispersion process is required.

  Therefore, in order to suppress the aggregation of organic pigments by coating the organic pigment with a compound, Patent Document 1 describes a coated pigment obtained by coating an organic pigment with an α-olefin copolymer having an acidic group. Yes. Patent Document 2 discloses a coated pigment obtained by coating an organic pigment with a surfactant such as polyoxyethylene styrene phenyl ether.

JP 2004-91520 A JP 2007-191556 A

  However, since the coated pigment of Patent Document 1 is a mixture of an organic pigment and an α-olefin copolymer having an acidic group using a high-speed mixer, the surface coating amount of the pigment is small and the generation of coarse particles is suppressed. It was difficult. Moreover, since the coating pigment of patent document 2 is coat | covered with surfactant, generation | occurrence | production of the coarse particle was not able to be suppressed by coating.

  An object of the present invention is to provide a fine coated pigment that suppresses coarse particles and can be easily dispersed.

The coated pigment of the present invention is a pigment whose surface is coated with a resin,
The resin is an α-olefin copolymer having an acidic group,
The resin coating amount of the coating pigment is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment (X) before coating.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide fine coated pigments and pigment dispersions which can suppress coarse particles and can be easily dispersed, and paints, toners, ink jet printing inks, printing inks and stationerys using these.

  The terms used in this specification are defined. The monomer is an ethylenically unsaturated group-containing monomer. For example, 1-10 mass% means 1 mass% or more and 10 mass% or less.

The coated pigment of the present invention is a pigment whose surface is coated with a resin,
The resin is an α-olefin copolymer having an acidic group,
The resin coating amount of the coating pigment is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment (X) (hereinafter also simply referred to as “pigment (X)”) before coating.
Thereby, when a pigment is refined | miniaturized, generation | occurrence | production of a coarse particle can be suppressed. Further, in the case of an aqueous dispersion containing water and a basic compound in addition to the coated pigment, an aqueous pigment dispersion having a good dispersion state of the coated pigment and good solution stability can be produced.

<Α-Olefin Copolymer Having Acidic Group>
The α-olefin copolymer having an acidic group is a copolymer of an α-olefin and an acidic group-containing monomer.

(Α-olefin)
The α-olefin is preferably a compound having 5 to 50 carbon atoms having an ethylenically unsaturated group. Moreover, as for carbon number of an alpha olefin, 10-30 are preferable. When the number of carbon atoms is 5 to 50, it becomes easier to coat the surface of the pigment, and the dispersibility of the coated pigment is further improved.

  The α-olefin is, for example, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene. 1-tetracocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratriacontene, 1-hexatriatainene, 1-octatriacontene and the like.

  The α-olefin can be used alone or in combination of two or more.

(Acid group-containing monomer)
The acidic group-containing monomer is a monomer other than an α-olefin and has an acidic group. Examples of the ethylenically unsaturated double bond include a vinyl group, an allyl group, and a (meth) acryl group. Examples of the acidic group include a carboxyl group, an acid anhydride group, a sulfo group, and a phosphoric acid group. Among these, a carboxyl group and an acid anhydride group are preferable in consideration of formation of a side chain.

  Examples of the acidic group-containing monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl ( And (meth) acrylate and ω-carboxypolycaprolactone (meth) acrylate. Among these, (meth) acrylic acid, maleic acid, and maleic anhydride are preferable.

  An acidic group containing monomer can be used individually or in combination of 2 or more types.

(Other monomers)
For the synthesis of the α-olefin copolymer having an acidic group, other monomers can be used as necessary.
Other monomers are monomers other than α-olefins and acidic group-containing monomers.
Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl Linear or branched alkyl (meth) acrylates such as (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate Cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy Cyclic alkyl (meth) acrylates such as ethyl (meth) acrylate and isobornyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, and heterocyclic rings such as 3-methyl-3-oxetanyl (meth) acrylate (meth) Acrylate: benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, Cumylphenoxypolyethylene glycol (meth) acrylate and (meth) acrylate having an aromatic ring such as nonylphenoxypolyethylene glycol (meth) acrylate; trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl Fluoroalkyl (meth) acrylates such as ethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethylsiloxane (silicone macromer); 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl ( (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, and polyethylene glycol monostearyl ether (meth) acrylate; (Meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl N-substituted (meth) acrylamides such as (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine; nitriles such as (meth) acrylonitrile; styrene, and α-methylstyrene Styrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; fatty acid vinyls such as vinyl acetate and vinyl propionate; (meth) acrylate monomers having a hydroxyl group, such as 2 -Hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2- N- (hydroxyalkyl) (meth) acrylamide such as hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, hydroxyalkyl vinyl ethers such as 2- (or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monos having a hydroxyl group Mer, for example, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, 2- (or 3- or 4-) hydroxybutyl allyl ether, Hydroxyl group-containing compounds such as ethylenically unsaturated monomers obtained by adding alkylene oxide and / or lactone to (meth) acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether; vinyl Sulfonic acid-containing compounds such as sulfonic acid, acrylonitrile t-butylsulfonic acid, ethylenically unsaturated double bond-containing compounds having a betaine structure; N, N-dimethylaminoethyl (meth) acrylate (Meth) acrylates having a tertiary amino group such as N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate; N, N -Tertiary amino groups such as dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide (Meth) acrylamide;

  Other monomers can be used alone or in combination of two or more.

(Synthesis of α-olefin copolymer having acidic group)
The α-olefin copolymer having an acidic group is synthesized by radical polymerization of an α-olefin and an acidic group-containing monomer. The radical polymerization can be arbitrarily selected from solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like, and solution polymerization and bulk polymerization are preferable.
The synthesis method in the solution polymerization is, for example, polymerization using an α-olefin and an acidic group-containing monomer, a polymerization initiator, an organic solvent, and, if necessary, a chain transfer agent. If no organic solvent is used in the reaction, bulk polymerization occurs.
In this specification, when maleic anhydride is used as the acidic group-containing monomer, an alternating polymer of α-olefin units and maleic anhydride units is easily formed. When (meth) acrylic acid is used as the product of the reaction, an α-olefin unit, (meth) acrylic acid, and a random copolymer are easily formed. Commercially available resins can also be used. For example, Diacarna M30 (manufactured by Mitsubishi Chemical Corporation), Ceramer series (manufactured by Baker Petrolite) and the like can be mentioned. Furthermore, these resins can be arbitrarily modified.

  In the synthesis, the molar ratio of α-olefin (O) and acidic group-containing monomer (M) is preferably O / M = 30/70 to 99/1, more preferably 40/60 to 95/5, 45 / 55 to 80/20 is more preferable. When an appropriate amount of the α-olefin (O) and the acidic group-containing monomer (M) are used, the dispersion stability of the coated pigment is further improved.

  The polymerization initiator is preferably an azo compound or a peroxide. Examples of the azo compound include azobisisobutyronitrile, azobis 2,4-dimethylvaleronitrile, and the like. Examples of the peroxide include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t- And butyl peroxy-2-ethylhexanoate.

  The acid value of the α-olefin copolymer having an acidic group is preferably 5 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, and still more preferably 30 to 160 mgKOH / g. Most preferably, it is 50-160 mgKOH / g. When the acid value is adjusted to an appropriate range, the dispersibility of the coated pigment is further improved.

  The weight average molecular weight of the α-olefin copolymer having an acidic group is preferably 1,000 to 50,000, and more preferably 1,000 to 35,000. When the weight average molecular weight is adjusted to an appropriate range, the dispersibility is further improved. Moreover, it is easy to adjust the viscosity of the pigment aqueous dispersion to an appropriate range.

(Α-olefin copolymer having side chain and acidic group)
In this specification, when the alpha olefin copolymer which has a side chain and an acidic group is used, the dispersibility of a coating pigment will improve more and it can suppress a coarse particle more. Moreover, the dispersion stability of the pigment aqueous dispersion is further improved.

The side chain can be formed, for example, by reacting a compound having a reactive functional group (hereinafter referred to as a reactive functional group) with the acidic group. In such a case, the acid group is preferably an acid anhydride group or a carboxyl group, and more preferably an acid anhydride group. When an acid anhydride group is used, an unreacted carboxyl group that does not contribute to side chain formation contributes to an improvement in hydrophilicity of the coated pigment. Examples of the reactive functional group include a hydroxyl group and an amino group.
Another side chain forming method can be formed, for example, by copolymerizing a macromonomer having a large molecular weight when synthesizing an α-olefin copolymer having an acidic group. Needless to say, the formation of side chains is not limited to these methods. A side chain is a structure derived from an acid group and another compound, or other monomer.

  The acid value and weight average molecular weight of the α-olefin copolymer having a side chain and an acidic group are the same as those already described.

  Examples of the partial structure of the side chain of the α-olefin copolymer having a side chain and an acidic group include structures represented by general formulas (1) to (5). In addition, the monovalent bond in the following structure is bonded to the acidic group —C (O) — in the α-olefin copolymer. The side chain is formed by a known reaction method.

[一般式（１）中、Ｒ₁は置換されているＣ₁〜Ｃ₃₀のアルキル基、置換されていてもよい脂環式構造、置換されていてもよいフェニル基を表す] Structure represented by general formula (1)

[In General Formula (1), R ₁ represents a substituted C _{1 to} C ₃₀ alkyl group, an optionally substituted alicyclic structure, or an optionally substituted phenyl group]

  The structure represented by the general formula (1) can be formed, for example, by a reaction between an acidic group and a hydroxyl group-containing compound. Examples of the hydroxyl group-containing compound include α-oxybutyric acid, 12-hydroxystearic acid, lactic acid, glycolic acid, cyclohexyl alcohol, and benzyl alcohol.

Structure represented by general formula (2)

[In General Formula (2), R ₁ and R ₂ are each a hydrogen atom, an optionally substituted C _{1 to} C ₃₀ alkyl group, an optionally substituted alicyclic structure, and optionally substituted. Represents a phenyl group. However, when _one of R ₁ and R ₂ is a hydrogen atom, the other is not a hydrogen atom. ]

  The structure represented by the general formula (1) can be formed, for example, by a reaction between an acidic group and an amino group-containing compound. An amino group-containing compound is a compound having one amino group, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, lauryl. Amine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o-toluidine, 2-ethylaniline, 2-fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2, Examples include 3-dimethylaniline, 5-aminoindane, aspartic acid, glutamic acid, and γ-aminobutyric acid.

Structure represented by general formula (3)

[In General Formula (3), R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms, and A ¹ O and A ² O independently represents an alkyleneoxy group having 1 to 6 carbon atoms, m and n represent an average number of added moles of the alkyleneoxy group, an integer of 0 to 100, and m + n is 1 or more. is there. ]

Structure represented by general formula (4)

[In General Formula (4), R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms, and A ¹ O and A ² O each independently represents an alkyleneoxy group having 1 to 6 carbon atoms, m and n represent the average number of added moles of the alkyleneoxy group, are integers of 0 to 100, and satisfy m + n = 1 or more. . ]

In the general formulas (3) and (4), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably a methyl group. The smaller the carbon number of R _1, the more the affinity with water is increased and the formation of coarse particles is difficult when forming an aqueous pigment dispersion using a coated pigment.
A ¹ O and A ² O are preferably an alkyleneoxy group having 1 to 6 carbon atoms. The alkyleneoxy group represented by A ¹ O and A ² O tends to reduce coarse particles when obtaining a pigment aqueous dispersion by relaxing the aggregation of the pigment when preparing a coated pigment. The carbon number of A ¹ O and A ² O is similar to R _1, and the smaller the carbon number, the higher the affinity with water and the easier to reduce coarse particles. Further, A ¹ O and A ² O act as a steric hindrance group, so that the dispersion stability of the coated pigment is improved. A ¹ O and A ² O have a high affinity with water, and ethyleneoxy group and propyleneoxy group are in the aspect of easily achieving both the reduction of coarse particles and the stability of the aqueous dispersion when obtaining an aqueous pigment dispersion. preferable.

In the general formulas (3) and (4), m + n is 1 or more and 100 or less. m + n
Is preferably 4 or more, more preferably 9 or more. Further, the upper limit of m + n is preferably 30 or less. When m + n is adjusted to an appropriate range, dispersion stability is improved.

  The structure represented by the general formula (3) can be formed, for example, by a reaction between an acidic group and an alkyleneoxy group-containing compound.

  Examples of the alkyleneoxy group-containing compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether. Oxyalkylene alkyl ethers. Of these, polyoxyethylene monomethyl ether is preferred. Commercial products of the alkyleneoxy group-containing compound include, for example, UNIOX M-400, M-550, and M-1000 (manufactured by NOF Corporation).

  The structure represented by the general formula (4) can be formed, for example, by a reaction between an acidic group and a polyalkylenediol monoester.

