JP3499530B2 - Colored resin particles and manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored resin particles for forming a coating film having good pigment dispersibility and excellent color sharpness and transparency. More specifically, powder coatings with excellent heat-melting property and powder fluidity, heat-melting molding resins, spacers for manufacturing electronic parts such as liquid crystals, standard particles for electronic measuring instruments, electrophotography, electrostatic recording, static The present invention relates to a colored resin particle useful as a toner used in electroprinting and other molding materials.

[0002]

2. Description of the Related Art Conventionally, resin particles obtained by a method in which a resin or a solvent solution of a resin is emulsified and dispersed in an aqueous medium or an organic solvent medium to obtain a resin particle dispersion, and then the medium is removed. Is capable of easily obtaining fine particles with high sphericity by means of adjusting the shearing force applied to the system during emulsification / dispersion, controlling the surface tension by adding a surfactant, a polymeric protective colloid, etc. From
Widely applied to powder coatings, resin powders for hot-melt molding, spacers for manufacturing electronic parts such as liquid crystals, standard particles for electronic measuring instruments, toners used in electrophotography, electrostatic recording, electrostatic printing, etc. There is. The above-mentioned method for producing resin particles by emulsification / dispersion is not suitable for granulating a polymer resin / crosslinking type resin or the like that is poorly soluble in an organic solvent, but an organic solvent-soluble prepolymer is used for organic conversion. A solvent solution is prepared, and this is emulsified / dispersed with a polyfunctional extender capable of reacting with a prepolymer, and a polymer resin is used during the emulsification / dispersion process in an aqueous medium.
By forming a cross-linking resin, it is possible to design a wide range of resin properties such as rheology required for the above applications.
However, when a pigment or the like is dispersed in order to color the particles in order to design it as a toner used for powder coating, electrophotography, electrostatic recording, electrostatic printing, etc., adjustment of organic solvent solution / dispersion, emulsification / dispersion In some cases, the secondary aggregation of the pigment may occur in each step of solvent removal, and there is a problem that the color sharpness and transparency of the coating film deteriorate. In order to solve this problem, it has been proposed to improve the pigment dispersibility with a pigment dispersant, and as an application example to a toner in JP-A No. 11-72958, an acid value of 11 mgKOH / g or more and 27 mg or more is proposed.
The utility of a polymer dispersant having a KOH / g or less and an amine value of 1 or more and 100 or less is disclosed. However, although this dispersant retains the pigment dispersibility at a temperature of about 30 ° C., it is inferior in the pigment dispersion stability at a high temperature of, for example, about 50 ° C., and it takes a long time for the solvent removal step. Have a point. Further, since the dispersibility of the pigment is deteriorated when the extender is added, there is a problem that the underwater elongation method cannot be adopted and a wide range of resin designs cannot be performed.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances in the prior art. That is, it is an object of the present invention to provide colored resin particles having good pigment dispersibility, color sharpness and transparency.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have obtained pigmented resin particles having good pigment dispersibility and excellent color sharpness and transparency of a coating film. On the other hand, they have found that it is effective to disperse the pigment with a dispersant having a specific functional group, and have arrived at the present invention. That is, the present invention provides colored resin particles obtained by dispersing a colorant (C) in a resin (B) with a dispersant (A) having a phosphoric acid (salt) group; a colorant (C) in the resin (B). Is dispersed by a dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group, and the main skeleton of the dispersant (A) is , A polyether, a polyester and a copolymer thereof, and the gel filtration chromatography of the dispersant (A) (G
PC) has a weight average molecular weight of 1,000 to 500,0
Colored resin particles of 00; colorant (C) in resin (B)
Is phosphoric acid (salt) group, sulfonic acid (salt) group and sulfuric acid (salt)
Colored resin particles dispersed by a dispersant (A) having a functional group selected from the group of groups, and the resin (B) being a resin selected from the group of polyurethane resin, epoxy resin and polyester resin; phosphoric acid ( A resin (B) in which a colorant (C) is dispersed by a dispersant (A) having a functional group selected from the group of a salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group, in an organic solvent. Dissolved in or dispersed in, and the resulting dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium and granulated; and a phosphoric acid (salt) group and a sulfonic acid (salt). Reactive group-containing prepolymer (α) which is a precursor of a resin (B) in which a colorant (C) is dispersed by a dispersant (A) having a functional group selected from the group consisting of a group and a sulfuric acid (salt) group. Is dissolved or dispersed in an organic solvent to dissolve the Is to emulsify or disperse the dispersion in an aqueous medium containing an extender and / or a cross-linking agent (β), and at the same time extend and / or cross-link (α) to form a resin (B) for granulation. And a method for producing colored resin particles.

[0005]

The present invention will be described in detail below. In the present invention, a dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group.
May be a low molecular weight compound or a high molecular weight compound, but from the viewpoint of dispersion stability and compatibility with the resin (B), preferably, the weight average molecular weight by gel filtration chromatography (GPC) is 1,000 to 500,000, particularly It is preferably 1500 to 300,000. The phosphoric acid (salt) group, the sulfonic acid (salt) group and the sulfuric acid (salt) group function as adsorption sites for the pigment. The phosphoric acid (salt) group also includes those partially converted to alkyl (C1-20) esters.
Examples of salts include alkali metal salts (lithium salt, sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, calcium salt, etc.), amine salts (trimethylamine, triethylamine, triethanolamine, dimethyloctylamine, dimethyllauryl). Amine, dimethylaminoethanol, aminomethylpropanol, pyridine, ethylenediamine, etc.), ammonium salt and the like. When the dispersant (A) is a polymer compound (including an oligomer), the main skeleton thereof is selected from the group consisting of (co) polymers of vinyl monomers, polyethers, polyesters and copolymers thereof. preferable. The content (molecular weight g / equivalent) of the phosphoric acid (salt) group, sulfonic acid (salt) group or sulfuric acid (salt) group in the dispersant (A) is usually 2
It is from 00 to 20000, preferably from 400 to 5000.

The dispersant (A) is, for example :; a vinyl-based monomer having a phosphoric acid (salt) group or a sulfonic acid (salt) group and another vinyl-based monomer are copolymerized; Directly esterifying or transesterifying a compound having a hydrogen group with a compound having a phosphoric acid (ester) group, a sulfonic acid (ester) group, or a sulfuric acid (ester) group, or one or more active hydrogens at the terminals A compound having a group is reacted with a sulfating agent or a sulfonating agent to introduce a sulfonic acid group or a sulfating group; a compound having a phenyl group is sulfonated with a sulfonating agent; a double bond in the molecule It can be synthesized by a method such as reacting a compound having the above with acidic sodium sulfite.

