JP3499531B2 - Method for producing colored resin particles - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing colored resin particles for forming a coating film having good pigment dispersibility and excellent color sharpness and transparency. For more details,
For powder coatings with excellent heat-melting properties and powder fluidity, heat-melting molding resins, spacers for the production of electronic components such as liquid crystals, standard particles for electronic measuring instruments, electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a method for producing colored resin particles which is useful for toners and other molding materials used.

[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. Powder coating, electrophotography, electrostatic recording,
When a pigment or the like is dispersed to color the particles for the purpose of designing a toner or the like used for electrostatic printing or the like, it is necessary to disintegrate the pigment into primary particles and uniformly disperse the pigment in the resin. If the dispersion of the pigment is not uniform in the resin, or if there are many secondary particles in which the primary particles of the pigment are aggregated, the color sharpness of the coating film,
There were problems such as deterioration of transparency. In order to solve such a problem, it has been proposed to improve the dispersibility of a pigment in a resin or a solvent solution of a resin which is emulsified and dispersed in an aqueous medium or an organic solvent medium, and JP-A-2-153361 has been proposed.
In the publication, as a method for producing a dry toner, a pigment is dispersed in a resin by melt-kneading and then dissolved in a solvent to prepare a toner preparation liquid, and the toner preparation liquid is emulsified and dispersed in water. A method for obtaining resin particles containing a pigment by volatilizing is disclosed. According to this method, the pigment dispersibility immediately after melt-kneading is good, but secondary agglomeration of the pigment occurs when the melt-kneaded product is dissolved in a solvent. Therefore, the pigment dispersibility of the obtained resin particles is not always good. However, there is a problem that the color sharpness and transparency of the coating film are inferior.

[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 found that colored resin particles having good pigment dispersibility and excellent color sharpness and transparency of a coating film can be industrially produced. The present invention has been accomplished by finding a more efficient method for obtaining the above.
That is, the present invention relates to a colorant (B) and an organic solvent (D).
Is mixed so that the solid content concentration is 1 to 50% by weight, and then the colorant is dispersed in an organic solvent by using a high pressure jet nozzle type disperser or an ultrasonic type disperser, and the resin (A ) The reactive group-containing prepolymer (A-1) which is the precursor of (1) is dissolved or dispersed so that the solid content concentration becomes 20 to 95% by weight, and the dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium. And extender and / or crosslinker (A-
In (2), (A-1) is elongated and / or crosslinked to form a resin (A), and granulated, which is a method for producing colored resin particles.

[0005]

The present invention will be described in detail below. The resin (A) in the present invention is a reactive group-containing prepolymer (A-
It is a reaction product of 1) with an elongation agent and / or a crosslinking agent (A-2). Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (A-1) and the extender and / or the crosslinking agent (A-2) include the following. The reactive group contained in (A-1) is a functional group (A-1-1) capable of reacting with an active hydrogen compound,
Is a combination of active hydrogen compounds (A-2-1). : The reactive group contained in (A-1) is an active hydrogen-containing group (A
-1-2), wherein (A-2) is a compound (A-2-2) capable of reacting with an active hydrogen-containing group.

Examples of the functional group (A-1-1) 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.

As the active hydrogen compound (A-2-1),
Examples thereof include polyamines (1), polyamines which may be blocked with a removable compound, polyols (2), polymercaptans and water. Among these, preferred are polyamines (1), polyamines which may be blocked with a removable compound, polyols and water.