  Examples of the polyalkylenediol monoester include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, and the like. Among these, polyoxyethylene monolaurate is preferable. Examples of commercially available polyalkylenediol monoesters include Nonion L-2, L-4, S-4, and O-4 (manufactured by NOF Corporation).

Structure represented by general formula (5)

[In General Formula (5), R ₁ is substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic structure which may be substituted, or an alkyl group having 1 to 9 carbon atoms. R ₂ represents a hydrogen atom, a C _{1 to} C ₃₀ alkyl group, an optionally substituted alicyclic structure, an optionally substituted phenyl group, (poly) alkylene oxide, (poly ) Represents a monoalkyl ether of alkylene oxide, an alkyl ester of (poly) alkylene oxide, A ¹ O and A ² O each independently represent an alkyleneoxy group having 1 to 6 carbon atoms, and m and n are The average addition mole number of an alkyleneoxy group is an integer of 0 to 100, and m + n satisfies 1 or more. ]

In the general formula (5), R _{1 is} substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic structure which may be substituted, or an alkyl group having 1 to 9 carbon atoms. It may be a phenyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group. The smaller the carbon number of R _1, the higher the affinity with water in obtaining a pigment aqueous dispersion, and the easier it is to reduce coarse particles. A ¹ O and A ² O are preferably an alkyleneoxy group having 1 to 6 carbon atoms. The alkyleneoxy group represented by A ¹ O and A ² O tends to reduce coarse particles when an aqueous pigment dispersion is obtained by relaxing the aggregation of the pigment during the production of the pigment. . The carbon number of A ¹ O and A ² O is similar to R _1, and the smaller the carbon number, the higher the affinity with water and the easier to reduce coarse particles. In addition, in an ink, a toner manufacturing process, and a paint using an aqueous pigment dispersion, an alkyleneoxy group spreads in the ink and acts as a steric hindrance group, contributing to stabilization of pigment dispersion. In particular, an ethyleneoxy group and a propyleneoxy group are preferable. If these are high, the affinity with water is high, and it is easy to achieve both the reduction of coarse particles and the stability of the aqueous dispersion when obtaining an aqueous pigment dispersion.
R ₂ is a hydrogen atom, a C ₁ -C ₃₀ alkyl group, an optionally substituted alicyclic structure, an optionally substituted phenyl group, (poly) alkylene oxide, (poly) alkylene oxide monoalkyl ether , Alkyl esters of (poly) alkylene oxides. Particularly preferred are a hydrogen atom, (poly) alkylene oxide, monoalkyl ether of (poly) alkylene oxide, and alkyl ester of (poly) alkylene oxide. More preferred is a hydrogen atom.

  The structure represented by the general formula (5) can be formed, for example, by a reaction between an acidic group and a polyalkylenediol monoamino ether. Examples of the polyalkylene diol monoamino ether include polyoxyethylene monomethyl ether amine, polyoxypropylene monomethyl ether amine, and polyoxyethylene / polyoxypropylene copolymer monomethyl ether amine. Examples of commercially available products include M-600, M-1000, M-2005, M-2070 of JEFFAMINE M series (manufactured by HUNTSMAN).

  The side chain can be used alone or in combination of two or more.

The coated pigment of the present specification is selected from the group consisting of a styrene- (meth) acrylic resin, a styrene- (anhydrous) maleic acid resin, and a (meth) acrylic resin in addition to the α-olefin copolymer having an acidic group. 1 or more types can be included.
These resins are known resins. For example, in the case of styrene (meth) acrylic resins, Joncryl series (made by BASF) represented by Joncryl 690, 67, X-1 (Seiko PMC) SMA resin series (manufactured by Cray Valley) represented by SMA 1440, SMA 2625, SMA 3840, etc. for styrene (anhydrous) maleic resin, and VS-1057, X-310, TS- for (meth) acrylic resin. 1316 (manufactured by Seiko PMC) or the like.

(Pigment before coating (X))
The pigment (X) before coating is an inorganic pigment or an organic pigment that can be used as a colorant. The pigment (X) before coating means that it is not coated with an α-olefin copolymer having an acidic group and another resin, and therefore does not prevent pretreatment using other compounds.

  The inorganic pigment is preferably a metal compound such as a metal oxide or a metal complex salt. Examples of the metal oxide include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides thereof.

Examples of organic pigments include dyed lake pigments, azo pigments, phthalocyanine pigments, polycyclic pigments, and other pigments.
For example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 32, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 147, 148, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 266, 269, 270 272,279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,231, C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37, 58, 62, 63,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

(Coating pigment)
In the coated pigment of the present specification, the surface of the pigment (X) before coating is coated with an α-olefin copolymer having an acidic group of the resin. The resin coating amount of the coating pigment is preferably 10 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the pigment (X) before coating. The pigment (X) before coating may be coated with an appropriate amount of resin, and the area to be coated is not limited as long as the problem can be solved. In the present specification, it is preferable to coat the entire surface of the pigment (X) before coating.
Since the coated pigment is coated with a predetermined amount of resin, it is difficult to produce coarse particles in which pigments aggregate in the subsequent dispersion step of the aqueous pigment dispersion, and the pigment can be easily dispersed.

(Measurement of resin coating amount of coated pigment)
A method for measuring the resin coating amount will be described. For example, a coating pigment is added to 100 g of ion-exchanged water so that the concentration of the pigment (X) is 15% by mass, and potassium hydroxide equivalent to the acid value of the resin treated when the pigment is produced is added. Dissolve. The liquid temperature is adjusted to 70 ° C. and stirred for 2 hours to prepare a pigment dispersion. Next, the pigment dispersion is centrifuged for 20 hours at 70,000 rpm by a centrifugal separator, and the supernatant liquid is collected all over, and further, the pigment is precipitated for 20 hours at 70,000 rpm by a centrifugal separator. Next, the whole supernatant of the solution is collected, the residue is dried at 150 ° C. for 20 minutes, and the non-volatile content is calculated. Based on this numerical value, the mass of the resin released from the coated pigment is determined, and the mass of the resin coated with the pigment is calculated from the mass of the resin used when the coated pigment is produced. Thereby, the resin coating amount with respect to 100 parts by mass of the pigment (X) before coating is calculated. The same calculation is performed when a resin other than an α-olefin copolymer having an acidic group is used in combination.

  The coated pigment of the present specification can be used for various purposes as a colorant, and is preferably used for, for example, inkjet ink, toner for developing an electrostatic image, paint, printing ink, and stationery. Since the coated pigment has moderate hydrophilicity, for example, when used for inkjet applications, it is difficult to impair the water resistance of the printed matter. However, when the hydrophilicity is excessively increased, there is a phenomenon that the water resistance of the printed matter is lowered in the inkjet application.

(Method for producing coated pigment and aqueous pigment dispersion)
The method for producing a coated pigment according to the present specification comprises mixing a water-soluble organic solvent, a water-soluble inorganic salt, a pigment (X) before coating and an α-olefin copolymer having an acidic group with a kneader, and then the pigment before coating. (X) The α-olefin copolymer having an acidic group is coated with 10 to 50 parts by mass with respect to 100 parts by mass to remove the water-soluble inorganic salt and the water-soluble organic solvent.

Moreover, the method of manufacturing from coating pigment manufacture to pigment aqueous dispersion performs the following process one by one.
Step 1: α-olefin copolymer having an acidic group, pigment (X) before coating, water-soluble inorganic salt, and a mixture containing a water-soluble organic solvent are kneaded and 100 parts by mass of pigment (X) before coating In contrast, a step of coating with 10 to 50 parts by mass of an α-olefin copolymer having an acidic group,
Step 2: removing the water-soluble inorganic salt and the water-soluble organic solvent,
Step 3: adding a basic compound to neutralize the acidic group,
Step 4: adding a crosslinking agent to react the acidic group with the crosslinking agent,

  The method for producing a coated pigment is, for example, adding pigment (X) before coating (hereinafter referred to as pigment (X)), a water-soluble inorganic salt, a water-soluble organic solvent, and a resin, and kneading and kneading the pigment (X). It is preferable to coat the surface with a resin. The production method is preferably, for example, a kneading step by salt milling. Specifically, Step 1 and Step 2 above.

(Process 1)
In the kneading method, at least a mixture containing the pigment (X), the water-soluble inorganic salt, the water-soluble organic solvent and the resin is mixed (kneaded) with a kneader.
Examples of the kneader include a kneader, a trimix, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, a vertical sand mill, and an annular bead mill. Among these, a kneader and a trimix are preferable.
When the kneader is used, the kneaded product can be kneaded with high viscosity, and the coating of the pigment (X) and the crushing / dispersing of the coarse particles of the pigment (X) proceed efficiently.
The kneading conditions can be appropriately adjusted according to the type of pigment (X), the amount of resin coating, and the like. It is preferable to heat at the time of kneading. The heating temperature is preferably set to a temperature equal to or higher than the melting point of the resin. Thereby, the pigment (X) can be efficiently coated. The upper limit temperature for heating can be arbitrarily set as long as the resin does not thermally decompose.
The water-soluble inorganic salt contributes to the dispersion of the aggregated pigment (X) before the process, and further grinds the pigment (X). In the salt milling process (step 1), the pigment (X) is crushed using the hardness of the water-soluble inorganic salt. By performing the salt milling treatment, the coated pigment has a fine average primary particle size. In addition, the coated pigment easily obtains a sharp particle size distribution with a narrow average primary particle size distribution.

(Water-soluble inorganic salt)
Examples of the water-soluble inorganic salt include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Among these, low-priced sodium chloride is preferable. The amount of the water-soluble inorganic salt used is preferably about 50 to 2,000 parts by mass and more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment (X). When an appropriate amount of the water-soluble inorganic salt is used, the coating efficiency of the pigment (X) and the production efficiency of the coated pigment are further improved.

(Water-soluble organic solvent)
The water-soluble organic solvent is preferably a solvent that is dissolved or mixed in water. Water-soluble organic solvents are, for example, glycerin, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , Dipropylene glycol monomethyl ether, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionine, tributyrin and 2-butyl-2-ethyl-1 , 3-propanediol. The use amount of the water-soluble organic solvent is preferably 5 to 1,000 parts by mass, and more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment (X).

(Process 2)
In step 2, the mixture is taken out from the kneader, and water is added to the mixture to stir to obtain a suspension containing the coated pigment. The amount of water may be an amount sufficient to obtain a suspension. For example, water having a mass of 10 to 10,000 times the total mass used in step (1) is added and mixed and stirred. When charging, it can be heated as necessary. Heating is preferably performed at a temperature of 25 to 90 ° C., for example. The solution is filtered by mixing and stirring, and the filtrate is removed to remove the water-soluble organic solvent and the water-soluble inorganic salt. Thereby, a coating pigment can be obtained. In addition, it is preferable to use the water which suppressed the ion derived from inorganic substances, such as distilled water, ion-exchange water, and purified water.

  Since the coated pigment obtained in the above step 2 contains water, a step of further removing water can be performed. Examples of the step include a drying process. The drying conditions are, for example, a method of drying at a temperature of 80 to 120 ° C. under normal pressure. Or it is the method of drying at the temperature of 25-80 degreeC under pressure reduction. Examples of the drying processing apparatus include a spray drying apparatus and a freeze drying apparatus. A pulverization process can be performed simultaneously with the drying process or after the drying process.

(Pigment aqueous dispersion)
In the present specification, the aqueous pigment dispersion preferably contains a coating pigment, water, and a basic compound. For example, it is produced by neutralizing the acidic group of the resin with a basic compound as in Step 3 above.
In the aqueous pigment dispersion, for example, an appropriate amount of a basic compound is added to water and dissolved in water. The coated pigment is then added and made by stirring while warming.
The addition amount of the basic compound is preferably about 50 to 120% of the mass necessary for neutralization, for example, with respect to the acid value of the resin. Stirring is, for example, a high-speed mixer, a homogenizer, a planetary mixer, a trimix, a kneader, an extruder, a horizontal sand mill, a vertical sand mill or / and an annula type bead mill, a paint shaker, a ball mill, etc. Machine, 2-roll mill, 3-roll mill and the like.

(Basic compound)
The basic compound is preferably an inorganic base or an organic base that is soluble in water. Examples of the inorganic base include potassium hydroxide, sodium hydroxide, sodium bicarbonate, sodium carbonate and the like. The organic base is preferably a primary to tertiary amine, for example. Examples of the organic base include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and other alkylamines; aminoethanol, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine and the like And an amine having a nonionic group such as methoxypoly (oxyethylene / oxypropylene) -2-propylamine.