The vinyl monomers having a sulfonic acid (salt) group described above include methyl vinyl sulfonate, styrene sulfonic acid (salt), α-methyl styrene sulfonic acid (salt), sulfopropyl (meth) acrylate, 2-Hydroxy-3- (meth) acryloxypropylsulfonic acid (salt), 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid (salt), 2- (meth) acryloyloxyethanesulfonic acid (salt) ), 3-
(Meth) acryloyloxy-2-hydroxypropanesulfonic acid (salt), 2- (meth) acrylamide-2-
Methylpropanesulfonic acid (salt), 3- (meth) acrylamido-2-hydroxypropanesulfonic acid (salt),
Examples thereof include alkyl (C3-18) allyl sulfosuccinic acid (salt). Examples of vinyl monomers having a phosphoric acid (salt) group include (meth) acrylic acid hydroxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2.
-Acryloyloxyethyl phosphate, (meth) acrylic acid alkylphosphonic acids, such as 2-acryloyloxyethylphosphonic acid (salt). Examples of other vinyl-based monomers include the following (1) to (6). (1) Aromatic vinyl hydrocarbons: styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, etc. (2) Carboxyl group-containing vinyl monomer and its Salt: (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, etc. (3) Hydroxyl group-containing vinyl monomer Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxyethyl propenyl ether, Sugar allyl ether, etc. (4) The amino group-containing vinyl monomer, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate, t-butylaminoethylmethacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-aceto Amino acrylate, vinyl imidazole,
N-vinylpyrrole, N-vinylthiopyrrolidone, N-
Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole,
Amino imidazole etc. are mentioned. The most desirable of these are dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
N-aminoethyl (meth) acrylamide, morpholinoethyl (meth) acrylate and 2-vinylpyridine. (5) Epoxy group-containing vinyl monomer glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc. (6) Alkyl (meth) acrylate Alkyl having an alkyl group having 1 to 20 carbon atoms (Meta)
Acrylates, such as methyl (meth) acrylate,
Examples thereof include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, and eicosyl (meth) acrylate.

In the above, the polymerization can be synthesized by a known polymerization method such as suspension, emulsion or solution polymerization of the above monomer using a radical polymerization catalyst. The content of the other vinyl-based monomer as a constituent unit is usually 0 to 98 mol%, preferably 5 to 95 mol%. The polymerization temperature is
It is usually 10 to 200 ° C., preferably 40 to 180 ° C., and the reaction time is generally 1 to 48 hours, preferably 4 to 2
4 hours. Examples of radical polymerization catalysts include azo-based catalysts: azoisobutyronitrile, azoisodimethylvaleronitrile, etc., peroxide-based catalysts: t-butylperoxide, cumylperoxide, etc., persulfate-based catalysts: sodium persulfate, persulfate. Ammonium sulfate, potassium persulfate and the like can be used. A polymerization solvent may be used during the reaction, and toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol or the like can be used.

In the above, the compound having at least one active hydrogen group at the terminal is 1 to 3 having 6 to 32 carbon atoms.
Examples thereof include polyhydric alcohols, polyethers, polyesters (polycondensation type aliphatic polyesters and aromatic polyesters, and polycaprolactone). 6 to 3 carbon atoms
Examples of the 1- to 2-hydric alcohols include hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, benzyl alcohol, 1,6-hexanediol and 1,8-octanediol. Is mentioned. Examples of the polyether include polyalkylene ether glycol having a weight average molecular weight of 100 to 10,000 (polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol having 5 to 18 carbon atoms (1,4-cyclohexanediene). Methanol, hydrogenated bisphenol A
Etc.) or bisphenols having 12 to 23 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) and alkylene oxides having 2 to 18 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, α-olefin oxide, etc.) (The number of added moles is 2 to 20) and the like.

Examples of aliphatic polyesters and aromatic polyesters include polycondensates of polyols with polycarboxylic acids or their acid anhydrides or their lower alkyl esters. The polyol is a diol (1) and a trivalent or higher valent polyol (2), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (3) and a trivalent or higher valent polycarboxylic acid (4). These acid anhydrides or lower alkyl esters are mentioned. The ratio of the polyol to the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1, more preferably 1.3
/1-1.02/1.

Examples of the diol (1) include alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, Dodecanediol, tetradecanediol, etc.); Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogen) Added bisphenol A); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (ethylene) Oxide, propylene oxide, butylene oxide, etc.) adduct; alkylene oxides of the above bisphenols (ethylene oxide,
Propylene oxide, butylene oxide, etc.) and the like. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycol having 2 to 12 carbon atoms. It is a combination of. Examples of the trihydric or higher polyol (2) include trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (trisphenol PA, etc.) ); Novolac resins (phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolak resins. Of these, preferred are polyhydric aliphatic alcohols having 3 to 8 valences or higher and alkylene oxide adducts of novolak resins, and particularly preferred are alkylene oxide adducts of novolak resins.

Examples of the dicarboxylic acid (3) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenylsuccinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acid (maleic acid, Fumaric acid, etc.); branched alkylene dicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid,
Pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid) Etc.) and the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the tricarboxylic or higher polycarboxylic acid (4) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid,
Pyromellitic acid, etc.) and the like. In addition, as the dicarboxylic acid (3) or the polycarboxylic acid (4) having a valence of 3 or more, an acid anhydride or a lower alkyl ester (such as a methyl ester, an ethyl ester or an isopropyl ester) of the above may be used.

Examples of the polycaprolactone include polyadducts of γ-butyrolactone and ε-caprolactone having a weight average molecular weight of 100 to 5,000.

Examples of the compound having a phosphoric acid (ester) group, a sulfonic acid (ester) group and a sulfuric acid (ester) group include phosphoric acid, a (mono-, di-, tri) alkyl ester having 1 to 12 carbon atoms, sulfuric acid and chloro. Examples thereof include sulfonic acid, sulfuric anhydride, fuming sulfuric acid, and sulfamic acid. Sulfating agent,
Examples of the sulfonating agent include sulfuric acid, chlorosulfonic acid, sulfuric acid anhydride, fuming sulfuric acid, sulfamic acid and the like. In the above, the reaction can be synthesized by esterification, sulfonation, and sulfation using the above compound by a known method. The reaction temperature is generally 0 to 150 ° C., preferably 10
The reaction time is usually 1 to 48 hours, preferably 4 to 24 hours.

In the above, examples of the compound having a phenyl group include polystyrene and the like. Examples of the sulfonating agent are the same as those mentioned above. The reaction temperature is usually 0 to 150 ° C., preferably 30 to
It is 120 ° C.

The dispersant (A) preferably has good compatibility with the resin (B) in order to stably disperse the pigment in the matrix. The SP value of the (A) and the resin (B) are The difference from the SP value (ΔSP) is usually 0 to 1.0, preferably 0 to 0.8, and particularly preferably 0 to 0.5 from the viewpoint of compatibility between the two.