The polyamines (1) include aliphatic polyamines (C2 to C18): aliphatic polyamines {C2 to C18].
C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, Tetraethylenepentamine, pentaethylenehexamine, etc.]; these alkyls (C1 to C4) or hydroxyalkyl (C
2 to C4) Substitute [Dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-
Hexamethylenediamine, methyliminobispropylamine, etc.]; Aliphatic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,
10-Tetraoxaspiro [5,5] undecane, etc.]; Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4-C15) : 1,3-
Heterocyclic polyamines (C4 to C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Diaminoethylpiperazine, 1,4
Aromatic polyamines (C6 to C20) such as 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, etc .; nuclear-substituted alkyl groups [methyl, ethyl, n-
And aromatic polyamines having C1 to C4 alkyl groups such as i-propyl, butyl, etc., such as 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 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 their isomers Mixtures in various proportions;
Aromatic polyamines having a nucleus-substituted electron-withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group) [methylenebis-o-
Chloroaniline, 4-chloro-o-phenylenediamine, 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 [-NH of the above-mentioned aromatic polyamines]
A part or all of 2 is replaced by -NH-R '(R' is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4'-di (methylamino) diphenylmethane, 1- Methyl-2-methylamino-4-aminobenzene and the like], polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (2 mol or more per 1 mol of acid) polyamines (the above alkylenediamine, polyalkylenepolyamine and the like) And low molecular weight polyamide polyamines obtained by condensation of polyether polyamines: hydrides of cyanoethylated products of polyether polyols: polyether polyols (such as polyalkylene glycols).

The polyamines which may be blocked with a removable compound include the polyamines (1)
And a ketimine compound and an oxazoline compound obtained by dehydration condensation of a ketone having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

Examples of the polyols include a diol (2) and a trivalent or higher valent polyol (3). Of these, the diol (2) alone or a mixture of the diol (2) and a small amount of a polyol (3) having 3 or more valences is preferable.
Examples of the diol (2) 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, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S
Etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the alicyclic diols; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the bisphenols, and the like. Of these, preferred ones have 2 to 1 carbon atoms.
2 are alkylene glycols and alkylene oxide adducts of bisphenols, and particularly preferable are alkylene oxide adducts of bisphenols and a combination of these with an alkylene glycol having 2 to 12 carbon atoms. As the trivalent or higher polyol (3), 3 to
Octahydric or higher polyhydric alcohols (glycerin, trimethylolethane, trimethylolpropane,
Pentaerythritol, sorbitol, etc.); trisphenols (Trisphenol PA, etc.); novolak resins (phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolak resins. . Of these, the preferred one is
An alkylene oxide adduct of a polyhydric aliphatic alcohol having a valence of 3 to 8 or more and a novolac resin,
Particularly preferred are alkylene oxide adducts of novolak resins. Polymercaptans include ethylenedithiol, 1,4-butanedithiol, 1,6-
Hexanedithiol and the like can be mentioned. Furthermore, if necessary, a reaction terminator can be used together with (A-2-1). As the reaction terminator, monoamine (diethylamine, dibutylamine, butylamine, laurylamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol, phenol); monomercaptan (butylmercaptan, (Lauryl mercaptan etc.)
And so on.

Prepolymer (A-1) in the above
Is an active hydrogen-containing group (A-1-2), an amino group, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), a mercapto group, a carboxyl group and an organic group blocked with a compound capable of leaving them. And so on. Of these, preferred are amino groups and hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups).
And an organic group whose amino group is blocked with a eliminable compound. 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 dehydration condensation of an amino group with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

A compound capable of reacting with an active hydrogen-containing group (A-
Examples of 2-2) include polyisocyanates (4), polyepoxides (5), polycarboxylic acids, polyanhydrides and polyacid halides. Among these, preferred are polyisocyanates (4),
And polyepoxides (5).

The polyisocyanates (4) include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in NCO group, the same applies hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and 4 to carbon atoms. 15 alicyclic polyisocyanates, araliphatic polyisocyanates 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, Isocyanurate 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 polyepoxides (5) 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 glycidyl ethers of polyhydric phenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A 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.

Examples of polycarboxylic acids include dicarboxylic acids (6), polycarboxylic acids having a valence of 3 or more (7), and acid anhydrides thereof. Examples of the dicarboxylic acid (6) 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 alkylenedicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenylsuccinic acid (dodecenylsuccinic acid, pentadecenylsuccinic acid Acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.);
Examples thereof include aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Tricarboxylic or higher polycarboxylic acid (7)
Examples thereof include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

Examples of polycarboxylic acid anhydrides include maleic anhydride, phthalic anhydride, and pyromellitic dianhydride. 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 (A-2-2). 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.); monool (methanol, ethanol, isopropanol, butanol, Phenol; monomercaptan (butyl mercaptan, lauryl mercaptan, etc.) and the like can be mentioned.