  Moreover, the pigment aqueous dispersion of this specification can contain a crosslinking agent further. In the manufacturing process, the process 4 can be performed after the process 3. As a result, the acidic groups are cross-linked and the coating of the coated pigment becomes stronger. This further improves the storage stability and pigment dispersion stability of the pigment aqueous dispersion. As a cause of this, the inventors bonded the pigment-coated resins together so that the surface of the coated pigment is bound in a network. It is presumed that an aggregate of coated pigments is formed. As a result, when there is some change in the dispersion medium (water or a mixed solvent containing water) in which the coating pigment is dispersed, and the dissolution equilibrium of the resin covering the pigment changes, the resin is difficult to dissolve in the dispersion medium. It is assumed that storage stability and pigment dispersion stability are obtained. According to another consideration, it is assumed that the crosslinking introduces a steric hindrance site to the resin coated with the pigment, and this steric hindrance site contributes to storage stability and pigment dispersion stability.

  In step 4, after the step 3, the acidic group and the crosslinking agent are reacted by further adding and stirring the crosslinking agent. The stirring device can be appropriately selected from known devices in addition to the devices already mentioned. It can be heated during stirring. Moreover, after completion | finish of crosslinking reaction, an acid can be added as needed and the pH of a solution can be adjusted. Examples of the acid include inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as citric acid. Centrifugation treatment and filtration treatment can be appropriately performed after the crosslinking is completed.

(Crosslinking agent)
The crosslinking agent is a compound having two or more functional groups capable of reacting with an acidic group. In consideration of crosslinking, the acidic group is preferably a carboxyl group. For example, the crosslinking agent is preferably one or more selected from the group consisting of isocyanate, aziridine, carbodiimide, oxetane, oxazoline, and epoxy, and more preferably epoxy. If it is an epoxy, it is easy to obtain the dispersion stability of the pigment aqueous dispersion after crosslinking and the ink using the dispersion. The blending amount of the crosslinking agent is preferably an amount capable of reacting with an acidic group (for example, carboxyl group) of the coated pigment in an amount of 1 to 100%, and more preferably 1 to 90%. When an appropriate amount of a crosslinking agent is used, a sufficient crosslinking effect is easily obtained. The molecular weight (formula) of the crosslinking agent is preferably 100 to 2000, more preferably 120 to 1500, and still more preferably 150 to 1000. The number of functional groups of the crosslinking agent is about 2 to 6 in terms of reaction efficiency.

  Isocyanates include, for example, aliphatic diisocyanates such as xamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; aromatic diisocyanates such as tolylene-2,4-diisocyanate and phenylene diisocyanate; alicyclic diisocyanates; aromatic triisocyanates Modified products such as urethane modified products thereof. The isocyanate group-terminated prepolymer can be synthesized by reacting polyisocyanate or its urethane-modified product with a molecular weight polyol or the like.

  Aziridine may have an aziridine group, for example, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridine). Carboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2 , 2′-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethane tri-β-aziridinylpropionate, tris -2,4,6- (1-aziridinyl) -1,3,5-triazine, 4,4'-bis (ethyleneiminoca) And rubonylamino) diphenylmethane.

  The carbodiimide only needs to have a carbodiimide group, and examples thereof include high molecular weight polycarbodiimide generated by decarboxylation condensation reaction of a diisocyanate compound in the presence of a carbodiimidization catalyst. Examples of such high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series.

  The oxetane may have an oxetane group, for example, 4,4 ′-(3-ethyloxetane-3-ylmethyloxymethyl) biphenyl (OXBP), 3-ethyl-3-hydroxymethyloxetane (EHO), 1 , 4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene (XDO), di [1-ethyl (3-oxetanyl)] methyl ether (DOX), di [1-ethyl (3-oxetanyl) )] Methyl ether (DOE), 1,6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane (HDB), 9,9-bis [2-methyl-4- {2- (3-oxetanyl)] } Butoxyphenyl] fluorene, 9,9-bis [4- [2- {2- (3-oxetanyl)} butoxy] ethoxyphenyl] fluorene, and the like.

  The oxazoline only needs to have an oxazoline group. For example, bisoxazoline compounds such as 2,2′-bis (2-oxazoline), 1,3-phenylenebisoxazoline, 1,3-benzobisoxazoline, The compound which has the terminal oxazoline group obtained by making it react with basic carboxylic acid is mentioned.

  The epoxy only needs to have an epoxy group. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, Examples include polyglycidyl ethers such as methylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, and hydrogenated bisphenol A type diglycidyl ether. Among these, ethylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, and the like are preferable.

  A crosslinking agent can be used individually or in combination of 2 or more types.

  It is also preferable that the crosslinking agent has an appropriate water solubility in order to increase the crosslinking efficiency. For example, when the cross-linking agent is dissolved in 100 g of water at 25 ° C., the water solubility is preferably 0.1 to 50 g, more preferably 0.2 to 40 g, and more preferably 0.5 to 30 g. . When the coated pigment is crosslinked, the basic compound used is preferably an inorganic base in terms of crosslinking efficiency.

  Aqueous pigment dispersions can be used in addition to crosslinking agents, water-soluble organic solvents, preservatives, leveling agents, surface tension modifiers, antifoaming agents, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric Surfactants such as surfactants, water-soluble resins, emulsions and the like can be included.

  The volume average particle diameter (D50) of the pigment dispersion is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, and further preferably 90 nm or less. Further, the lower limit of the volume average particle diameter (D50) is preferably 30 nm or more. When the volume average particle diameter (D50) is adjusted to an appropriate range, the ink containing the coating pigment can form a printed matter that is clear and has coloring power and good color reproducibility. Further, the volume average particle diameter (D99) of the pigment dispersion is preferably 500 nm or less. For example, when used for toner applications, the toner particle size is generally about 1 to 5 μm. The particle diameter of the coating pigment needs to be appropriately smaller than the particle diameter of the toner, but if it is 500 nm or less, it is sufficient for the particle diameter of the toner.

(Ink for inkjet printing)
The ink jet printing ink of the present specification preferably includes a coating pigment, an aqueous pigment dispersion, and an aqueous pigment dispersion (crosslinked pigment dispersion) treated with the above-described crosslinking agent. It is preferable that the inkjet printing ink of this specification contains water, a water-soluble solvent, surfactant, and resin in addition to this.

The volume average particle diameter (D50) of the inkjet printing ink using the coated pigment of the present specification is preferably 150 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less. When the volume average particle diameter (D50) is 100 nm or less, the ejection stability from the inkjet nozzle is improved, and the saturation and image density (OD value) of the image are also improved.
1-15 mass% is preferable as pigment (X) in 100 mass% of inkjet printing inks, and, as for content of a coating pigment, 2-10 mass% is more preferable. When the content is less than 1% by mass, the color developability and image density of the ink may be extremely low. When the content exceeds 15% by mass, the ink is thickened and the discharge property is deteriorated. In some cases, it is also not economical.

(Water-soluble solvent)
Water-soluble solvents include polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other water-soluble solvents in addition to the polyhydric alcohols already described. Is mentioned. Including a water-soluble solvent prevents drying and improves dispersion stability.

  Examples of the polyhydric alcohol include triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,3. -Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 3-methyl-1,3-butanediol, trimethylolethane, trimethylolpropane, 1,2,6-hexane Triol, 1,2,4-butanetriol, 1,2,3 Butanetriol, petriol, 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-methyl 2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2-diol, etc. Can be mentioned. Among these, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, and 1,2-heptanediol are preferred.

Examples of the polyhydric alcohol alkyl ether include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether and the like.
Examples of the polyhydric alcohol aryl ether include ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, tetraethylene glycol chlorophenyl ether, ethylene glycol monobenzyl ether, and ethylene glycol monoallyl ether.

  Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, and γ-butyrolactone. . Examples of the amide include formamide, N-methylformamide, and N, N-dimethylformamide. Examples of the amine include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine. Examples of the sulfur-containing compound include dimethyl sulfoxide, sulfolane, and thiodiethanol.

  Other water-soluble solvents are preferably saccharides. Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Examples of the saccharide include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like. Here, the polysaccharide means a saccharide in a broad sense and includes substances widely present in nature such as α-cyclodextrin and cellulose. Examples of derivatives of these saccharides include reducing sugars of the saccharides (for example, sugar alcohol [general formula: HOCH2 (CHOH) nCH2OH (where n is an integer of 2 to 5)), oxidized sugar (For example, aldonic acid, uronic acid, etc.), amino acids, thioic acid, etc. Among these, sugar alcohols are preferable, and maltitol and sorbit are more preferable.

(resin)
The resin is preferably a water-soluble resin or a water-dispersible resin (emulsion) in terms of form. In terms of the material, the resin includes, for example, a condensation synthetic resin, an addition synthetic resin, a natural polymer compound, and the like. Examples of the condensed synthetic resin include polyester resins, polyurethane resins, polyepoxy resins, polyamide resins, polyether resins, and silicon resins. Examples of the addition type synthetic resin include polyolefin resin, polystyrene resin, polyvinyl alcohol resin, polyvinyl ester resin, polyacrylic resin, and unsaturated carboxylic acid resin. Examples of the natural polymer compound include cellulose, rosin, and natural rubber.

(PH adjuster)
Examples of the pH adjuster include alcohol amine, alkali metal hydroxide, ammonium hydroxide, phosphonium hydroxide, alkali metal carbonate, and the like.

Examples of the alcohol amine include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

(Other)
The other components are not particularly limited and can be appropriately selected as necessary. For example, antiseptic / antifungal agents, chelating reagents, antioxidants, ultraviolet absorbers, oxygen absorbers, light stabilizers, Etc.

(Antiseptic and antifungal agent)
Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

(Chelating reagent)
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

(anti-rust)
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole.

(Antioxidant)
Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidant (including hindered phenolic antioxidant) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propio Nate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and the like.

Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl β. , Β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, trinonylphenyl phosphite, and the like.

(UV absorber)
Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II), and the like.

(Production of inkjet printing ink)
The ink-jet printing ink may be prepared by mixing the materials already described and using the mixing device already described.

<Toner for electrostatic image development>
The electrostatic image developing toner of the present specification preferably contains a coated pigment and an aqueous pigment dispersion. The electrostatic image developing toner of the present specification further contains a binder resin, and if necessary, a release agent, a charge control agent, a lubricant, a fluidity improver, an abrasive, a conductivity imparting agent, and an image peeling prevention. Agents and the like.

(Binder resin)
As the binder resin, it is preferable to use a colorless / transparent or white to light color resin that does not inhibit the hue of the coating pigment.

The binder resin is, for example, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, or a substituted product thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene- Vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Styrene copolymers such as styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, Crosslinked styrene copolymer Polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, Polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be mentioned. Among these, polyester resins and styrene copolymers are preferable.
As for the compounding quantity of binder resin, 900-5000 mass parts is preferable with respect to 100 mass parts of coating pigments.

  The charge control agent is used to control the charge of the toner particles. As the charge control agent, a positive charge control agent or a negative charge control agent is used depending on the polarity of the toner particles.

  The positive charge control agent is a quaternary ammonium salt compound (for example, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylbenzylammonium tetrafluoroborate), a quaternary ammonium salt, an organic tin oxide (for example, dibutyltin oxide). , Dioctyltin oxide, dicyclohexyltin oxide), diorganotin borate (dibutyltin borate, dioctyltin borate, dicyclohexyltin borate), polymers having amino groups, and the like.

  The negative charge control agent includes aromatic hydroxycarboxylic acid zinc salt, calcium salt, chromium salt, aryloxycarboxylic acid divalent or trivalent metal salt such as salicylic acid or salicylic acid derivative, metal chelate (complex), fatty acid soap And naphthenic acid metal salts.

  0.1-10 mass parts is preferable with respect to 100 mass parts of binder resin, and, as for the usage-amount of a charge control agent, 0.5-8 mass parts is more preferable.

The fluidity improver is a fine powder that functions not only to impart fluidity to the toner particles but also to impart chargeability to the toner particles. Examples of the fluidity improver include silica, alumina, titania, magnesia, amorphous silicon-aluminum cooxide, and amorphous silicon-titanium cooxide.
The fluidity improver is preferably coated with a silane compound, silicone oil, silane coupling agent or the like on the surface thereof. As a result, the surface of the toner particles can be made hydrophobic so that the chargeability can be easily controlled.

  In this specification, a carrier can be used instead of the charge control agent. The carrier is preferably particles used in a two-component dry development toner. Carrier is ferromagnetic metal such as iron powder or alloy powder of ferromagnetic metal, metal oxide such as iron oxide, magnetism such as ferrite powder composed of elements such as nickel, copper, zinc, magnesium, barium, magnetite powder, etc. Examples thereof include a magnetic powder carrier made of powder, a magnetic powder resin-coated carrier in which these magnetic powders are coated with a resin, a binder carrier made of magnetic powder and a binder resin, and glass beads with or without resin coating. The average particle size of the carrier is preferably 15 to 100 μm, and more preferably 20 to 80 μm.