The amount of the dispersant (A) to be used is usually 1 to 100 parts by weight of the pigment from the viewpoint of improving the pigment dispersibility and affecting various characteristics (chargeability, fluidity, etc.) due to moisture absorption.
150 parts by weight, preferably 3 to 120 parts by weight, particularly preferably 5 to 100 parts by weight, and usually 0.01 to 90 parts by weight, preferably 0.
05 to 80 parts by weight, particularly preferably 0.1 to 70 parts by weight.

In the present invention, any resin can be used as the resin (B) as long as it is a known resin. For example, as the addition polymerization resin (vinyl resin), polyethylene, polypropylene, polystyrene, styrene- ( (Meth) alkyl acrylate copolymer, styrene-butadiene copolymer, acrylic acid-alkyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Maleic anhydride copolymer; Polycondensation resin, polyester resin, unsaturated polyester resin, polyamide resin, polyimide resin, polycarbonate resin, silicon resin; Polyaddition resin, polyurethane resin, polyurea resin, epoxy resin; addition Examples of the polymer resin include a phenol resin, a melamine resin, and an aniline resin; and other resins such as an ionomer resin. Of these, preferred are vinyl resins, polyester resins,
Polyurethane resin, polyurea resin and epoxy resin.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl-based monomer include the same ones as described above. The vinyl resin can be synthesized by a known polymerization method such as suspension, emulsion or solution polymerization of the above monomer using a radical polymerization catalyst. The polymerization temperature is generally 10 to 200 ° C., preferably 40 to 180 ° C., and the reaction time is generally 1 to 48 hours, preferably 4 to 24 hours. Examples of radical polymerization catalysts include azo-based catalysts: azoisobutyronitrile, azoisodimethylvaleronitrile, etc., peroxide-based catalysts: t-butylperoxide, cumylperoxide, etc., persulfate-based catalysts: sodium persulfate, persulfate. Ammonium sulfate, potassium persulfate and the like can be used.
A polymerization solvent may be used during the reaction, and toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol or the like can be used.

Examples of the polyester resin include polycondensates of the above-mentioned polyol and the above-mentioned polycarboxylic acid or its acid anhydride or its lower alkyl ester. Examples of the polyol include those similar to the diol (1) and the polyol (2) having a valence of 3 or more, and examples of the polycarboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof include the dicarboxylic acid (3) and a valence of 3 or more. The same as the polycarboxylic acid (4) and the acid anhydride or lower alkyl ester thereof.

As the polyurethane resin, polyisocyanate (5) and active hydrogen group-containing compound (D) {water, polyol [the diol (1) and trivalent or higher valent polyol (2)], dicarboxylic acid (3), 3 -Valent polycarboxylic acid (4), polyamine (6), polythiol (7)
Etc.} and the like.

As the polyisocyanate (5), aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in NCO group, the same applies hereinafter), aliphatic polyisocyanate having 2 to 18 carbon atoms, and 4 to 15 carbon atoms. Alicyclic polyisocyanate, araliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanate) Nulate groups, oxazolidone group-containing modified products, etc.) and mixtures of two or more thereof.
Specific examples of the aromatic polyisocyanate include 1,
3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or
Or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane with a small amount (for example, 5 to 20% by weight)] Mixture with trifunctional or higher functional polyamine]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanate Natophenyl sulfonyl isocyanate, etc. Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate. 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6
-Diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,
Examples thereof include aliphatic polyisocyanates such as 6-diisocyanatohexanoate. Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4′-.
Diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl)
-4-cyclohexene-1,2-dicarboxylate,
2,5- and / or 2,6-norbornane diisocyanate and the like can be mentioned. Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′,
α'-Tetramethylxylylene diisocyanate (TM
XDI) and the like. The modified polyisocyanate includes modified MDI (urethane modified MDI,
Carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI and other modified polyisocyanates, and mixtures of two or more thereof [eg, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer) in combination] are included. Be done.
Of these, preferred are 6 to 15 aromatic polyisocyanates, C4 to C12 aliphatic polyisocyanates, and C4 to C15 alicyclic polyisocyanates, and particularly preferred are TDI, MDI, HD
I, hydrogenated MDI, and IPDI.

Examples of the polyamine (6) include aliphatic polyamines (C2 to C18): aliphatic polyamine {C2
-C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine,
Iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; these alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substitution products [dialkyl (C1 ~ C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,
5-hexamethylenediamine, methyliminobispropylamine, etc.]; Alicyclic or heterocyclic ring-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] 5] Undecane, etc.]; Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine,
Tetrachloro-p-xylylenediamine, etc.), alicyclic polyamine (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,
Heterocyclic polyamines (C4 -C1) such as 4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline)
5): piperazine, N-aminoethylpiperazine, 1,
Aromatic polyamines (C6 to C20) such as 4-diaminoethylpiperazine and 1,4 bis (2-amino-2-methylpropyl) piperazine: unsubstituted aromatic polyamines [1,2-, 1,3- and 1 , 4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-
4,4 ', 4 "-triamine, naphthylenediamine and the like; nuclear-substituted alkyl groups [methyl, ethyl, n- and i
-Aromatic polyamines having C1 -C4 alkyl groups such as propyl, butyl, etc., eg 2,4- and 2,6-
Tolylenediamine, crude tolylenediamine, diethyl tolylenediamine, 4,4'-diamino-3,3'-
Dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone,
1,3-dimethyl-2,4-diaminobenzene, 1,3
-Diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-
2,5-diaminobenzene, 1,4-diisopropyl-
2,5-diaminobenzene, 1,4-dibutyl-2,5
-Diaminobenzene, 2,4-diaminomesitylene,
1,3,5-triethyl-2,4-diaminobenzene,
1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-
Diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1, 5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl-4,4' -Diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3
′, 5,5′-Tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-Diaminodiphenylmethane, 3,5-diisopropyl-3′-methyl-2
', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-
Diamino-3,3'-dimethyldiphenylmethane, 3,
3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraisopropyl-4,4'-diaminobenzophenone, 3,3 ',
5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone], and mixtures of these isomers in various proportions. An aromatic polyamine having a nucleus-substituted electron-withdrawing group (halogen such as Cl, Br, I, F; an alkoxy group such as methoxy and ethoxy; a nitro group) [methylenebis-o-chloroaniline, 4-chloro-o-phenylene Diamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine,
5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,
3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-) Chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide,
Bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2
-Bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; aromatic polyamine having a secondary amino group [of the above-mentioned aromatic polyamines -NH2 Part or all of which is replaced by -NH-R '(R' is an alkyl group such as a lower alkyl group such as methyl and ethyl)] [4,4'-di (methylamino) diphenylmethane, 1-methyl- 2-Methylamino-4-aminobenzene, etc.], Polyamide polyamine: Condensation of dicarboxylic acid (such as dimer acid) and excess polyamines (more than 2 mol per mol of acid) (the above alkylenediamine, polyalkylenepolyamine, etc.) Polyether polyamines such as low molecular weight polyamide polyamines obtained by Ren glycol etc.)
And hydrides of cyanoethylated compounds.