The equivalent ratio of the reactive group in the reactive group-containing prepolymer (A-1) to the active hydrogen-containing group in (A-2) is
Usually 1/2 to 2/1, preferably 1.5 / 1 to 1/1.
5, more preferably 1.2 / 1 to 1 / 1.2.
When (A-2) is water, water is treated as a divalent active hydrogen compound.

Examples of the prepolymer (A-1) include prepolymers such as polyester, epoxy resin, polyurea resin and polyurethane. Examples of polyesters include polycondensates of polyols with polycarboxylic acids or their acid anhydrides or their lower alkyl esters. The above-mentioned diol (2) and trivalent or higher valent polyol (3) are used as the polyol, and the above-mentioned dicarboxylic acid (6) and trivalent or higher valent polycarboxylic acid are used as the polycarboxylic acid or its acid anhydride or its lower alkyl ester. Preferred examples are the same as (7) and acid anhydrides or lower alkyl esters thereof. The ratio of the polyol to the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH].
/ 1, and more preferably 1.3 / 1 to 1.02 / 1. The polyester is obtained by mixing a polycarboxylic acid and a polyol in the presence of a known esterification catalyst such as tetrabutoxytitanate and dibutyltin oxide at 150 to 280.
Obtained by heating to ℃ and dehydration condensation. It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.

As the epoxy resin, the polyepoxides (5) and the active hydrogen compound (D) {water, polyol [the diol (2) and trivalent or higher valent polyol (3)], dicarboxylic acid (6) are used. Trivalent or higher polycarboxylic acid (7), polyamine (1) and the like}, dicarboxylic acid (6) or polyaddition product of trivalent or higher polycarboxylic acid (7) with an acid anhydride, and the like, The same applies to the preferred ones.

As the polyurethane, the above polyisocyanates (4) and the above active hydrogen compound (D) {water, polyol [the above diol (2) and trivalent or higher valent polyol (3)], dicarboxylic acids (6), 3 Polycarboxylic acids (7) having a valency or more, polyamines (1), and the like} and polyaddition products thereof are mentioned, and preferable ones are also the same.

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 the 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. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of the polyol to the polycarboxylic acid is the hydroxyl group [OH] and the carboxyl group [C
The molar ratio of [OHH] / [COOH] is 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.

In the method described above, an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in (1) with a polyisocyanate, and a blocked isocyanate group-containing prepolymer is obtained by reacting a blocked polyisocyanate, 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 polyisocyanates (4), and preferred ones are also the same.

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 content of reactive groups in the prepolymer (A-1) is usually 150 to 30,000, preferably 300 to 20, in terms of number average molecular weight of prepolymer / number of reactive groups.
It is 000. The number average molecular weight of (A-1) is usually 50.
0 to 30,000, preferably 1,000 to 20,000
It is 0, and more preferably 2,000 to 10,000. The weight average molecular weight of (A-1) is 1,000 to 5
10,000, preferably 2,000 to 40,000, and more preferably 4,000 to 20,000.

Furthermore, if necessary, a reaction terminator can be used together with (A-2). Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and blocked products thereof (ketimine compounds).

The extension and / or cross-linking reaction time is selected depending on the reactivity of the combination of the reactive group structure of the prepolymer (A-1) and the extender and / or cross-linking agent (A-2). It is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 15
The temperature is 0 ° 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.

In the present invention, (A-1) and (A-2)
The glass transition point (Tg), the molecular weight, the SP value and the inter-crosslinking point molecular weight of the resin produced by the elongation and / or the crosslinking reaction vary depending on the application and may be appropriately adjusted.