  Examples of the coating resin for the magnetic powder resin-coated carrier include silicon-containing resins such as polyethylene and silicone resin, fluorine-containing resins, styrene resins, acrylic resins, styrene-acrylic resins, polyvinyl acetate, cellulose derivatives, Maleic acid resin, epoxy resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinylidene bromide, polycarbonate, polyester, polypropylene, phenol resin, polyvinyl alcohol, fumarate ester resin, polyacrylonitrile, polyvinyl ether, chloroprene rubber , Acetal resin, ketone resin, xylene resin, butadiene rubber, styrene-butadiene copolymer, polyurethane, polyamide resin, ionomer resin, polyphenylene sulfide resin, etc. That. Among these, fluorine-containing resins and silicon-containing resins are particularly preferable because the formation of spent toner is small. This magnetic powder resin coated carrier includes conductive fine particles (carbon black, conductive metal oxide, metal powder), inorganic fillers (silica, silicon nitride, boron nitride, alumina, zirconia, silicon carbide, boron carbide, oxidized (Titanium, clay, talc, glass fiber), the charge control agent exemplified above, and the like may be contained as necessary. The resin coating thickness on the carrier core material is preferably about 0.1 to 5 μm.

  A known toner production method can be used for producing an electrostatic charge image developing toner (hereinafter referred to as toner). The toner production methods are roughly classified into two types: a pulverization method obtained through kneading and pulverization steps, and a polymerization method obtained by chemical polymerization. In the case of the pulverization method, for example, the materials described above are sufficiently mixed by a mixer such as a ball mill or a Henschel mixer, and then kneaded well using a hot kneader such as a hot roll kneader, a uniaxial or biaxial extruder. Then, after cooling and solidification, there is a method of coarsely pulverizing mechanically using a pulverizer such as a hammer mill, and then finely pulverizing with a jet mill, mechanical pulverizer or the like, followed by classification.

  In addition, in order to uniformly disperse and blend the coating pigment in the binder resin, the coating pigment and the binder resin are mixed in advance to produce a colorant dispersion (conc) in which the colorant component is dispersed in the binder resin. Then, it is preferable to add the material constituting the remaining toner and then go through a melting and kneading step. The colorant dispersion (conc) comprises at least the magenta colorant of the present invention and a binder resin. The colorant content in the colorant dispersion (conc) is preferably 10 to 70% by mass.

In the case of a toner obtained by a polymerization method, the use of the pigment component in the form of a crosslinked pigment dispersion further improves the dispersibility of the pigment during the agglomeration step, stabilizes the charge amount, and reduces fog. An image can be obtained.

On the other hand, in the case of the polymerization method, a method for producing toner by the so-called microcapsule method in which other toner constituent materials are dispersed in a binder resin solution and then spray-dried, and a predetermined material as a monomer for forming the binder resin And a method of obtaining toner by carrying out emulsion or suspension polymerization. In the emulsion polymerization method, resin fine particles having a particle size of submicron are associated with an internal additive such as a pigment component and wax that have been dispersed in water in advance in an agglomeration step to obtain a particle size of a desired toner size. In the suspension polymerization method, necessary materials such as a polymerization initiator, a pigment component, a release agent (wax), and a charge control agent are dispersed in a monomer and heated to perform polymerization. The pigment component dispersed in water in advance can be produced by the same method as the above-described method for producing the pigment dispersion.

It is preferable to use the toner base particles thus obtained by sufficiently mixing the external additive with a mixer such as a Henschel mixer.

In the present specification, the toner preferably has a weight average particle diameter of 3 to 15 μm, and more preferably 5 to 10 μm.
The weight average particle size and particle size distribution of the toner can be measured using, for example, a Coulter counter (Multisizer 3).

  In the present specification, the toner may further contain a release agent, a charge control agent, a lubricant, an abrasive, a conductivity imparting agent, an image peeling preventing agent, and the like.

<Coating composition>
The coating composition of the present specification preferably contains a coating pigment and an aqueous pigment dispersion, and more preferably contains a binder resin.

(Binder resin)
The binder resin is a resin containing a crosslinkable functional group. The binder resin is preferably, for example, an acrylic resin, a styrene / acrylic resin, a polyester resin, an alkyd resin, a fluororesin, a urethane resin, or a silicon-containing resin.
Moreover, as a crosslinking agent of binder resin, a melamine resin, a urea resin, a polyisocyanate compound, a block polyisocyanate compound, an epoxy compound etc. are mentioned, for example.
Among these, a combination of an acrylic resin and a melamine resin is preferable.

  The coating composition of this specification can mix | blend suitably a pigment dispersant, an antisettling agent, a curing catalyst, an antifoamer, antioxidant, a ultraviolet absorber, a surface conditioning agent, an extender, etc. as needed. Moreover, water or an organic solvent can be contained appropriately.

  The coating composition can be prepared by mixing and dispersing the materials already described.

<Inks for flexographic printing>
The flexographic ink of the present specification (hereinafter referred to as ink) preferably contains a coating pigment and an aqueous pigment dispersion, and may further contain a binder resin, a solvent, a crosslinking agent and the like.

(resin)
Examples of the resin include an acrylic resin and a urethane resin.
The acrylic resin functions as a dispersant. Examples of the acrylic resin include a styrene / acrylic resin, an acrylic / maleic acid resin, and an acrylic / styrene / maleic acid resin in addition to a copolymer of acrylic monomers.

  The acid value of the acrylic resin is preferably 40 to 180 mgKOH / g, and more preferably 40 to 100 mgKOH / g. When the acid value is appropriate, the re-solubility of the ink is further improved, and the compatibility between the materials is further improved.

The weight average molecular weight of the acrylic resin is preferably 200,000 to 800,000. Also,
The glass transition temperature (Tg) of the acrylic resin is preferably -30 ° C to 30 ° C.

(Urethane resin)
The urethane resin functions as a binder resin. As the urethane resin, in addition to the urethane resin, a urethane-urea resin can be used. The polyurethane resin preferably has an acid value from the viewpoint of film forming properties, and the acid value is preferably 10 to 50 mgKOH / g.

  As for content of resin contained in ink, 10-40 mass% is preferable in 100 mass% of non volatile matters.

  The ink can be added as required. Examples of the additive include a leveling agent, a wetting agent, a water repellent, an antifoaming agent, a wax such as polyethylene, polypropylene, and polyfluorinated ethylene, and a crosslinking agent.

  Examples of the solvent include water, alcohol, and glycol. Examples of the alcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, and decanol. Glycol is, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monooctyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monopro Ether, propylene glycol monobutyl ether, dipropylene glycol, dipyropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipyropyrene glycol monobutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, tri Examples include propylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, and glycerin.

  The ink can be produced by mixing and dispersing the materials already described.

  The content of the coating pigment is preferably 1 to 50% by mass as the pigment (X) before coating in 100% by mass of the ink. In addition, the viscosity of the ink is preferably 10 mPa · s or more and 1000 mPa · s or less from the viewpoint of preventing the pigment from settling and appropriately dispersing. The viscosity is a viscosity measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “part” is “part by mass”, and “%” is “% by mass”.

(Acid value)
About 1 g of a sample is accurately weighed in an Erlenmeyer flask and dissolved by adding 50 ml of a distilled water / dioxane (weight ratio: distilled water / dioxane = 1/9) mixture. A 0.1 mol / L potassium hydroxide / ethanol solution (titer a) is used for the sample solution by using a potentiometric measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., apparatus name “potentiometric automatic titrator AT-710M”). The amount of potassium hydroxide / ethanol solution (b (mL)) required until the end of titration was measured. The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
However,
S: Sample collection amount (g)
a: Consumption of 0.1 mol / L potassium hydroxide / ethanol solution (ml)
F: Potency of 0.1 mol / L potassium hydroxide / ethanol solution

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) is a polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8320GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of conversion.

(Synthesis of α-olefin copolymer (Q-1) having acidic group)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 46.2 g of 1-hexene and 53.8 g of maleic anhydride were charged as α-olefin, 10 g of xylene was charged into a flask, and the atmosphere was replaced with nitrogen. Heated and stirred at 130 ° C. Thereto, a mixture of peroxide perbutyl O (NOF Corporation) 1.0 g and xylene 20 g was added dropwise over 2 hours with stirring. Thereafter, the mixture was further stirred for 1 hour while maintaining the temperature at 130 ° C., and xylene was concentrated under reduced pressure to completely remove it to obtain a copolymer BQ-1. The resulting copolymer Q-1 had a weight average molecular weight (Mw) of about 10,000 and an acid value of 615.7 mgKOH / g.

(Alpha-olefin copolymer Q-2 to Q-10 having an acidic group)
Except having changed into the raw material and preparation amount which were described in Table 1, it synthesize | combined like (Q-1), and copolymer Q-2 to Q-10 was obtained, respectively. The molecular weight was adjusted appropriately by changing the amount of perbutyl O added. Each weight average molecular weight (Mw) and acid value are as described in Table 1.

(Production of α-olefin copolymer RQ-1 having acidic group)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 32.2 g of copolymer Q-1 and 67.8 g of compound (3) -2 shown in Table 3 were used, and diazabicycloundecene was used as a catalyst. 0.2g was added and it heated at 130 degreeC, stirring. After 1 hour, the temperature was changed to 110 ° C. and held for another hour, and further changed to 90 ° C. and held for 4 hours to carry out an ester reaction. In the general formula (2), R ₁ = methyl group, A ¹ An α-olefin maleic anhydride copolymer RQ-1 having a side chain of O═C ₂ H ₄ O, m = 12, and n = 0 was obtained. The obtained copolymer had a weight average molecular weight (Mw) of about 13,000 and an acid value of 99 mgKOH / g.

(Production of α-olefin copolymers RQ-2 to RQ-19 and RQ-27 to RQ-31 having an acidic group)
Except having changed into the raw material and preparation amount which were described in Tables 2-4, it synthesize | combined similarly to (RQ-1), and copolymer (RQ-2)-(RQ-19), (RQ-27)- (RQ-31) was obtained. Each weight average molecular weight (Mw) and acid value are as having described in Tables 2-4.

(Production of α-olefin copolymer RQ-20 having acidic group)
Add 61.7 g of copolymer Q-5 and 38.3 g of stearylamine to a reaction vessel equipped with a gas inlet tube, thermometer, condenser and stirrer, and react for 5 hours at a reaction temperature of 180 ° C. in a nitrogen stream while stirring. Went. After completion of the reaction, the contents were taken out when heated to obtain an α-olefin copolymer (RQ-20) having an acidic group. The weight average molecular weight (Mw) of the obtained copolymer was about 11,000, and the acid value was 79.7 mgKOH / g.

(Production of α-olefin copolymers RQ-21 to RQ-26 having acidic groups)
Except having changed into the raw material and preparation amount which were described in Tables 2-4, it synthesize | combined similarly to (RQ-20), and obtained the copolymer (RQ-21)-(RQ-26). Each weight average molecular weight (Mw) and acid value are as having described in Tables 2-4.

The abbreviations in Tables 2 to 4 are shown below. In the following description, compounds having hydrogen atoms bonded to all the monovalent bonds in the general formulas (1) to (6) were used.
(3) -1: A compound in which R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, m = 4, and n = 0 in the general formula (3).
(3) -2: A compound in which R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, m = 12, and n = 0 in general formula (3).
(3) -3: A compound in which R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, m = 22, n = 0 in the general formula (3).
(3) -4: In general formula (3), R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, A ² O = C ₃ H ₆ O, m = 3, n = 6.
(3) -5: In the general formula (3), R ₁ = C ₈ H ₁₇ , A ¹ O = C ₂ H ₄ O, A ² O = C ₃ H ₆ O, m = 3, and n = 6. Compound.
(3) -6: A compound in which R ₁ = C ₁₈ H ₃₇ , A ² O = C ₃ H ₆ O, m = 0, n = 7 in the general formula (3).
(4) -1: A compound in which R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, m = 12, and n = 0 in the general formula (4).
(4) -2: A compound in which R ₁ = C ₁₁ H ₂₃ , A ¹ O = C ₂ H ₄ O, m = 12, and n = 0 in the general formula (4).
(4) -3: A compound in which R ₁ = C ₁₁ H ₂₃ , A ² O = C ₃ H ₆ O, m = 0, n = 8 in the general formula (4).
(5) -1: (JEFFAMINE M-600 (manufactured by HUNTSMAN) was used. In general formula (5), R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, A ² O = C ₃ H) _A compound in which ₆ O, m = 1, n = 9, and R1 = hydrogen atom.
(5) -2: (JEFFAMINE M-1000 (manufactured by HUNTSMAN) was used. In general formula (5), R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, A ² O = C ₃ H) _A compound wherein ₆ O, m = 19, n = 3, and R1 = hydrogen atom.
(5) -3: (JEFFAMINE M-2005 (manufactured by HUNTSMAN) was used. In general formula (5), R ₁ = methyl group, A ¹ O = C ₂ H ₄ O, A ² O = C ₃ H) _A compound in which ₆ O, m = 6, n = 29, and R1 = hydrogen atom.
Cyclohexyl alcohol: A compound in which R ₁ = cyclohexyl group in the general formula (1).
Benzyl alcohol: A compound in which R ₁ = benzene ring in the general formula (1).
Lactic acid: A compound in which R ₁ is represented by the following general formula (6) in the general formula (1).