Examples of the polyurea resin include the reaction products of the above poly (di, tri) isocyanate (3) and amines (4).

Examples of the polythiol (7) include ethylenedithiol, 1,4-butanedithiol and 1,6-hexanedithiol.

As the epoxy resin, polyepoxide (8) and active hydrogen group-containing compound (D) {water, polyol [the above-mentioned diol (1) and trivalent or higher valent polyol (2)], dicarboxylic acid (3), trivalent The above polycarboxylic acid (4), polyamine (6), polythiol (7)
Etc., and a polyaddition product of a dicarboxylic acid (3) or a polycarboxylic acid (3) having a valence of 3 or more with an acid anhydride and the like.

The polyepoxide (8) of the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. As the polyepoxide (8), preferred is one having an epoxy group of 2 to 2 in the molecule from the viewpoint of mechanical properties of the cured product.
It has 6 pieces. The epoxy equivalent (molecular weight per one epoxy group) of the polyepoxide (8) is usually 65.
˜1000, preferably 90 to 500.
If the epoxy equivalent exceeds 1,000, the crosslinked structure becomes loose and the physical properties of the cured product such as water resistance, chemical resistance and mechanical strength deteriorate, while it is difficult to synthesize those with an epoxy equivalent of less than 65. is there.

Examples of the polyepoxide (8) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds and aliphatic polyepoxy compounds. Examples of aromatic polyepoxy compounds include glycidyl ethers and glycidyl esters of polyhydric phenols, glycidyl aromatic polyamines, and glycidyl compounds of aminophenols. Examples of the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4 ′
-Dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether, p-glycidyl phenyl dimethyltolyl bisphenol A glycidyl ether, trismethyl-tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furo orange glycidyl ether, 4,4'-oxybis (1 , 4-Phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-
Phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolac resin, glycidyl ether of limonenephenol novolac resin, obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin Examples thereof include a polyglycidyl ether body of polyphenol obtained by a condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde, and a polyglycidyl ether body of a polyphenol obtained by a condensation reaction of resorcin and acetone. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′,
N'-tetraglycidyl xylylenediamine, N, N,
N ', N'- tetraglycidyl diphenyl methanediamine etc. are mentioned. Furthermore, in the present invention, as the aromatic system, a triglycidyl ether of P-aminophenol, a diglycidyl urethane compound obtained by an addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, and a polyol obtained by reacting the two reaction products with a polyol are also obtained. Also included are glycidyl group-containing polyurethane (pre) polymers and diglycidyl ethers of alkylene oxide (ethylene oxide or propylene oxide) adducts of bisphenol A. Examples of the heterocyclic polyepoxy compound include trisglycidyl melamine; examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, and bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale,
3,4-epoxy-6-methylcyclohexylmethyl-
3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,3
4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester and the like can be mentioned. The alicyclic compounds also include nuclear hydrogenated products of the above aromatic polyepoxide compounds; the aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols and polyglycidyl esters of polyhydric fatty acids. Body, and glycidyl fatty amines. Examples of the polyglycidyl ether of polyhydric aliphatic alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol. Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerolin polyglycidyl ether, etc. Is mentioned. Examples of polyglycidyl ester of polyhydric fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In addition, in the present invention, the aliphatic system also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. The polyepoxide of the present invention may be used in combination of two or more kinds.

Examples of the colorant (C) in the present invention include white pigments, yellow pigments, orange pigments, red pigments, purple pigments,
Examples include blue pigments, green pigments, brown pigments, black pigments and the like. Each of the above pigments includes an inorganic pigment and an organic pigment, and specific examples of the inorganic pigment include titanium oxide, carbon black, chromium oxide, ferrite, red iron oxide, and dark blue.

Specific examples of carbon black include carbon blacks # 2400 and # 2350 manufactured by Mitsubishi Chemical Corporation.
# 2300, # 2200, # 1000, # 980, # 9
70, # 960, # 950, # 900, # 850, # 6
50, # 4000, # 4010, # 55, # 52, # 4
7, # 45, # 44, # 40, # 33, # 32, # 3
0, # 20, # 10, # 5, # 3050, # 3150,
# 3250, # 3750, # 3950, MCF88, M
A600, MA7, MA8, MA11, MA100, M
A220, IL30B, IL31B, IL7B, IL1
1B, IL52B, CF9, Diamond Black A, N22
0M, 234, I, LI, II, N339, SH, SH
A, LH, HA, SF, N550M, E, G, R, G
(Both are trade names). Among these carbon blacks, carbon blacks having a pH of 2 to 9 are preferable from the viewpoint of dispersion stability. Further, carbon black that has been subjected to a surface treatment can be used. Examples of the surface treatment method include polymer grafting, surface oxidation treatment, and surface adsorption treatment. These can be performed by a known method.

Organic pigments include phthalocyanine pigments,
Azo lake type, monoazo type, disazo type, condensed azo type,
Examples thereof include chelate azo type, quinacridone type, dioxazine type, isoindolinone type, thioindigo type, perylene type, quinophthalone type, anthraquinone type, carmine type, naphthol type, pyrazolone type and dibromoanthrone type.

Specific examples of the organic pigment include the following. [Displayed by color index (CI) number] Yellow pigment: CI Pigment Yellow 11, 20, 24, 3
1, 53, 83, 86, 93, 99, 108, 109,
110, 117, 125, 129, 137, 138, 1
39, 147, 148, 150, 151, 153, 15
4, 166, 167, 168 Orange pigment: CI Pigment Orange 36, 38, 43, 5
1, 55, 59, 61 Red pigment: CI Pigment Red 9, 97, 105, 12
2, 123, 149, 150, 155, 168, 17
1, 175, 176, 177, 180, 192, 20
9, 215, 216, 217, 220, 223, 22
4, 226, 227, 228, 240 Purple pigment: CI Pigment Violet 19, 23, 29, 3
0, 32, 37, 39, 40, 50 Blue pigment: CI Pigment Blue 1, 2, 15, 15:
3, 15: 4, 15: 6, 22, 60, 64, 66 Green pigment: CI Pigment Green 7, 36, 37 Brown pigment: CI Pigment Brown 23, 25, 26, 28 Black pigment: CI Pigment Black 1, 7 The preferred system varies depending on the application, and may be appropriately selected.

The content of the colorant (C) is usually 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, particularly preferably 2 to 2 parts by weight based on 100 parts by weight of the resin (B).
0 parts by weight. A known dye, magnetic powder, or the like may be used in combination with the above pigment.