The colorant (B) in the present invention includes white pigments, yellow pigments, orange pigments, red pigments, violet 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. The carbon black may be surface-treated for the purpose of improving functions such as dispersibility, hydrophobicity and hydrophilicity. Examples of the surface treatment method include polymer grafting, surface oxidation treatment, surface adsorption treatment with wax, surfactant and the like. 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, the composition of the resin (A), and may be appropriately selected. The organic pigment may be surface-treated for the purpose of improving functions such as dispersibility, hydrophobicity and hydrophilicity. Examples of the surface treatment method include polymer grafting, surface oxidation treatment, surface adsorption treatment with wax, surfactant and the like. These can be performed by a known method.

As the other resin (C) in the present invention, any resin can be used as long as it is a known resin and is used as required. For example, as an addition polymerization resin (vinyl resin), Polyethylene, polypropylene, polystyrene, styrene-alkyl (meth) acrylate copolymer, styrene-butadiene copolymer, acrylic acid-alkyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer Polyester resin, polyamide resin, polyimide resin, polycarbonate resin, silicon resin as polycondensation resin; polyurethane resin, polyurea resin, epoxy resin as polyaddition resin; addition polymerization resin,
Phenolic resins, melamine resins, aniline resins; other resins include unsaturated polyester resins and ionomer resins. Among these, vinyl resins, polyester resins, polyurethane resins, polyurea resins and epoxy resins are preferable.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of vinyl monomers include the following (1) to (13).

(1) Vinyl hydrocarbons: (1) -1) Aliphatic vinyl hydrocarbons: Alkenes having 2 to 20 carbon atoms, such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene. , Dodecene, octadecene, α-olefins other than the above; alkadienes having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene, 1,6
-Hexadiene, 1,7-octadiene. (1) -2) alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidene bicycloheptene, etc .; terpenes,
For example, pinene, limonene, indene, etc. (1) -3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products such as α-
Methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene and the like; and Vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomer and salt thereof: unsaturated monocarboxylic acid having 3 to 30 carbon atoms,
Unsaturated dicarboxylic acids and their anhydrides and their monoalkyl (C1-24) esters, such as (meth)
Acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester Carboxyl group-containing vinyl monomers such as cinnamic acid.

(3) Sulfone group-containing vinyl monomer, vinyl sulfuric acid monoester and salts thereof: carbon number 2
To 14 alkene sulfonic acids, such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and C 2-24 alkyl derivatives thereof, such as α-methyl styrene sulfonic acid; sulfo ( Hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, for example sulfopropyl (meth) acrylate, 2-hydroxy-3-
(Meth) acryloxypropyl sulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropane sulfone Acid, 2- (meth) acrylamide-
2-methylpropanesulfonic acid, 3- (meth) acrylamido-2-hydroxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n =
2 to 30) oxyalkylene (ethylene, propylene,
Butylene: single, random, or block) sulfuric acid ester of mono (meth) acrylate [poly (n = 5 to 5
15) Oxypropylene monomethacrylate sulfate ester and the like] and polyoxyethylene polycyclic phenyl ether sulfate ester; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomer and its salt: (meth) acryloyloxyalkyl (C1 to C2
4) Phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (having 1 to 24 carbon atoms) phosphonic acids,
For example, 2-acryloyloxyethylphosphonic acid

Examples of the salts (2) to (4) include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), ammonium salt, amine salt or 4 Included are primary ammonium salts.