General formula (6)

Stearylamine: a compound in which R ₁ = CH ₃ (CH ₂ ) ₁₇ -and R ₂ = hydrogen atom in the general formula (2).
Diisopropylamine: a compound in which R ₁ = (CH ₃ ) ₂ CH-, R ₂ = (CH ₃ ) ₂ CH- in the general formula (2) cyclohexylamine: in the general formula (2), R ₁ = cyclohexyl group, A compound in which R ₂ = a hydrogen atom.

(Production of coated pigment (Wet) PRQ-1 to PRQ-82)
(Production of PRQ-1)
As pigment (X), 250 parts of PR122 ("Toner Magenta E" manufactured by Clariant), 1250 parts of sodium chloride as a water-soluble inorganic salt, 87.5 parts of (RQ-1) as a resin, and 250 parts of diethylene glycol as a water-soluble organic solvent Was placed in a stainless steel 3 L kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was placed in 7,500 parts of water and allowed to stand for 24 hours, stirred for about 1 hour with a high speed mixer to form a slurry, filtered, and washed repeatedly to remove sodium chloride and the water-soluble organic solvent. As a result, a pigment (coated pigment) (PRQ-1) solution whose surface was coated with a resin was obtained. (Nonvolatile content concentration: 30.5%) The nonvolatile content concentration was calculated by measuring the weight of the nonvolatile content after 30 minutes at 105 ° C.

(Production of PRQ-2 to PRQ-78)
A pigment (coated pigment) (PRQ-2 to PRQ-78) solution, which was treated in the same manner as (PRQ-1) except that the raw materials and preparation amounts described in Tables 5 to 7 were changed, was coated in the same manner as (PRQ-1). Obtained.
In addition, the coating pigments (PRQ-76) to (PRQ-78) were prepared by changing 87.5 parts of (RQ-1) used in the production of (PRQ-1) to the combined use of the following resins and the composition. Except for the change, the same processing as in (PRQ-1) was performed.
Coating pigment (PRQ-76)
Resin 1: (RQ-5) 60 parts Resin 2: Joncyl 690 27.5 parts Covered pigment (PRQ-77)
Resin 1: (RQ-5) 60 parts Resin 2: X-1 27.5 parts coated pigment (PRQ-78)
Resin 1: (RQ-5) 60 parts Resin 2: SMA 1440 27.5 parts

The coated pigments (PRQ-75) and (PRQ-79) to (PRQ-80) were changed from 87.5 parts (RQ-1) used in the production of (PRQ-1) to the resins and compositions shown below. The process was the same as (PRQ-1) except that.
Coating pigment (PRQ-75)
Resin 1: (RQ-5) 200.0 parts Coating pigment (PRQ-79)
Resin 1: (RQ-5) 37.5 parts Covered pigment (PRQ-80)
Resin 1: (RQ-5) 250.0 parts

Coated pigments (PRQ-81) to (PRQ-83) were prepared in the same manner as in (PRQ-1) except that 87.5 parts of (RQ-1) used in the production of (PRQ-1) were changed to the resins and compositions shown below. ).
Coating pigment (PRQ-81)
Resin 1: 87.5 parts of Joncyrl 690 Covering pigment (PRQ-82)
Resin 1: X-1 87.5 parts coated pigment (PRQ-83)
Resin 1: 87.5 parts of SMA 1440 The concentration of nonvolatile components and the amount of resin adsorbed are as described in Table 5. In addition, resin adsorption amount was shown by the ratio (%) of resin adsorption amount (mass part) with respect to 100 mass parts of pigment (X).

(Production of pigment PRQ-84 not coated with resin)
(Production of PRQ-83)
250 parts of PR122 (“Toner Magenta E” manufactured by Clariant) as a pigment, 1250 parts of sodium chloride as a water-soluble inorganic salt, 250 diethylene glycol as a water-soluble organic solvent
The portion was charged into a stainless steel 3 L kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours.
This mixture was put into 7,500 parts of water and allowed to stand for 24 hours, stirred for about 1 hour with a high speed mixer to form a slurry, filtered and washed repeatedly to remove sodium chloride and water-soluble organic solvent to remove the coated pigment (PRQ -84) (actually uncoated pigment). (Non-volatile content 34.2%). The nonvolatile content concentration was calculated by measuring the weight of the nonvolatile content after 30 minutes at 105 ° C.

Below, it shows about the name and comment in Tables 5-7.
(name)
Joncyl 690: Styrene (meth) acrylic resin (manufactured by BASF)
X-1: Styrene (meth) acrylic resin (manufactured by Seiko PMC)
SMA 1440: Styrene (anhydrous) maleic resin (manufactured by Cray Valley)
(Note)
(PRQ-84) is a pigment that is classified as a coated pigment but is not actually coated.
(Note)
In Tables 5 to 7 in which a plurality of CI Nos are described ((PRQ-47) to (PRQ-74)), a plurality of pigments were simultaneously used in the parts by mass described in the tables to produce coated pigments. For example, the coated pigment (PRQ-47) was manufactured in the same manner as the coated pigment (PRQ-1) except that 250 parts of toner magenta E was changed to 125 parts of toner magenta E and 125 parts of PERMANENT CARLINE FBB02-JP. The coated pigment (PRQ-47) was obtained by the same method as the method for producing the coated pigment (PRQ-1). The coated pigments (PRQ-48) to (PRQ-74) were also treated in the same manner as the coated pigment (PRQ-47).

(Production of aqueous pigment dispersion)
[Example 1-1]
(Production of aqueous pigment dispersion (DPRQ-1))
Of the 100 parts of pigment aqueous dispersion (DPRQ-1), the acid value of the resin contained in the coated pigment (PRQ-1), ion-exchanged water, and the coated pigment so that the pigment contained in the coated pigment would be 15 parts Weighed out to neutralize an equal amount of dimethylaminoethanol calculated from parts by mass, stirred with a high-speed mixer at a liquid temperature of 70 ° C. for 1 hour, adjusted the volatilized water with ion-exchanged water, and added a pigment aqueous dispersion (DPRQ- 1) 100 parts were obtained. The particle size distribution of the obtained pigment aqueous dispersion was evaluated as the particle size distribution of the coated pigment (PRQ-1). The particle size distribution was measured by diluting with ion-exchanged water using Nanotrac Wave (manufactured by Microtrack Bell). The particle size distribution of the aqueous pigment dispersion (DPRQ-1) was d50 = 58 nm (volume average particle diameter).
In addition, the mass part of the pigment contained in the coating pigment was calculated by the following method.
Mass part of pigment contained in coated pigment = (1) x (2) ÷ ((2) + (3))
(1) Non-volatile content of coated pigment
(2) Mass parts of the pigment (X) used in the production of the coated pigment
(3) Mass parts of resin used when producing coated pigment The mass parts of resin contained in the coated pigment were calculated by the following method.
Mass parts of resin contained in coating pigment = (1) x (2) ÷ ((2) + (3))
(1) Non-volatile content of coated pigment
(2) parts by mass of the resin used when producing the coated pigment
(3) Part by mass of the pigment (X) used in producing the coated pigment The part by mass of neutralizing equivalent of dimethylaminoethanol was calculated by the following method.
Parts by weight of dimethylaminoethanol = ((1) x (2) ÷ 1000) ÷ (3) x (4)
(1) Mass parts of resin contained in the coating pigment
(2) Acid value of resin contained in coated pigment (mgKOH / g)
(3) Molar mass of potassium hydroxide (56.11 g / mol mol)
(4) Molar mass of dimethylaminoethanol (89.14 g / mol)

[Examples 1-2 to 1-78, Comparative Examples 1-1 to 1-5]
A pigment aqueous dispersion dispersion (DPRQ) was prepared in the same manner as in Example (1-1) except that the coated pigment (PRQ-1) in Example (1-1) was changed to the coated pigment shown in Tables 8 to 10. -1) to (DPRQ-83) were obtained. About the obtained pigment aqueous dispersion, the particle size distribution was measured like Example 1-1. The measurement results are shown in Tables 8-10.

[Comparative Example 1-6]
5.3 parts of resin (RQ-5), dimethylaminoethanol calculated from the acid value and parts by weight of (RQ-5) and neutralizing equivalents were added, and ion-exchanged water was weighed out to make the total amount of solution 56.1. Adjusted. Next, the mixture was stirred and mixed with a high-speed mixer for 1 hour while heating to 70 ° C., and the evaporated water was adjusted with ion-exchanged water to obtain an aqueous dispersion of resin (RQ-5). The obtained aqueous dispersion of (RQ-5) was weighed with 43.9 parts of coated pigment (PRQ-84) (pigment that was not actually coated), stirred at a liquid temperature of 70 ° C. for 1 hour with a high speed mixer and volatilized. The water content was adjusted with ion-exchanged water to obtain 100 parts of an aqueous pigment dispersion (DPRQ-84). The particle size distribution was measured by the same method as in Example 1-1, but the pigment settled and could not be evaluated. The measurement results are shown in Table 10 as “sedimentation”.

[Inkjet printing ink production method (1)]
[Example 1-1]
26.7 parts of pigment aqueous dispersion (DPRQ-1) and 73.3 parts of the following diluent A were mixed by stirring at 500 rpm with a high speed mixer to obtain inkjet printing ink (1-1).

(Diluent A)
Glycerin 10.0 parts 1,3-propanediol 15.0 parts Surfinol DF110D (air products Japan antifoam) 0.5 parts Proxel GXL (LONZA antiseptic) 0.2 parts ion-exchanged water 47. 6 copies

[Examples 1-2 to 1-78, Comparative Examples 1-1 to 1-6]
Inkjet printing inks (1-2) to (1-84) were obtained by the same composition and method as in Example (1-1) except that the dilutions shown in Tables 8 to 10 were changed.

(Evaluation of aqueous pigment dispersion)
The following items were evaluated for the obtained pigment aqueous dispersion. The evaluation results are shown in Tables 8-10.
(1) Filtration test The amount of coarse particles in the pigment aqueous dispersion was evaluated by a filtration test. Evaluation was made based on the passage time of a certain amount of pigment aqueous dispersion to a 25 mmφ glass fiber filter (manufactured by GF / B GE Healthcare Life Sciences). When there are many coarse particles, the filter is clogged and the passage time is observed long. Further, when there are more coarse particles, the filter is clogged, and the entire pigment aqueous dispersion cannot be filtered. Generally, the filter used for the ink supply path to the inkjet head is larger than 1 μm, and the pigment concentration of inkjet printing ink is generally lower than that of the aqueous pigment dispersion. That's enough. Specific evaluation conditions are shown below. 25mm diameter filter holder (manufactured by ADVANTEC) with a funnel with a 15ml scale and a 25mmφ glass fiber filter (manufactured by GF / B GE Healthcare Life Science) on a suction vessel with a vacuum pump via a cock ). The decompression pump is operated using a cock so that the inside of the suction vessel is not decompressed. 15 g of the pigment aqueous dispersion is weighed into a funnel. Starting with the opening pressure of the pump and the suction vessel, the time (seconds) for the total amount of the pigment aqueous dispersion to pass through the filter is measured. At this time, the pressure in the suction vessel is 0.05 MPa to 0.07 MPa. When the filtration filter was clogged within 60 seconds and the aqueous pigment dispersion did not pass, the amount (g) of the aqueous pigment dispersion remaining in the funnel was measured. In addition, evaluation is so favorable that passage time is short. Samples that took 60 seconds or longer to pass through the filter and samples in which the filter was clogged and the dispersion did not pass through the filter paper had many coarse particles and poor dispersibility.
Samples that took 60 seconds or more to pass through the filter were measured for the amount of dispersion (g) on the filter paper when 60 seconds passed. For the sample in which the filter was clogged and the total amount of the dispersion did not pass through the filter paper, the amount of dispersion (g) on the filter paper at the time when 60 seconds had elapsed was measured.