The colored resin particles of the present invention can be obtained by the following method. (I): The resin (B) in which the colorant (C) is dispersed by the dispersant (A) is dissolved or dispersed in an organic solvent, and the dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium. , Granulate. (II): The reactive group-containing prepolymer (α), which is a precursor of the resin (B) in which the colorant (C) is dispersed by the dispersant (A), is dissolved or dispersed in an organic solvent, The solution or dispersion is emulsified or dispersed in an aqueous medium containing an extender and / or a crosslinking agent (β), and (α) is extended and / or crosslinked to form a resin (B),
Granulate.

In the above method (I), the colorant (C)
Can be dispersed in the resin (B) without a solvent in the presence of the dispersant (A) or, if necessary, with a solvent. As the solvent, toluene, xylene, ethyl acetate,
Methyl ethyl ketone or a mixed solvent of two or more thereof can be used. The amount of the solvent used is usually 0 to 300 parts, preferably 0 to 100 parts, and more preferably 5 to 50 parts, based on 100 parts by weight of the resin (B), the colorant (C) and the dispersant (A). . When a solvent is used, it is heated and removed under normal pressure or reduced pressure after the completion of emulsion dispersion.

As a method for dispersing the colorant (C) in the above-mentioned dissolution / dispersion liquid, a wet dispersion by a medium using zirconia beads or the like, a high shear of a disper, a homomixer, a roll mill, a twin-screw kneader or the like is used. It can be carried out by dispersion. When emulsifying / dispersing a solution / dispersion liquid of the resin (B), the colorant (C) and the dispersant (A), in order to make the particle size distribution sharp, organic and inorganic fine particles are previously dispersed in an aqueous dispersion medium. A method of emulsifying / dispersing the above-mentioned dissolved / dispersed liquid is preferable. Organic fine particles include styrene,
As inorganic fine particles such as copolymers of vinyl monomers such as (meth) acrylic acid and (meth) acrylic acid ester, calcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide. , Aluminum hydroxide and the like.

The size of the fine particles is usually 0.01 to 100.
μm, which may be appropriately selected depending on the intended use of the resin fine particle composition. The amount of the fine particles used is usually 1 to 100 parts of the above-mentioned dissolution / dispersion liquid.

As the emulsifier or dispersant used in combination, known surfactants, aqueous polymers and the like can be used. The amount of the emulsifier or dispersant used is usually 0.1 to 10 parts of the above-mentioned dissolution / dispersion liquid.

As the surfactant, anionic surfactants such as carboxylic acid or its salt, sulfate ester salt, carboxymethylated salt, sulfonate salt and phosphate ester salt; quaternary ammonium salt type, amine salt Type cationic surfactants; carboxylate type amphoteric surfactants (amino acid type amphoteric surfactants, betaine type amphoteric surfactants, etc.), sulfate ester type amphoteric surfactants, sulfonate type amphoteric surfactants Examples thereof include amphoteric surfactants such as activators and phosphoric acid ester salt type amphoteric surfactants; nonionic surfactants such as alkylene oxide addition type and polyvalent alcohol type.

Examples of the aqueous polymer include cellulosic compounds such as carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof; polyvinyl alcohol, gelatin, starch, gum arabic, chitin,
Chitosan: Polyalkylene oxide such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide and the like are used.

When the dispersion of the resin (B), the colorant (C) and the dispersant (A), or a solvent solution of this dispersion is emulsified and dispersed in an aqueous medium to obtain the colored resin particles of the present invention. The dispersing device used for is not particularly limited as long as it is commercially available as an emulsifying machine or a dispersing machine, and examples thereof include a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), and TK auto homomixer (special machine). Chemical Industry Co., Ltd.) and other batch type emulsifiers, Ebara Milder (manufactured by Arihara Seisakusho Co., Ltd.), TK pipeline homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantec Co., Ltd.),
Continuous emulsifiers such as slasher, trigonal wet type fine pulverizer (Mitsui Miike Kakoki Co., Ltd.), Capitron (Eurotec Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizho Kogyo Co., Ltd.), High-pressure emulsifiers such as Nanomizer (made by Nanomizer), APV Gaulin (made by Gaulin), membrane emulsifiers such as membrane emulsifier (made by Chilling Industry Co., Ltd.), vibrating emulsion such as vibro mixer (made by Chilling Industry Co., Ltd.) And an ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson).

As the aqueous medium, water may be used alone, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methylethylketone, etc.), and the like. As the temperature at the time of dispersion,
Usually 0 to 150 ° C (under pressure), preferably 40 to 98 ° C
Is. The higher temperature is preferable because the viscosity of the dispersion of the resin (B), the colorant (C) and the pigment dispersant (A), or the solvent solution of this dispersion is low, and the dispersion is easy.

The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 100 parts by weight, based on 100 parts of the solution / dispersion of the resin (B), the colorant (C) and the dispersant (A).
~ 1,000 parts by weight. Less than 50 parts by weight (α)
The dispersion state of becomes worse. If it exceeds 2,000 parts by weight, it is not economical.

Size of Colored Resin Particles Obtained (D50)
Is usually 0.1 to 500 μm, and the particle size distribution (volume average particle size Dv / number average particle size Dn) is usually 1.05 to 5.0, and any of them may be appropriately set according to the intended use. Good.

In the method (II), the reactive group-containing prepolymer (α), which is a precursor of (B), is used in place of the resin (B) in the method (I), and it is emulsified in an aqueous medium or This is a method of granulating by performing elongation and / or cross-linking reaction with a stretching agent and / or a cross-linking agent (β) in an aqueous medium when forming a resin (B), and granulating. It is possible to lower the viscosity and emulsify
It is more preferable than the method (I) in that it is advantageous in reducing the particle size of the particles at the time of dispersion and sharpening the particle size distribution, and that the polymer resin and cross-linking resin that are poorly soluble in an organic solvent can be made into particles.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) with the extender and / or the crosslinking agent (β) include the following. : A combination of the reactive group contained in (α) is a functional group (α-1) capable of reacting with an active hydrogen compound, and the (β) is a compound containing an active hydrogen group (β-1). : The reactive group of (α) is an active hydrogen group (α-2), and the compound (β-) capable of reacting with the active hydrogen group (β-
Combination of 2).

In the above, examples of the functional group (α-1) capable of reacting with the active hydrogen compound include an isocyanate group, a blocked isocyanate group, an epoxy group, an acid anhydride group and an acid halide group. Among these, preferred are an isocyanate group, a blocked isocyanate group and an epoxy group. Examples of the blocked isocyanate group include those obtained by blocking the isocyanate group with a phenol derivative, oxime, caprolactam, or the like.

Examples of the active hydrogen group-containing compound (β-1) include polyamines, polyamines which may be blocked with a removable compound, polyols, polymercaptans and water. Among these, preferred are polyamines, polyamines optionally blocked with a removable compound, polyols and water. Examples of the polyamines include the same as the above polyamines (4).