(5) Vinyl monomer containing hydroxyl group: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene- 1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether,
Sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer: (6) -1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butyl Aminoethyl methacrylate, N
-Aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4
-Vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole , Aminopyrrole, aminoimidazole, aminomercaptothiazole, their salts, etc. (6) -2) Amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N
-Butyl acrylamide, diacetone acrylamide,
N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamic acid amide,
N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6) -3) Nitrile group-containing vinyl monomer: (meth)
(6) -4) Quaternary ammonium cation group-containing vinyl-based monomer: acrylonitrile, cyanostyrene, cyanoacrylate, etc .: dimethylaminoethyl (meth) acrylate,
3 such as diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine
Quaternary product of vinyl amine monomer containing primary amine group (quaternized using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate) (6) -5) Vinyl monomer containing nitro group : Nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer: glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromstyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone: (9) -1) Vinyl ester such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate , Isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α
-Ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups have 2 to 8 carbon atoms, straight chain, A branched or alicyclic group), a dialkyl maleate (two alkyl groups are a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) Allyloxyalkanes [Diaryloxyethane, triaryloxyethane, tetraallyloxye Emissions, tetra allyloxy propane, tetra Ali Loki Shiv Tan, tetra meth allyloxy ethane], and the like, polyalkylene glycol chain vinyl monomers [polyethylene glycol having a (molecular weight 30
0) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylate [Poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (Meth) acrylate and the like], etc .; (9) -2) Vinyl (thio) ether, for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, Vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2
-Butoxyethyl ether, 3,4-dihydro 1,2-
Pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, (9) -3) vinyl ketone, for example vinyl methyl ketone,
Vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone and divinyl sulfoxide.

(10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

Examples of the vinyl-based monomer copolymer include polymers obtained by copolymerizing the above-mentioned arbitrary monomers (1) to (10) with each other in a binary or more number in an arbitrary ratio.

The vinyl resin can be synthesized by a known polymerization method such as suspension, emulsion or solution polymerization of the above-mentioned monomer using a radical polymerization catalyst. The polymerization temperature is usually 10 to 2
The temperature is 00 ° 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, such as toluene, xylene, ethyl acetate, butyl acetate,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol and the like can be used.

Examples of the polyester resin are the same as those mentioned above, and the preferable ones are also the same.

Examples of the polyurethane resin are the same as those mentioned above, and the preferable ones are also the same.

Examples of the polyurea resin include the reaction products of the above polyisocyanates (4) and amines (1).

Examples of the epoxy resin are the same as those mentioned above, and the preferred ones are also the same.

Organic solvent (D) used in the present invention
Has a boiling point of usually 50 to 150 ° C., preferably 50.
~ 120 ° C, specifically, n-hexane,
It is n-octane, toluene, xylene, ethyl acetate, n-butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide, or a mixed solvent of two or more thereof. Of these, preferred organic solvents are toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, and tetrahydrofuran, and particularly preferred are toluene, ethyl acetate, acetone, methyl ethyl ketone, and tetrahydrofuran.

In the present invention, the colorant (B) is mixed with an organic solvent and then dispersed in the organic solvent using a high pressure jet nozzle type disperser or an ultrasonic type disperser. The high-pressure jet nozzle type disperser allows high-speed passage through an extremely thin flow path by applying high pressure to the liquid treatment product, and suddenly bends the flow path at a right angle or abruptly diffuses it, colliding with a barrier plate. Then, it is a device for applying high-density energy due to cavitation and collision to a liquid processing object to disperse and emulsify it.
An ultrasonic disperser is a device that applies high pressure to a liquid processed material and ejects it at a high speed from an orifice and hits the blade to cause the blade to generate self-excited vibration, which causes cavitation and dispersion of the liquid processed material. There is a device in which an ultrasonic transducer connected to an acoustic wave oscillator is vibrated at a high frequency in an irradiation cell, and ultrasonic waves are applied to a liquid-processed product sent in the cell to disperse the liquid-processed material. By applying the colorant (B) together with an organic solvent to a high pressure jet nozzle type disperser or an ultrasonic disperser,
The colorant (B) is finely dispersed in the organic solvent according to the above principle.

Specific examples of the high pressure jet nozzle type disperser include Microfluidizer (manufactured by Mizuho Industry Co., Ltd.) and De.
BEE2000 (manufactured by Nippon BEE Co., Ltd.), Gorin homogenizer G15, G1000, Lanier homogenizer R56, R118, R2000 (manufactured by APV Homogenizer), Nanomizer (manufactured by Nanomizer), Ultra Turrax T50 (manufactured by Squid Japan), etc. Can be mentioned. Further, as a disperser that also uses dispersion by ultrasonic waves, a sonolator (manufactured by Sonic Co.), T.I. K. Examples include Micromizer (made by Tokushu Kika Kogyo Co., Ltd.).