[Evaluation of inkjet printing ink (1)]
The following was evaluated about the obtained inkjet printing ink. The results are shown in Tables 8-10.
(1) Ejectable ink jet printing ink (A1) is filled in an ink jet printer equipped with an ink jet head having a piezo element in an environment of 25 ° C., and 30 sheets are continuously printed on copy paper (Xerox 4024) to observe missing dots. did. Regarding the percentage of nozzles with missing dots relative to all nozzles,
0%: S Good More than 0% and less than 5%: A More than 5% practical area: B Not practical

(2) Water-resistant inkjet printing ink (A1) is filled in an inkjet printer equipped with an inkjet head having a piezo element in an environment of 25 ° C., and cyan, magenta, yellow, black, orange on copy paper (Xerox 4024) , Green, violet, and white ink were used for printing, and the printed matter was immersed in tap water immediately after printing under the conditions of a temperature of 25 ° C. and a humidity of 50%, and bleeding of the printed matter was observed and evaluated according to the following criteria. .
No smearing of printing occurs after 1 hour of immersion: S Smearing of printing occurs after 10 minutes to less than 1 hour: A Smearing of printing occurs immediately after less than 10 minutes of immersion in the practical area T: B Not practical

It shows below about the dilution liquid in Tables 8-10.
(Diluent A)
Glycerin 10.0 parts 1,3-propanediol 15.0 parts Surfinol DF110D (air products Japan antifoam) 0.5 parts Proxel GXL (LONZA antiseptic) 0.2 parts ion-exchanged water 47. 6 copies

(Diluent B)
Boncoat 4001 (manufactured by DIC) 6.0 parts glycerin 10.0 parts triethylene glycol 25.0 parts 2,2,4-trimethyl-1,3-pentanediol 4.0 parts Polyfox PF-151N (manufactured by OMNOVA) ) 2.0 parts Proxel LV (preservative made by LONZA) 0.2 parts triethanolamine 0.1 parts ion-exchanged water 26.0 parts

(Diluent C)
Hydran HW-940 (manufactured by DIC) 7.0 parts glycerin 6.0 parts 3-methyl-1,3-butanediol 19.0 parts 2-ethyl-1,3-hexanediol 2.0 parts Zonyl FS-300 (Dupont) 2.5 parts Proxel LV (LONZA antiseptic) 0.2 parts 2-amino-2-ethyl-1,3-propanediol 0.1 part ion-exchanged water 36.5 parts

(Diluent D)
ACRYT WEM-321U (manufactured by Taisei Kako) 7.9 parts glycerin 7.5 parts 1,3-butanediol 22.5 parts 2-ethyl-1,3-hexanediol 4.0 parts Polyfox PF-156A (OMNOVA) 3.3 parts Proxel LV (LONZA preservative) 0.2 parts 2-amino-2-ethyl-1,3-propanediol 0.1 part ion-exchanged water 27.8 parts

(Diluent E)
Boncoat 4001 (manufactured by DIC) 7.0 parts glycerin 7.5 parts diethylene glycol 22.5 parts 2,2,4-trimethyl-1,3-pentanediol 4.0 parts polyfox PF-151N (manufactured by OMNOVA) 2 0.0 part Proxel LV (preservative made by LONZA) 0.2 part 2-amino-2-ethyl-1,3-propanediol 0.1 part ion-exchanged water 30.0 parts

In Tables 8 to 10, the pigment aqueous dispersions of Examples (1-1) to (1-78) were good results, and the dispersibility of coarse particles was excellent. On the other hand, the total amount of Comparative Examples (1-1) and (1-3) to (1-6) did not pass through the filtration test.

In Tables 8-10, the inkjet printing inks of Examples (1-1) to (1-78) are superior in ejection properties compared to Comparative Examples (1-1) and (1-3) to (1-6). It was. In particular, Comparative Example (1-6) could not be ejected by an ink jet printer. Moreover, the printed matter printed using the inkjet printing ink of Example (1-1)-(1-78) was excellent in water resistance compared with the comparative example (1-2). In Comparative Example (1-6), the water resistance evaluation was not performed because the printed matter could not be produced because it could not be ejected by an ink jet printer equipped with an ink jet head having a piezoelectric element.

(Production of the crosslinked dispersion of the present invention)
[Example 2-1]
Coated pigment (PRQ-1) and ion-exchanged water were measured so that the pigment contained in the coated pigment was 20 parts out of 100 parts of pigment aqueous powder (DPRQ-1 '), and further measured. Weigh out the equivalent amount of potassium hydroxide calculated from the mass part of resin contained in (PRQ-1) and the acid value, and stir with a high-speed mixer for 1 hour at a liquid temperature of 70 ° C. Adjustment with water gave 100 parts of an aqueous pigment dispersion (DPRQ-1 ′). In 100 parts of the pigment aqueous dispersion (DPRQ-1 ′), the molar number of potassium hydroxide and the number of epoxy groups used in producing the pigment aqueous dispersion (DPRQ-1 ′) are equimolar. Denacol EX321 (epoxy crosslinking agent, manufactured by Nagase ChemteX, non-volatile content: 100%, epoxy equivalent: 140 g / eq) is added as a crosslinking agent, and the mixture is stirred at 70 ° C. for about 2 hours. A dispersion (CPRQ-1 ′) was obtained. Further, out of 100 parts of the crosslinked pigment dispersion (CPRQ-1 ′), the crosslinked pigment dispersion (CPRQ-1 ′) was adjusted using ion-exchanged water so that the pigment contained in the coated pigment was 15 parts. 100 parts of a crosslinked pigment dispersion (CPRQ-1) were obtained.
In addition, the mass part of the pigment contained in the coating pigment and the mass part of the resin contained in the coating pigment were calculated in the same manner as in Example (1-1).
In addition, the mass part of potassium hydroxide was computed with the following method.
Mass parts of potassium hydroxide = (1) x (2) ÷ 1000
(1) Mass part of resin contained in coated pigment (2) Acid value of resin contained in coated pigment (mgKOH / g)

[Examples 2-2 to 2-78, Comparative examples 2-1 to 2-5]
Crosslinked pigment dispersions (CPRQ-2 to CPRQ-83) were obtained in the same manner as in Example (2-1) except that the compositions shown in Tables 11 to 13 were changed.

[Comparative Example 2-6]
7.0 parts of resin (RQ-5), potassium hydroxide equivalent to the acid value calculated from (RQ-5), and ion-exchanged water were weighed so that the total amount would be 34.5 parts. The mixture was stirred and mixed with a high-speed mixer for 1 hour while heating, and the evaporated water was adjusted with ion-exchanged water to obtain an aqueous dispersion of resin (RQ-5). Weighing 58.5 parts of the coated pigment (PRQ-84) (pigment that is not actually coated) into the aqueous dispersion of the obtained resin (RQ-5) and stirring with a high speed mixer at a liquid temperature of 70 ° C. for 1 hour. The volatilized water was adjusted with ion exchange water to obtain 100 parts of an aqueous pigment dispersion (DPRQ-84 ′). Further, 100 parts of pigment aqueous dispersion (DPRQ-84 ′) is equimolar with the number of moles of potassium hydroxide and the number of epoxy groups used in producing pigment aqueous dispersion (DPRQ-84 ′). Denacol EX321 (epoxy crosslinking agent, manufactured by Nagase ChemteX, non-volatile content: 100%, epoxy equivalent: 140 g / eq) was added as a crosslinking agent, and the mixture was stirred at 70 ° C. for about 2 hours. A pigment dispersion (CPRQ-84 ′) was obtained. Further, out of 100 parts of the crosslinked pigment dispersion (CPRQ-84 ′), the crosslinked pigment dispersion (CPRQ-84 ′) is ionized so that the pigment contained in the coated pigment (actually not coated) is 15 parts. It adjusted using exchange water and obtained 100 parts of crosslinked pigment dispersions (CPRQ-84). In addition, as for the mass part of the pigment contained in the coated pigment, the solid content of the coated pigment (PRQ-84) was used as the mass part of the pigment.

[Comparative Example 2-7]
A pigment aqueous dispersion was prepared in the same manner as in Comparative Example (1-5) except that dimethylaminoethanol was changed to potassium hydroxide to obtain a pigment aqueous dispersion (DPRQ-5-2) without a crosslinking agent treatment. It was.

[Production of inkjet printing ink (2)]
[Example 2-1]
In obtaining 100 parts of the ink jet printing ink, the cross-linked pigment dispersion (CPRQ-1) and 16.0 parts of 1,2-hexanediol, 1 part, 1, so that the pigment contained in the coating pigment in the ink jet printing ink is 4 parts. 2-butanediol 16.0 parts, Surfynol DF110D (air products Japan antifoam) 0.5 parts, Proxel GXL (LONZA antiseptic) 0.2 parts, ion-exchanged water at 500 rpm with a high speed mixer The mixture was stirred and mixed to obtain inkjet printing ink (2-1).

[Examples 2-2 to 2-78, Comparative examples 2-1 to 2-7]
The crosslinked pigment dispersion (CPRQ-1) shown in Example (2-1) is changed to the crosslinked pigment dispersions (CPRQ-2) to (CPRQ-84) shown in Tables 11 to 13, and the non-crosslinked pigment aqueous dispersion. Inkjet printing inks (2-2) to (2-85) were obtained in the same manner as in Example (2-1) except that the product was changed to the body (DPRQ-5-2).

[Evaluation of inkjet printing ink (2)]
The following was evaluated about the obtained inkjet printing ink (2). The results are shown in Tables 11-13.

(Particle size distribution stability)
The particle size distribution of the manufactured inkjet printing ink (2) is Nanotrac Wave (manufactured by Microtrack Bell), and the inkjet printing ink (2) is diluted by ion exchange so that the loading index becomes 15-20. Measured (volume average particle diameter). Further, the inkjet printing ink (2) was stored in a thermostat at 70 ° C. for 1 week, and the particle size distribution was measured in the same manner to determine the rate of change. The evaluation criteria are as follows.
S: Change rate of particle size distribution (D50) before and after storage at 70 ° C. for 1 week is less than ± 10% (good)
A: Change rate of particle size distribution (D50) before and after storage at 70 ° C. for 1 week ± 10% or more and less than ± 20% (no problem in practical use)
B: Particle size distribution (D50) change rate before and after storage at 70 ° C. for 1 week is ± 20% or more (defect)

(Viscosity stability)
The viscosity of the produced inkjet printing ink (2) was measured using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. under the condition of a rotation speed of 20 rpm. Furthermore, after the inkjet printing ink (2) was stored in a thermostat at 70 ° C. for 1 week, the viscosity was measured in the same manner to determine the rate of change. The evaluation criteria are as follows.
S: Viscosity change rate before and after storage at 70 ° C. for 1 week is less than ± 10% (good)
A: Viscosity change rate before and after storage at 70 ° C. for 1 week ± 10% or more and less than ± 20% (no problem in practical use)
B: Viscosity change rate before and after storage at 70 ° C. for 1 week is ± 20% or more (defect)

In Tables 11-13, Example (2-1)-(2-78) was excellent in the stability of the viscosity and particle size distribution after using it as an inkjet printing ink by using a crosslinking agent. On the other hand, since Comparative Example (2-7) did not use a crosslinking agent, the storage stability after aging acceleration of the particle size distribution and viscosity could not be sufficiently obtained. In Comparative Examples (2-1) and (2-3) to (2-5), the pigment is not sufficiently covered with the resin, so that a sufficient crosslinking effect cannot be obtained. The storage stability after the acceleration could not be obtained sufficiently. In Comparative Example (2-6), the pigment was settled and a dispersion could not be prepared, so it was described as sedimentation. The viscosity could not be measured.

(toner)
Hereinafter, the present invention will be specifically described with reference to examples of toner. In addition, the coated pigment (coated pigment) of the present invention was dried to form a powder for the production of toner.

(Manufacture of coated pigment (dry))
[Examples 3-1 to 3-4, Comparative example 3-1]
Each of the coated pigments (Wet) (PRQ-1) to (PRQ-84) shown in Table 14 was stored at 40 ° C. under reduced pressure (−0.9 MPa) for 24 hours, and the coated pigment (dry) (PRQ-1D) To (PRQ-84D). The obtained Dry pigment was observed with a scanning electron microscope.