Examples of the polyamines which may be blocked with a removable compound include the polyamines (4)
And ketomine compounds and oxazoline compounds obtained from ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

The polyols are preferably the same as the above-mentioned polyol (1), a diol alone or a mixture of a diol and a small amount of a trivalent or more polyol. Polymercaptans include ethylenedithiol, 1,4
Examples include butanedithiol and 1,6-hexanedithiol. Furthermore, if necessary, a reaction terminator can be used together with (β-1). As a reaction terminator,
Monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.); monoamines blocked (ketimine compounds, etc.); monools (methanol, ethanol, isopropanol, butanol, phenol; monomercaptans (butylmercaptan, laurylmercaptan, etc.), etc. Can be mentioned.

As the active hydrogen group (α-2) contained in the prepolymer (α) in the above, an amino group, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), a mercapto group, a carboxyl group and those capable of being eliminated. Examples thereof include an organic group blocked with a compound. Among these, preferred are organic groups blocked with a compound capable of eliminating an amino group, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) and an amino group. Examples of the organic group blocked with a compound capable of leaving an amino group include a ketimine group and an oxazoline group obtained by reacting an amino group with a ketone (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone).

Compound (β-2) capable of reacting with active hydrogen group
Examples thereof include polyisocyanates, polyepoxides, polycarboxylic acids, polyacid anhydrides and polyacid halides. Of these, preferred are polyisocyanates and polyepoxides.

Examples of the polyisocyanates include the same as the above polyisocyanates (3), and the preferred ones are also the same.

The polyepoxides include polyglycidyl ether (ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac glycidyl tether, etc .; diene oxide (pentadiene dioxide,
Hexadiene dioxide etc.) and the like. Of these, preferred is polyglycidyl ether.

As the polycarboxylic acid, the same as the above-mentioned polycarboxylic acid (2) can be mentioned, and the preferable ones are also the same.

Examples of the polycarboxylic acid anhydride include pyromellitic acid anhydride. Examples of the polyacid halides include the above-mentioned acid halides (acid chloride, acid bromide, acid iodide) and the like. Furthermore, if necessary, a reaction terminator can be used together with (β-2). As the reaction terminator, monoisocyanate (lauryl isocyanate, phenyl isocyanate, etc.), monoepoxide (butyl glycidyl ether, etc.), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, etc.); monoamine blocked (ketimine compound, etc.) Monools (methanol, ethanol, isopropanol, butanol, phenol); monomercaptans (butyl mercaptan, lauryl mercaptan, etc.) and the like.

The proportion of the extender and / or the cross-linking agent (β) is such that the number of moles of reactive groups in the reactive group-containing prepolymer (α) [α] and the number of active hydrogen groups in β are [β]. Mole ratio of
[α] / [β] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1.
~ 1 / 1.2. If (β) is water, the water is 2
Treated as a valent active hydrogen compound.

The prepolymer (α) is polyester,
Prepolymers such as epoxy resins and polyurethanes may be mentioned. Examples of the epoxy resin include addition condensation products of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) and epichlorohydrin. Examples of polyurethanes include polyaddition products of the above polyols and the above polyisocyanates.

As a method of incorporating a reactive group into polyester, epoxy resin, polyurethane, etc .: A method of leaving one functional component in excess to leave a functional group of the structural component at the terminal: And a method of reacting a compound containing a functional group with a reactive group.

By the method described above, a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate. A group-containing polyurethane prepolymer is obtained. In the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of the polyol (1) to the polycarboxylic acid (2) is the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ], Usually 2/1 to 1/1, preferably 1.5 / 1 to 1 /
1, more preferably 1.3 / 1 to 1.02 / 1. In the case of the other constituents and the terminal prepolymer, the ratio is the same except that the constituents are changed.

By the method of (1), the prepolymer obtained in (1) is reacted with polyisocyanate to obtain an isocyanate group-containing prepolymer, and the blocked polyisocyanate is reacted to obtain a blocked isocyanate group-containing prepolymer. An epoxy group-containing prepolymer is obtained by reacting polyepoxide,
An acid anhydride group-containing prepolymer is obtained by reacting a polyanhydride. Examples of the polyisocyanate include those similar to the above polyisocyanate (3),
The same applies to the preferred ones.

The ratio of the compound containing a reactive group is such that when a polyester containing hydroxyl group is reacted with polyisocyanate to obtain a polyester prepolymer containing an isocyanate group, the ratio of polyisocyanate is such that the isocyanate group [NCO] and the hydroxyl group are Hydroxyl group of contained polyester
The molar ratio [NCO] / [OH] of [OH] is usually 5/1 to
It is 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. In the case of the other constituents and the terminal prepolymer, the ratio is the same except that the constituents are changed.

The number of reactive groups contained in one molecule in the prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average.
It is an individual. Within the above range, the molecular weight of the elongation and / or crosslinking reaction product of (α) becomes high. The number average molecular weight of (α) is usually 500 to 30,000, preferably 1,000 to 20,000, and more preferably 2,000.
It is 0 to 10,000. The weight average molecular weight of (α) is
1,000-50,000, preferably 2,000-4
10,000, more preferably 4,000 to 20,000
It is 0. The melt viscosity of (α) at 100 ° C. is usually 2,000 poise or less, preferably 1,000 poise or less. It is preferable that the porosity is 2,000 poise or less, since resin particles having a sharp particle size distribution can be obtained with a small amount of solvent.

Furthermore, if necessary, a reaction terminator may be used together with (β). Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and blocked products thereof (ketimine compounds).

The elongation and / or crosslinking reaction time depends on the reactive group structure of the prepolymer (α) and the elongation agent and / or
Alternatively, it is selected depending on the reactivity due to the combination of the crosslinking agents (β), but is usually 10 minutes to 40 hours, preferably 2 to
24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 50 to 120 ° C. Further, a known catalyst can be used if necessary. Specifically, for example, in the case of an isocyanate reaction, dibutyltin laurate, dioctyltin laurate and the like can be mentioned.

Further, together with the prepolymer (α),
A polymer [so-called dead polymer] which does not react with (α) and (β) during the reaction of (α) and (β) in an aqueous medium may be contained in the system. That is, it is also possible to contain a resin that has not been subjected to an elongation reaction or a crosslinking reaction, together with a resin in which the prepolymer (α) has been subjected to an elongation reaction and / or a crosslinking reaction in an aqueous medium.

In the present invention, the Tg, the molecular weight, the SP value and the inter-crosslinking point molecular weight of the resin produced by the elongation and / or crosslinking reaction of (α) and (β) vary depending on the use, and may be appropriately adjusted. Good.

In the present invention, other known additives may be used depending on the application when forming the colored resin particles. Examples of the additive include a filler, an antistatic agent, a colorant, a release agent, a charge control agent, an ultraviolet absorber and an antioxidant. The above-mentioned other additives may be mixed when the dispersion is formed in the aqueous medium, but after (α) and the additive are mixed in advance, the mixture is added and dispersed in the aqueous medium. Is more preferable. Further, in the present invention, the additive does not necessarily have to be mixed when the particles are formed in the aqueous medium, and may be added after the particles are formed. For example, the colorant may be added by a known dyeing method after forming particles not containing the colorant.