The solid content concentration of the mixed liquid of the colorant (B) and the organic solvent in the above dispersion step is usually 1 to 50% by weight, preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight. When the solid content concentration exceeds 50% by weight, the thixotropy after dispersion becomes too high, which makes handling difficult, and when repeated dispersion occurs, bubbles are caught and a predetermined pressure is not applied. If it is less than wt%, it is not suitable from the economical viewpoint.

The pressure applied to the mixed liquid of the colorant (B) and the organic solvent in the dispersion step is usually 10 to 255 MPa, preferably 50 to 2,000 MPa, particularly preferably 100 to 100 MPa.
It is 1,000 MPa. When the pressure is less than 10 MPa,
Colorant (A) dispersed particle size does not become small, 2,500MP
If it exceeds a, it is not preferable from the viewpoint of durability of the device. The temperature of the mixed liquid of the colorant (B) and the organic solvent in the dispersion step is usually 0 to 100 ° C, preferably 20 ° C to 80 ° C, particularly preferably 30 to 60 ° C. Since a large amount of collision energy is generated during processing, a large cooling device is required to keep the processing temperature below 0 ° C, which is economically disadvantageous. When the treatment temperature exceeds 60 ° C., reaggregation of the pigment is likely to occur, which is not preferable. Depending on the type of the colorant (B), the dispersity of the target level may not be reached in one treatment, and in this case, it is preferable to repeatedly pass through the disperser for treatment. Usually 1 to 50 times
Times, preferably 1 to 30 times, particularly preferably 1 to 10 times.

The dispersed particle diameter d50 of the colorant (B) treated with the high pressure jet nozzle type disperser is usually 20 μm or less, preferably 10 μm or less, and particularly preferably 0.01 to 3 μm.
Is. When the dispersed particle diameter d50 of the colorant (B) exceeds 20 μm, the color sharpness at the time of forming a coating film is poor.

When the colorant (B) is dispersed in an organic solvent, it is preferable to use a pigment dispersant for the purpose of improving the dispersibility of the (B). Examples of the pigment dispersant include a pigment dispersant containing a functional group having adsorptivity to the pigment. Examples of the functional group having adsorptivity for pigments include acidic groups such as phosphoric acid groups, carboxylic acid groups, sulfonic acid groups, sulfamic acid groups and their neutralizing bases, amino groups and neutralizing bases of amino groups, and quaternary groups. Ammonium base,
Examples thereof include an amide group and an imide group. Examples of the main skeleton of the pigment dispersant include (co) polymers of vinylic monomers such as acrylic acid ester, styrene and vinyl acetate, and polyethers, polyesters, polycaprolactones, polyamide polyamines and copolymers thereof.

The pigment dispersant may be a low molecular weight compound or a high molecular weight compound, but preferably has a weight average molecular weight of 1000 by gel filtration chromatography (GPC) from the viewpoint of dispersion stability and compatibility with the resin (A). ~ 500,
000, particularly preferably 1500 to 300,000. The pigment dispersant preferably has good compatibility with the resin (A) in order to stably disperse the pigment in the matrix. The SP value of the pigment dispersant and the SP of the resin (A) are preferable.
The difference from the value (ΔSP) is usually 0 from the viewpoint of compatibility between the two.
~ 1.0, preferably 0-0.8, particularly preferably 0
It is 0.5.

As the above-mentioned pigment dispersant, "Dispe
rbyk-170 "," Disperbyk-111 "
(Manufactured by Big Chemie Japan Co., Ltd.), "Texahole" (manufactured by San Nopco Co., Ltd.), "Disparon DA-7"
05 "(manufactured by Kusumoto Kasei Co., Ltd.)," Addisper PN41
1 ”and the like.