<Toner production method>
[Example 3-1]
(Manufacture of magenta toner 1)
(1) Preparation of magenta concrete 1 The following materials (3 kg in total) were mixed and kneaded in a pressure kneader at a set temperature of 150 ° C. for 10 minutes and taken out. Further, the mixture was kneaded with three rolls at a roll temperature of 95 ° C., cooled and roughly crushed to 10 mm or less to obtain magenta concrete 1 as a magenta colorant dispersion.
Toner binder resin 1 60.0 parts Pigment (coated pigment) (PRQ-5D) 40.0 parts * Toner binder resin 1: Consists of terephthalic acid, isophthalic acid, trimellitic acid, propylene oxide-added bisphenol A, and ethylene glycol Thermoplastic polyester resin.
Acid value: 10 mg KOH / g OH value: 43 mg KOH / g Tg 58 ° C. Softening temperature Ts 65 ° C. True density 1.32 g / cc Molecular weight Mw: 28200 Mn: 2500
(2) Preparation of magenta toner base particles 1 Next, the following materials (total 5 kg) were mixed (3000 rpm, 3 minutes) with a Henschel mixer having a volume of 20 L, and then supplied with a twin-screw kneading extruder (PCM30) 6 kg. / Hr, at a discharge temperature of 145 ° C., cooled and solidified, coarsely pulverized with a hammer mill, then finely pulverized with an I-type jet mill (IDS-2 type) and classified (DS-2 type). A classified product (magenta toner base particles 1) having a weight average particle size of about 8.3 μm was obtained.
Toner binder resin 1 77.0 parts Magenta concrete 1 20.0 parts Charge control agent (zinc salt compound of 3,5-di-tert-butylsalicylic acid) 1.0 part Release agent (Sazole wax H1N4 Melting point 110 ° C. ) 2.0 parts (3) Preparation of magenta toner 1 Next, 100 parts of the classified product obtained above, 1.0 part of hydrophobic silica (NY-50 manufactured by Nippon Aerosil Co., Ltd.) and hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd.) R-974) 0.5 part was mixed with a 10 L Henschel mixer (3000 rpm, 3 minutes) and passed through a sieving step (150 mesh) to obtain magenta toner 1.

[Example 3-2]
(Manufacture of cyan toner 1)
Cyanconc 1, which is a cyan colorant dispersion, in the same manner as in Example 3-1, except that the coated pigment (PRQ-18D) was used instead of the coated pigment (PRQ-5D) of Example 3-1. Cyan toner base particles 1 and cyan toner 1 as classified products having a weight average particle diameter of about 8.2 μm were obtained.

[Example 3-3]
(Manufacture of yellow toner 1)
Yellow concrete 1 which is a yellow colorant dispersion is the same as Example 3-1, except that the coated pigment (PRQ-23D) is used instead of the coated pigment (PRQ-5D) of Example 3-1. Thus, yellow toner base particles 1 and yellow toner 1 which are classified products having a weight average particle diameter of about 8.6 μm were obtained.

[Example 3-4]
(Manufacture of black toner 1)
A black colorant (carbon black) dispersion was used in the same manner as in Example 3-1, except that the coated pigment (PRQ-45D) was used instead of the coated pigment (PRQ-5D) of Example 3-1. A black toner 1 and black toner mother particles 1 and black toner 1 which are classified products having a weight average particle diameter of about 8.4 μm were obtained.

[Example 3-5]
(Manufacture of magenta toner 2)
Magenta toner 2 was obtained by the following method using an aqueous pigment dispersion (DPRQ-5).
(1) Preparation of dispersion 3 parts of sodium dodecylbenzenesulfonate (Neopelex G-15, manufactured by Kao Corporation) was added to 97 parts of pigment aqueous dispersion (DPRQ-5), and stirred at 500 rpm for 1 hour with a high speed mixer. A magenta pigment dispersion was obtained.
(2) Preparation of polymer emulsion In a reactor, 320 parts of ester wax emulsion (SELOSOLR-586, manufactured by Chukyo Yushi Co., Ltd.) and 14,000 parts of ion-exchanged water are added, and the temperature is raised to 90 ° C. 3 parts of sodium acid, 2500 parts of styrene, 650 parts of n-butyl acrylate, 170 parts of methacrylic acid, 330 parts of 8% aqueous hydrogen peroxide solution and 330 parts of 8% ascorbic acid aqueous solution were added. The reaction was continued at 90 ° C. for 7 hours to obtain a polymer emulsion.
(3) Production of Magenta Toner Base Particles 2 16.5 parts of the magenta pigment dispersion was injected into 150 parts of the polymer emulsion and mixed and stirred. Into this, 40 parts of 0.5% aluminum sulfate solution was poured while stirring. The temperature was raised to 60 ° C. and stirring was continued for 2 hours, followed by filtration, washing and drying to obtain magenta toner mother particles 2 of the present invention.
(4) Preparation of magenta toner 2 Next, 100 parts by mass of magenta toner mother particles 2 obtained above, 1.0 part by mass of hydrophobic silica (NY-50 manufactured by Nippon Aerosil Co., Ltd.) and hydrophobic silica (Nippon Aerosil Co., Ltd.) (Made by R-974) 0.5 parts by mass was mixed with a 10 L Henschel mixer (3000 rpm, 3 minutes), passed through a sieving step (150 mesh), and magenta toner 2 was obtained.

[Example 3-6]
(Manufacture of magenta toner 4)
A magenta toner 4 was obtained by the following method using the crosslinked pigment dispersion (CPRQ-5).
(1) Preparation of dispersion 3 parts of sodium dodecylbenzenesulfonate (Neopelex G-15, manufactured by Kao Corporation) was added to 97 parts of the crosslinked pigment dispersion (CPRQ-5) and stirred at 500 rpm for 1 hour with a high speed mixer. A magenta pigment dispersion was obtained.
(2) Preparation of polymer emulsion In a reactor, 320 parts of ester wax emulsion (SELOSOLR-586, manufactured by Chukyo Yushi Co., Ltd.) and 14,000 parts of ion-exchanged water are added, and the temperature is raised to 90 ° C. 3 parts of sodium acid, 2500 parts of styrene, 650 parts of n-butyl acrylate, 170 parts of methacrylic acid, 330 parts of 8% aqueous hydrogen peroxide solution and 330 parts of 8% ascorbic acid aqueous solution were added. The reaction was continued at 90 ° C. for 7 hours to obtain a polymer emulsion.
(3) Production of Magenta Toner Base Particles 4 16.5 parts of the magenta pigment dispersion was poured into 150 parts of the polymer emulsion and mixed and stirred. Into this, 40 parts of 0.5% aluminum sulfate solution was poured while stirring. The temperature was raised to 60 ° C., and stirring was continued for 2 hours, followed by filtration, washing and drying to obtain magenta toner mother particles 4 of the present invention.
(4) Preparation of magenta toner 4 Next, 100 parts by mass of magenta toner mother particles 4 obtained above, 1.0 part by mass of hydrophobic silica (NY-50 manufactured by Nippon Aerosil Co., Ltd.) and hydrophobic silica (Nippon Aerosil Co., Ltd.) (Made by R-974) 0.5 part by mass was mixed with a 10 L Henschel mixer (3000 rpm, 3 minutes), passed through a sieving step (150 mesh: aperture 0.1 mm) to obtain magenta toner 4.

[Comparative Example 3-1]
Production of (Magenta Toner 3) A magenta colorant was prepared in the same manner as in Example 3-1, except that the coated pigment (PRQ-84D) was used instead of the coated pigment (PRQ-5D) of Example 3-1. Magenta concrete 3 as a dispersion, magenta toner base particles 3 and magenta toner 3 as classified products having a weight average particle diameter of about 8.6 μm were obtained.

<Evaluation of toner>
The obtained toner was evaluated by the following method. The results are shown in Table 15.
(Image density)
Using a color printer (a modified N6100 machine manufactured by Casio Computer Co., Ltd.), a live-action test was performed under an environmental condition of 23 ° C / 50% RH. At this time, the image production conditions were output in the evaluation toner single color. About the obtained image, the image density at the time of initial and 3,000 copies was measured using a Macbeth photometer. The density may be 1.3 or more (1.2 or more in the case of yellow toner) at the initial stage and at the time of copying 3,000 sheets.

(Fog evaluation)
In the same manner as the image density evaluation, fogging at the initial stage and when copying 3,000 sheets was measured by measuring the reflectance with a photovolt. 1.0% or less is a good value.

(Appearance evaluation)
In the same manner as the image density evaluation, after 3,000 copies were made, the toner particles were scattered in the machine and the resulting image was visually judged. The toner was scattered in the machine by checking whether or not the scattered toner was present around the developing unit and the photosensitive drum. When toner scattering is observed, image stains accompanying this occur.

(Charge amount)
The charge amount of the classified product and the toner was measured as follows. Powder Tech Iron Powder Carrier (trade name: MF-70) 19.0g, dried product or 1.0g of toner is weighed into a 50cc plastic bottle, shaken 5 times, and then ball mill (manufactured by Shinei Koki Sangyo Co., Ltd.) (PLASTIC PLANT SKS type) was mixed for 30 minutes under the condition that the rotation number was 230 rotations (120 rotations for the main body of the poly bottle). The obtained sample after mixing was subjected to charge amount measurement using a blow-off charge amount measuring device manufactured by Toshiba Chemical Corporation. At this time, the blow pressure was 1 kgf / cm @ 2, the maximum value was read at a measurement time of 20 seconds, and the mesh was 400 mesh. The measurement environment was 23 ° C./50% RH.

Regarding Table 15, in Examples 3-1 to 3-6, even in the image test of 3000 sheets from the initial stage, the image density is high and stable, the fog on the white background is small, and no in-flight scattering is observed. It was. In addition, even when the pigment is changed, there is no fluctuation in the charge amount due to the different colors in both the classified product (toner base particles) and the toner, and it can be seen that the charge level can be easily adjusted in designing the process color.

(paint)
(Manufacturing method of coating composition)
[Example 4-1]
(Coating composition (4-1))
The pigment aqueous dispersion (DPRQ-1) and the binder resin were blended in a solid amount so as to have the following composition to obtain a coating composition (4-1).
Pigment aqueous dispersion (DPRQ-1): 4.1 parts Watersol S-751: 60.0 parts (acrylic resin for baking paints manufactured by DIC)
Cymel 303: 45.0 parts (Melamine Cytec Melamine resin)

[Example 4-2 to Example 4-156, Comparative examples 4-1 to 4-4]
A coating composition (4) was prepared in the same manner as in Example (4-1) except that the aqueous pigment dispersion described in Example (4-1) was changed to the aqueous pigment dispersion or crosslinked pigment dispersion described in Tables 15-20. -2) to (4-156) were obtained.

(Evaluation of coating composition)
About the obtained coating composition, it applied with an applicator so that a film thickness may be set to 37 ± 2 μm on a corona discharge-treated PET film or a BT-144 treated steel plate, set for 30 minutes, and then dried at 60 ° C. for 20 minutes. Then, baking was performed at 140 ° C. for 20 minutes to prepare test pieces of each coating composition. The test piece was evaluated as follows. The results are shown in Tables 15-20.

(Deep feeling)
About the coating film of the test piece applied to the PET film, the depth of color was visually observed at a low angle under white light, and sensory evaluation was performed according to the following criteria.
S: Excellent color depth Good A: Color deep Practical area B: No color deep

(Glossy)
What was coated on the “BT-144 treated steel plate” was measured with a 60 ° specular gloss. Evaluation was performed according to the following criteria. S having excellent gloss is desirable.
S: [Gloss value]> 50 (good)
B: [Gloss value] ≦ 50 (defect)

(Color development)
The test piece coated on the PET film was visually judged. Evaluation was performed according to the following criteria.
S: Color density and high opacity Good A: Color density and opacity are normal levels Practical area B: Color density and opacity are inferior Impractical

(Haze value)
About the coating film of the test piece coated on PET film, the haze value was measured with the haze meter (made by Nippon Denshoku Industries Co., Ltd.). Evaluation was performed according to the following criteria.
S: [Haze value] <60 (good)
A: 60 ≦ [Haze value] <80 (Practical area)
B: [Haze value] ≧ 80 (not practical)

(Flip-flop property)
About the test piece coated on PET film, it observed visually and evaluated by the following reference | standard.
S: Excellent change in color tone / brightness depending on viewing angle of coating surface Good A: Change in color tone / brightness depending on viewing angle of coating surface Practical area B: Color tone even if the viewing angle is changed・ Small change in brightness

(Particle size distribution stability)
The particle size distribution of the coating composition was measured by diluting with ion exchange water using the Nanotrac Wave (manufactured by Microtrac Bell). (Volume average particle diameter). Further, the coating composition was stored in a thermostat at 40 ° C. for 1 week, and the particle size distribution was measured in the same manner to determine the rate of change. The evaluation criteria are as follows.
S: Change rate of particle size distribution (D50) before and after storage at 40 ° C. for 1 week is less than ± 10% (good)
A: Change rate of particle size distribution (D50) before and after storage at 40 ° C. for 1 week ± 10% or more and less than ± 20% (no problem in practical use)
B: Particle size distribution (D50) change rate before and after storage at 40 ° C. for 1 week is ± 20% or more (defect)

From the results of Tables 16 to 18, the coating compositions of Examples (4-1) to (4-78) have a feeling of depth, gloss, color developability, compared with Comparative Examples (4-1) to (4-2). Excellent haze value and flip-flop properties. Furthermore, in Examples (4-79) to (4-156), coating compositions using a crosslinked pigment dispersion using a crosslinking agent in the pigment aqueous dispersion are comparative examples (4-3) to (4). Compared with -4), the particle size distribution stability after accelerated aging was excellent.