The colored resin particles of the present invention are obtained by solid-liquid separation with a centrifugal separator, a spakura filter, a filter press, etc., and drying the resulting powder.
As a method for drying the obtained powder, known equipment such as a fluidized bed dryer, a reduced pressure dryer and a circulating air dryer can be used. Further, if necessary, the particles can be classified by using an air classifier or the like to obtain a predetermined particle size distribution.

[0070]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following description, "part" means part by weight and "%" means% by weight.

Production Example 1 Synthesis of [Dispersant (A-1) Having Phosphate Group] 50 parts of methanol and 50 parts of xytoluene were charged into an autoclave equipped with a stirring bar and a thermometer, and 2-hydroxyethyl (meta) was added. ) Acryloyl phosphate / methyl methacrylate / styrene (10 wt% / 50 wt%
/ 40 wt% /) mixed monomer 100 parts, methanol 100 parts and azobisisobutyronitrile 1 part 60 parts
Dropwise polymerization was carried out at 4 ° C. for 4 hours. Volatilize under atmospheric pressure while raising the temperature to 120 ° C, switch to depressurization when 120 ° C is reached, and devolatilize under reduced pressure over 2 hours,
A dispersant (A-1) having a phosphate group having a number average molecular weight of 3,200 and a weight average molecular weight of 9,400 was obtained.

Production Example 2 Synthesis of [Acrylic / Styrene Resin (B-1)] 12 parts of xylene was put into an autoclave equipped with a stirring bar and a thermometer, and glycidyl methacrylate / methyl methacrylate / styrene / acrylic acid was added. 100 parts of a mixed monomer of 2-ethylhexyl (25% by weight / 33% by weight / 40% by weight / 2% by weight) and 0.1 part of cumyl peroxide were subjected to dropwise polymerization at 170 ° C. for 3 hours. Devolatilize under normal pressure while heating up to 180 ℃
At this point, the pressure was switched to reduced pressure, and devolatilization was performed for 2 hours under reduced pressure to obtain a resin (B-1) having a number average molecular weight of 10,500 and a weight average molecular weight of 120,000.

Production Example 3 [Synthesis of low molecular weight polyester (B-2)] 378 parts of bisphenol A ethylene oxide 2 mol adduct, bisphenol A pyropyrene oxide 2 mol adduct 402
Parts, 100 parts of isophthalic acid, 205 parts of terephthalic acid and 2 parts of dibutyltin oxide, and 230
Polycondensation at ℃ for 6 hours, then reacting for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, number average molecular weight 280
A low molecular weight polyester having a weight average molecular weight of 5,100 was obtained.

Production Example 4 [Synthesis of isocyanate group-containing prepolymer (a-1)] 358 parts of bisphenol A ethylene oxide 2 mol adduct and bisphenol A were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube. 381 parts of propylene oxide 2 mol adduct, 200 parts of isophthalic acid, 127 parts of terephthalic acid and 2 parts of dibutyltin oxide were added,
React at atmospheric pressure at 230 ° C for 8 hours, then 10-15mm
After reacting for 5 hours while dehydrating under a reduced pressure of Hg, it was cooled to 80 ° C. and reacted with 110 parts of isophorone diisocyanate in ethyl acetate for 2 hours to give a number average molecular weight of 3,20.
0, weight average molecular weight 12,000, NCO content 1.02
% Of isocyanate group-containing prepolymer (a-1-1)
To give an ethyl acetate solution (solid concentration: 75%).

Production Example 5 [Synthesis of Ketimine Compound (Blocked Amine: β-1)] 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer, and the mixture was heated at 50 ° C. for 5 hours. A ketimine compound (β-
1) was obtained.

Example 1 [Synthesis of Colored Resin Particles (1)] The resin (B
-1) 100 parts, phthalocyanine blue 5 parts, a dispersant having a phosphoric acid group described in Production Example 1 as a dispersant (A-1).
After mixing 2 parts and 230 parts of ethyl acetate, 350 parts of zirconia beads (particle size: 0.8) were added, and the mixture was dispersed for 2 hours with a Glen Mill (manufactured by Asada Iron Works Co., Ltd.) to obtain [Pigment dispersion liquid (1)]. It was 200 parts of deionized water in the beaker,
Hydroxyapatite 10% suspension (Nippon Kagaku Kogyo)
35 parts of SUPERTITE 10 manufactured by Co., Ltd. and 0.1 part of sodium dodecylbenzenesulfonate were added and uniformly dissolved. Then, the temperature was adjusted to 20 ° C and 5,000 with a TK homomixer.
While stirring at rpm, 100 parts of the above pigment dispersion was added and stirred for 10 minutes. Then, this mixed solution was transferred to a Kolben equipped with a stirring rod and a thermometer, the temperature was raised to 50 ° C. to remove the solvent under reduced pressure, and after filtration, the cake was dispersed and washed in 450 parts of 5% hydrochloric acid and filtered again. Repeat this operation with 5% hydrochloric acid 2
00 parts once, 5% sodium hydroxide 200 parts once,
After repeating 3 times with 250 parts of ion-exchanged water, it was dried with a normal air dryer and subjected to air classification to obtain [colored resin particles (1)] having a particle size d50 of 20 μm.

Example 2 [Synthesis of Colored Resin Particles (2)] 100 parts of an ethyl acetate solution of the isocyanate group-containing prepolymer (a-1) described in Production Example 4, 5 parts of permanent red 4R, and Disper byk- as a pigment dispersant. 111 (manufactured by BYK Chemie Japan: phosphate ester of ethylene glycol / polycaprolactone block copolymer, number average molecular weight 700,
The same operation as in Example 1 was carried out except that 2 parts of a weight average molecular weight of 2,200) and 350 parts of ethyl acetate were used.
[Pigment dispersion liquid (2)] and [colored resin particles (2)] having a particle size d50 of 20 μm were obtained. In this case, water is the extender.

Production Example 3 [Synthesis of Colored Resin Particles (3)] 100 parts of the low molecular weight polyester (B-2) described in Production Example 3, 20 parts of an ethyl acetate solution of benzidine yellow (concentration 20%), as a pigment dispersant After mixing 2 parts of Texahol (manufactured by San Nopco Ltd .: triethanolamine salt of sulfuric acid ester of higher alkyl alcohol and polyol, number average molecular weight 900, weight average molecular weight 5,300) and 230 parts of ethyl acetate,
350 parts of zirconia beads (particle size: 0.8) were added, and the mixture was dispersed for 2 hours with a Glen Mill (manufactured by Asada Iron Works Co., Ltd.), and further 20 parts of an ethyl acetate solution of the above-described isocyanate group-containing prepolymer (a-1) and a production example were prepared. 1.2 parts of the ketimine compound (β-1) described in 5 was mixed to obtain [Pigment dispersion liquid (3)]. The same operation as in Example 1 was carried out except that this mixed dispersion liquid was used, and the particle size d50 was 20 μm.
[Colored resin particles (3)] were obtained.