In the present invention, the reactive group-containing prepolymer (A-) which is a precursor of the resin (A) is added to the dispersion of the colorant (B) and the organic solvent treated by the high pressure jet nozzle type disperser.
1), the elongation agent and / or the crosslinking agent (A-2) and, if necessary, the other resin (C) are dissolved or dispersed.
The content of the colorant (B) in the dispersion of the prepolymer (A-1) and the dispersion containing the colorant (B) treated with the disperser and the organic solvent is the resin (A). And 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the other resin (C) optionally used.
Parts by weight, particularly preferably 2 to 20 parts by weight. Before being emulsified or dispersed in an aqueous medium, the above-mentioned dissolved dispersion is dissolved or dispersed in an organic solvent so that the solid content concentration becomes 20 to 95% by weight, preferably 25 to 90% by weight. The organic solvent used is the same as in (D) above.

When the above-mentioned dissolved dispersion is emulsified or dispersed in an aqueous medium, the prepolymer (A-1) and the elongation agent and / or the crosslinking agent (A-2) are allowed to undergo elongation and / or crosslinking reaction, The colored resin particles of the present invention can be obtained by granulating while forming the resin (A). On this occasion,
The extender and / or the cross-linking agent (A-2) may be mixed in the above-mentioned dissolution / dispersion liquid in advance, or may be dissolved or dispersed in an aqueous medium. This method, it is possible to reduce the viscosity of the solution or dispersion, the particle size of the particles at the time of emulsification and dispersion, is advantageous in sharpening the particle size distribution, a polymer resin that is sparingly soluble in organic solvents, It has a feature that the crosslinked resin can be made into particles.

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. The amount of solvent used is 1 water
It is usually 0 to 50 parts by weight, preferably 0 to 30 parts by weight, relative to 00 parts by weight.

The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 70 to 800 parts by weight, based on 100 parts by weight of the solution.

As the emulsifier or dispersant used, 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 solution or dispersion.

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, starch, gum arabic; polyalkylene oxides such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide. Sides etc. are used.

In order to sharpen the particle size distribution of the emulsified or dispersed product, it is preferable to carry out the emulsified or dispersed product in the presence of organic or inorganic fine particles. The organic or inorganic fine particles are previously dispersed in an aqueous dispersion medium and emulsified or dispersed. Organic fine particles include copolymers of vinyl monomers such as styrene, (meth) acrylic acid and (meth) acrylic acid ester, and inorganic fine particles include calcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, aluminum hydroxide, etc. Is mentioned.

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 by weight based on 100 parts by weight of the above-mentioned dissolution or dispersion liquid. The temperature at the time of emulsification or dispersion is usually 0 to 150.
C, preferably 20 to 98C. It does not matter whether it is under normal pressure or under pressure.

The device for emulsifying or dispersing is not particularly limited as long as it is commercially available as an emulsifying machine or a dispersing machine. For example, a homogenizer (manufactured by IKA),
Batch type emulsifiers such as Polytron (Kinematica), TK Auto Homomixer (made by Tokushu Kika Kogyo), Ebara Milder (made by Arihara Seisakusho), TK Pipeline Homomixer (made by Tokushu Kika Kogyo), Continuous emulsifiers such as colloid mill (Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (Mitsui Miike Kakoki Co., Ltd.), Capitron (Eurotec Co., Ltd.), fine flow mill (Pacific Machine Co., Ltd.), Microfluidizer (made by Mizuho Industry Co., Ltd.), Nanomizer (made by Nanomizer Co., Ltd.), high-pressure emulsifier such as APV Gaulin (made by Gaurin Co.), membrane emulsifier such as membrane emulsifier (made by Refrigeration Industry Co., Ltd.), vibro mixer (cooled) Examples include a vibrating emulsifier such as Chemical Industry Co., Ltd., an ultrasonic homogenizer such as an ultrasonic homogenizer (manufactured by Branson), and the like.