(Flexographic printing ink)
Prior to the production of flexographic printing ink, polyurethane resin was produced.
(Production of polyurethane resin (1))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a stirrer, a refluxing device, and a nitrogen gas introduction tube, PTG-3000SN (Hodogaya Chemical polytetramethylene glycol functional group number 2 hydroxyl value 37 number average molecular weight 3000) ) 121.8 parts, PEG # 2000 (Nippon polyethylene glycol functional group number 2 hydroxyl value 56 number average molecular weight 2000) 24.4 parts, 2,2-dimethylolpropionic acid 32.7 parts and isophorone diisocyanate 6 6.9 Parts were charged and reacted at 90 ° C. for 3 hours. After cooling, the resulting water-soluble resin was neutralized by gradually dropping and neutralizing a mixed solution of 16.6 parts of 25% aqueous ammonia and 73.0 parts of ion-exchanged water to obtain an aqueous solution of the polyurethane resin (1). Got. The obtained polyurethane resin (1) had an acid value of 55 mgKOH / g and a weight average molecular weight (Mw) of 36000.

(Measurement of acid value)
Number of milligrams of potassium hydroxide required to neutralize acidic components contained in 1 g of resin. The dried polyurethane resin (1) was calculated by performing potentiometric titration with a potassium hydroxide / ethanol solution according to the method described in JIS K2501.

(Measurement of weight average molecular weight (Mw))
A value in terms of polystyrene as measured by GPC (gel permeation chromatography). The dried polyurethane resin (1) is dissolved in tetrahydrofuran to prepare a 0.1% solution, which is weighted by Tosoh HLC-8320-GPC (column number M-0053, molecular weight measurement range of about 2,000 to about 4,000,000). Average molecular weight was measured.

(Manufacture of flexographic printing ink)
[Example 5-1]
Of 100 parts of the flexographic ink (5-1), calculated from the coating pigment (PRQ-5) and the mass part of the resin contained in the coating pigment and the acid value so that the pigment contained in the coating pigment is 15 parts, etc. Amount of potassium hydroxide, polyurethane resin (1) 35.0 parts, nonionic surfactant (Surfinol 104PA, manufactured by Air Products) 0.1 part, n-propanol 2.0 parts, polyethylene wax (Aqua Petro DP2502B) 2.0 parts of Toyo Adre Co., Ltd., 0.2 parts of antifoaming agent (Tegoformex 1488, Evonik Co., Ltd.) and ion-exchanged water were added, heated to 70 ° C. and stirred with a high speed mixer. A volatilized amount of ion exchange water was added to obtain 100 parts of flexographic printing ink (5-1). In addition, the mass part of the pigment contained in the coated pigment, the mass part of the resin contained in the coated pigment are the same as in Example (1-1), and the mass part of potassium hydroxide is the same as in Example (2-1). It was calculated by the method.

[Examples 5-2 to 5-6, Comparative Example 5-1]
Flexographic inks (5-2) to (5-6) and (5-13) were obtained in the same manner as in Example 5-1, except that the coated pigment was changed to the coated pigment shown in Table 21.

[Comparative Example 5-2]
While adding 5.3 parts of (RQ-5) and an equivalent amount of potassium hydroxide calculated from the acid value and parts by weight of (RQ-5), add 30 parts of ion-exchanged water, and then warm to 70 ° C. The mixture was stirred and mixed with a high-speed mixer for 1 hour, and the evaporated water was adjusted with ion-exchanged water to obtain an aqueous dispersion (RQ-5). Furthermore, 15 parts of coated pigment (PRQ-84) (not actually coated), 35.0 parts of polyurethane resin (1), nonionic surfactant (Surfinol 104PA, manufactured by Air Products) 0.1 Parts, 2.0 parts of n-propanol, 2.0 parts of polyethylene wax (Aqua Petro DP2502B, manufactured by Toyo Adre), 0.2 part of antifoaming agent (Tegoformex 1488, manufactured by Evonik), and ion-exchanged water added The mixture was heated to 70 ° C. and stirred with a high speed mixer. A volatilized amount of ion exchange water was added to obtain 100 parts of flexographic printing ink (5-14).

[Example 5-7]
Of 100 parts of flexographic ink (5-7), the coated pigment (PRQ-5) is measured so that the pigment contained in the coated pigment is 15 parts, and is included in the measured coated pigment (PRQ-1). Equivalent amount of potassium hydroxide calculated from mass part of resin and acid value, polyurethane resin (1) 35.0 parts, n-propanol 2.0 parts, polyethylene wax (Aqua Petro DP2502B, manufactured by Toyo Adre) 2 0.0 part, Denacol EX321 (epoxy crosslinking agent, manufactured by Nagase Chemitex, nonvolatile content 100%, epoxy equivalent 140 g / eq) was cross-linked so that the number of moles of potassium hydroxide and the number of moles of epoxy group were equal. It was added as an agent, adjusted to 99 parts with ion-exchanged water, heated to 70 ° C., and stirred for 2 hours with a high speed mixer. Thereafter, 0.1 part of a nonionic surfactant (Surfinol 104PA, manufactured by Air Products), 0.2 part of an antifoaming agent (Tegoformex 1488, manufactured by Evonik), and ion-exchanged water were added to the flexographic printing ink ( 5-7) 100 parts were obtained.
In addition, the mass part of the pigment contained in the coated pigment, the mass part of the resin contained in the coated pigment are the same as in Example (1-1), and the mass part of potassium hydroxide is the same as in Example (2-1). It was calculated by the method.

[Examples 5-8 to 5-12, Comparative Example 5-3]
The flexographic inks (5-8) to (5-12) and (5-15) were prepared in the same manner as in Example 5-7 except that the coated pigment was changed to the coated pigment shown in Table 21.

[Comparative Example 5-4]
While adding 5.3 parts of (RQ-5) and an equivalent amount of potassium hydroxide calculated from the acid value and parts by weight of (RQ-5), add 30 parts of ion-exchanged water, and then warm to 70 ° C. The mixture was stirred and mixed with a high-speed mixer for 1 hour, and the evaporated water was adjusted with ion-exchanged water to obtain an aqueous dispersion (RQ-5). Furthermore, 15 parts of coated pigment (PRQ-84) (not actually coated), 35.0 parts of polyurethane resin (1), 2.0 parts of n-propanol, polyethylene wax (Aqua Petro DP2502B, Toyo Adre Co., Ltd.) 2.0 parts, Denacol EX321 (epoxy crosslinking agent, manufactured by Nagase ChemteX, non-volatile content 100%, epoxy equivalent 140 g / eq, so that the number of moles of potassium hydroxide and the number of moles of epoxy group is equal moles) ) Was added as a cross-linking agent, adjusted to 99 parts with ion-exchanged water, heated to 70 ° C., and stirred for 2 hours with a high speed mixer. Thereafter, 0.1 part of a nonionic surfactant (Surfinol 104PA, manufactured by Air Products), 0.2 part of an antifoaming agent (Tegoformex 1488, manufactured by Evonik), and ion-exchanged water were added to the flexographic printing ink ( 5-16) 100 parts were obtained.

(Evaluation of flexographic printing ink)
The obtained flexographic printing ink was evaluated for storage stability over time of particle size distribution and viscosity. Furthermore, coarse particle evaluation of flexographic ink was carried out. The results are shown in Table 19.

(Evaluation of coarse particles)
The presence or absence of coarse particles of flexographic printing ink was confirmed using a grind gauge (according to JIS K5600-2-5). The evaluation criteria are as follows.
S: Less than 60 μm (good)
A: 60 or more and less than 90 μm (no problem in practical use)
B: 90 μm or more (defect)

(Particle size distribution stability)
The particle size distribution of the flexographic ink was evaluated in the same manner as the coating composition.

(Viscosity stability)
The viscosity of the flexographic ink at 25 ° C. was measured using a Zahn cup (No. 4). Further, after being stored for 1 week in a thermostat at 40 ° C. and accelerated over time, the rate of change in viscosity before and after aging was determined. The evaluation criteria are as follows.
S: Viscosity change rate before and after storage at 40 ° C. for 1 week is less than ± 10% (good)
A: Viscosity change rate before and after storage at 40 ° C. for 1 week ± 10% or more and less than ± 15% (no problem in practical use)
B: Viscosity change rate before and after storage at 40 ° C. for 1 week is ± 15% or more (defect)

  From the results of Table 19, the flexographic inks using the coated pigments of the present invention from Examples 5-1 to 5-12 were excellent in dispersibility of coarse particles. Furthermore, from Examples 5-7 to 5-12, the flexographic inks further using a crosslinking agent as the coating pigment were excellent in the stability of the particle size distribution and viscosity over time.

Claims (12)

A coated pigment whose surface is coated with a resin,
The resin is an α-olefin copolymer having an acidic group,
The coating pigment whose resin coating amount of a coating pigment is 10 to 50 mass parts with respect to 100 mass parts of pigment (X) before coating.   The coated pigment according to claim 1, wherein the resin is an α-olefin copolymer having a side chain and an acidic group. The coated pigment according to claim 2, wherein the side chain is a partial structure selected from the group consisting of structures represented by the following general formulas (1) to (5).
General formula (1)

[In General Formula (1), R ₁ represents a substituted C _{1 to} C ₃₀ alkyl group, an optionally substituted alicyclic structure, or an optionally substituted phenyl group]
General formula (2)

[In General Formula (2), R ₁ and R ₂ are each independently a hydrogen atom, an optionally substituted C ₁ -C ₃₀ alkyl group, an optionally substituted alicyclic structure, or a substituted group. Represents an optionally substituted phenyl group. However, when _one of R ₁ and R ₂ is a hydrogen atom, the other is not a hydrogen atom. ]
General formula (3)

[In General Formula (3), R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms, and A ¹ O and A ² O independently represents an alkyleneoxy group having 1 to 6 carbon atoms, m and n represent an average number of added moles of the alkyleneoxy group, an integer of 0 to 100, and m + n is 1 or more. is there. ]
General formula (4)

[In General Formula (4), R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms, and A ¹ O and A ² O each independently represents an alkyleneoxy group having 1 to 6 carbon atoms, m and n represent the average number of added moles of the alkyleneoxy group, are integers of 0 to 100, and satisfy m + n = 1 or more. . ]
General formula (5)

[In General Formula (5), R ₁ is substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic structure which may be substituted, or an alkyl group having 1 to 9 carbon atoms. R ₂ represents a hydrogen atom, a C _{1 to} C ₃₀ alkyl group, an optionally substituted alicyclic structure, an optionally substituted phenyl group, (poly) alkylene oxide, (poly ) Represents a monoalkyl ether of alkylene oxide, an alkyl ester of (poly) alkylene oxide, A ¹ O and A ² O each independently represent an alkyleneoxy group having 1 to 6 carbon atoms, and m and n are The average addition mole number of an alkyleneoxy group is an integer of 0 to 100, and m + n satisfies 1 or more. ]   The said resin further contains 1 or more types selected from the group which consists of a styrene- (meth) acrylic resin, a styrene- (anhydrous) maleic acid resin, and a (meth) acrylic resin, The any one of Claims 1-3 The coated pigment described in 1.   An aqueous pigment dispersion comprising the coated pigment according to claim 1, water, and a basic compound.   Furthermore, the pigment aqueous dispersion of Claim 5 containing a crosslinking agent.   An ink for inkjet printing comprising the coated pigment according to any one of claims 1 to 4 or the pigment aqueous dispersion according to claim 5 or 6.   The ink for flexographic printing containing the coated pigment of any one of Claims 1-4, or the pigment aqueous dispersion of Claim 5 or 6.   An electrostatic image developing toner comprising the coated pigment according to any one of claims 1 to 4 or the pigment aqueous dispersion according to claim 5 or 6.   The coating composition containing the coated pigment of any one of Claims 1-4, or the pigment aqueous dispersion of Claim 5 or 6.   The water-soluble organic solvent, the water-soluble inorganic salt, the pigment (X) before coating and the α-olefin copolymer having an acidic group are mixed in a kneader, and the acidic group is added to 100 parts by mass of the pigment (X) before coating. The manufacturing method of the coating pigment which coat | covers 10 mass parts-50 mass parts of (alpha) -olefin copolymer which has this, and removes a water-soluble inorganic salt and a water-soluble organic solvent. The manufacturing method of the pigment aqueous dispersion which performs the following process sequentially.
Step 1: α-olefin copolymer having an acidic group, pigment (X) before coating, water-soluble inorganic salt, and a mixture containing a water-soluble organic solvent are kneaded and 100 parts by mass of pigment (X) before coating In contrast, the step of coating with 10 parts by mass or more and 50 parts by mass or less of an α-olefin copolymer having an acidic group Step 2: Step of removing water-soluble inorganic salt and water-soluble organic solvent Step 3: Add basic compound Step of neutralizing the acidic group Step 4: Adding a crosslinking agent to react the acidic group with the crosslinking agent