Comparative Example 1 [Synthesis of Colored Resin Particles (4)] The pigment dispersant of Example 1 was "Disparlon DA-725" (Kusuki Kasei: polyester acid amide amine salt, acid value 20, amine value 48, number average). The same operation as in Example 1 was performed except that the molecular weight was changed to 1,100 and the weight average molecular weight was 4,200) [Pigment dispersion (4)] and particle size d50 was 20 μm [Colored resin particles (4)]. Got

Comparative Example 2 [Synthesis of Colored Resin Particles (5)] The pigment dispersant of Example 2 was "Disparlon DA-725" (Kusuki Kasei: polyester acid amide amine salt, acid value 20, amine value 48, number average). The same operation as in Example 2 was repeated except that the molecular weight was changed to 1,100 and the weight average molecular weight was 4,200) [Pigment dispersion (5)] and particle size d50 was 20 μm [Colored resin particles (5)]. Got

Comparative Example 3 [Synthesis of Colored Resin Particles (6)] The pigment dispersant of Example 3 was "Disparlon DA-725" (Kusuki Kasei: polyester acid amide amine salt, acid value 20, amine value 48, number average). The same operation as in Example 3 was carried out except that the molecular weight was changed to 1,100 and the weight average molecular weight was 4,200) [Pigment dispersion (6)] and particle size d50 was 20 μm [Colored resin particles (6)]. Got

Physical Property Measurement Example 1 [Pigment Dispersion (1)] to [Pigment Dispersion (3)] and [Pigment Dispersion (4)] to [Pigment] obtained in Examples 1 to 3 and Comparative Examples 1 to 3. Dispersion (6)] pigment particle size (particle size d
50) and the content of pigment aggregates (particle size 1 μm or more) were measured with a laser diffraction particle size distribution analyzer “LA-920” (manufactured by Horiba Ltd.). Add each dispersion to 30 ℃ and 50 ℃.
The same measurement was performed after 24 hours and 48 hours. The evaluation results are shown in Tables 1 and 2. The pigment particle size is small,
The smaller the aggregate content, the better the pigment dispersibility and the stability of the pigment dispersed state over time.

Physical Property Measurement Example 2 0.1 g of [colored resin particles (1)] to [colored resin particles (6)] obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were 5 cm in length.
× A glass film having a width of 5 cm was placed on the glass plate, and while heating on a hot plate, another glass was placed on the glass plate and pressure was applied to form a resin film. The color difference and haze degree of this resin film were measured with a color difference meter "NDH-300A" (manufactured by Nippon Denshoku Industries Co., Ltd.). The evaluation results are shown in Table 3. Color difference (a *, b *) is
The larger the absolute value of each measured value, the more vivid the color, and the smaller the measured value, the more transparent the haze.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

The colored resin particles of the present invention have good pigment dispersibility in the resin particles, and the resulting coating film has excellent color sharpness and transparency. From the above effects, the colored resin particles obtained by the method of the present invention are powder coatings, thermofusible molding resins, spacers for producing electronic components such as liquid crystals, standard particles for electronic measuring devices, and electrophotography. It is extremely useful as a toner used for electrostatic recording, electrostatic printing, various hot melt adhesives, and resin particles useful for other molding materials.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Hidetoshi Noda 1-11-11 Hitotsubashi-honhoncho, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd. (56) Reference JP-A-6-167833 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 18/00-18/87 C08G 59/00-59/72 C08J 3/12-3/16

Claims (11)

(57) [Claims] 1. Colored resin particles obtained by dispersing a colorant (C) in a resin (B) with a dispersant (A) having a phosphoric acid (salt) group. 2. A dispersant (A) wherein the colorant (C) has a functional group selected from the group consisting of phosphoric acid (salt) groups, sulfonic acid (salt) groups and sulfuric acid (salt) groups in the resin (B). The main skeleton of the dispersant (A) is selected from the group consisting of polyethers, polyesters and copolymers thereof, and the gel filtration chromatography (G) of the dispersant (A) is used.
PC) has a weight average molecular weight of 1,000 to 500,0
00 colored resin particles. 3. A dispersant (A) wherein the colorant (C) has a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group in the resin (B). And the resin (B) is a resin selected from the group consisting of polyurethane resin, epoxy resin and polyester resin. 4. The dispersant (A) has a main skeleton selected from the group consisting of (co) polymers of vinyl monomers, polyethers, polyesters and copolymers thereof. The colored resin particles according to claim 1 or 3, wherein the weight average molecular weight by gel filtration chromatography (GPC) is 1,000 to 500,000. 5. The colored resin particles according to claim 1, wherein the resin (B) is a resin selected from the group consisting of polyurethane resin, epoxy resin, vinyl resin and polyester resin. 6. The amount of the dispersant (A) is such that the colorant (C) 10
1 to 150 parts by weight relative to 0 parts by weight, and the resin (B)
The colored resin particles according to claim 1, which are 0.01 to 90 parts by weight with respect to 100 parts by weight. 7. The colorant (C) is a white pigment, a yellow pigment,
Orange pigment, red pigment, purple pigment, blue pigment, green pigment,
The colored resin particle according to any one of claims 1 to 6, comprising a brown pigment or a black pigment. 8. A resin in which a colorant (C) is dispersed by a dispersant (A) having a functional group selected from the group consisting of phosphoric acid (salt) groups, sulfonic acid (salt) groups and sulfuric acid (salt) groups. (B)
Is dissolved or dispersed in an organic solvent, the dissolved or dispersed solution is emulsified or dispersed in an aqueous medium, and granulated, and a method for producing colored resin particles. 9. A resin in which a colorant (C) is dispersed by a dispersant (A) having a functional group selected from the group consisting of phosphoric acid (salt) groups, sulfonic acid (salt) groups and sulfuric acid (salt) groups. (B)
The reactive group-containing prepolymer (α), which is a precursor of, is dissolved or dispersed in an organic solvent, and the solution or dispersion is emulsified in an aqueous medium containing an extender and / or a crosslinking agent (β). Or it is dispersed and (α) is expanded and / or
Alternatively, a method for producing colored resin particles is characterized in that the resin (B) is formed by cross-linking and granulated. 10. The reactive group of the prepolymer (α) is a reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and the (β) has active hydrogen. Alternatively, the production method according to claim 9, which is a compound (β-1) that occurs. 11. The production method according to claim 10, wherein the (β-1) is water or a ketimine compound.