The obtained emulsion or dispersion is desolvated to obtain colored resin particles. Particle size of colored resin particles (D
50) 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
It is 5.0, and may be set as appropriate according to the intended use.

In the present invention, other known additives may be used depending on the application when forming the resin fine particle composition. Examples of the additive include a filler, an antistatic agent, a dye, a release agent, a charge control agent, an ultraviolet absorber and an antioxidant.

Examples of the filler include titanium oxide and talc. Examples of the antistatic agent include neutralized products of polystyrene sulfonic acid, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. As a dye, Sudan Black S
M, Fast Yellow G, Rhodamine FB, Rhodamine B Lake, Oil Yellow GG, Orazol Brown B and the like. As the release agent, polyolefin wax (polyethylene wax, polypropylene wax, etc.), long-chain hydrocarbon (paraffin wax, Sazol wax, etc.), carbonyl group-containing wax (carnauba wax, montan wax, trimethylolpropane tribehenate, etc.) Tristearyl trimellitate,
Ethylenediamine dibehenylamide, distearyl ketone, etc.) and the like. Examples of the charge control agent include nigrosine dyes, quaternary ammonium salt group-containing compounds, quaternary ammonium salt group-containing polymers, metal-containing azo dyes, salicylic acid metal salts, substituted salicylic acid metal salts, sulfonic acid group-containing polymers and phosphoric acid group-containing polymers. Can be mentioned. Examples of the ultraviolet absorber include hindered amine and hindered phenol. BH as an antioxidant
Examples include T and the like.

The colored resin particles and the above-mentioned other additives may be mixed in the aqueous medium when the dispersion is formed. However, after (A-1) and the additives are mixed in advance, the colored resin particles are mixed in the aqueous medium. More preferably, the mixture is added to and dispersed.
Further, in the present invention, the additive does not necessarily have to be mixed when the particles are formed in the aqueous medium,
It may be added after the particles are formed. For example, the dye may be added by a known dyeing method after forming particles containing no dye.

The colored resin particles of the present invention can be obtained by solid-liquid separation using 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, a circulating air dryer, and an airflow 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.

[0076]

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 High Molecular Weight Polyester (A-1)] 542 parts of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct 192
Parts, 300 parts of isophthalic acid and 49 parts of terephthalic acid are polycondensed at 230 ° C. for 6 hours under normal pressure, then 10 to 15 mm
The reaction was carried out for 5 hours while dehydrating under a reduced pressure of Hg to obtain a high molecular weight polyester having a number average molecular weight of 7,300 and a weight average molecular weight of 28,000.

Production Example 2 [Synthesis of Low Molecular Weight Polyester (A-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 3 [Synthesis of Isocyanate Group-Containing Prepolymer (A-1-1)] In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 358 parts of a 2 mol adduct of bisphenol A ethylene oxide, Bisphenol A propylene oxide 2
381 parts of molar adduct, 200 parts of isophthalic acid, 127 parts of terephthalic acid and 2 parts of dibutyltin oxide were added, and the mixture was reacted at 230 ° C. for 8 hours under normal pressure, and further 10-15
After reacting for 5 hours while dehydrating under reduced pressure of mmHg, 80
The mixture was cooled to ℃ and reacted with 110 parts of isophorone diisocyanate in ethyl acetate for 2 hours to give a weight average molecular weight of 12
000, an ethyl acetate solution of an isocyanate group-containing prepolymer (A-1-1) having an NCO content of 1.02% (solid content concentration 75%) was obtained.

Production Example 4 [Ketimine compound (blocked amine: A-1-
Synthesis of 2)] 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged in a reaction vessel equipped with a stir bar and a thermometer and reacted at 50 ° C for 5 hours to obtain a ketimine compound.

Example 1 [Synthesis of Colored Resin Particles (1)] Cyanine Blue KRO
(Sanyo dye) 20 parts, ethyl acetate 67 parts, pigment dispersant (Disper Byk-170: made by Big Chemie Japan) 13 parts are mixed and dispersed by a high-pressure jet nozzle disperser [Gorin homogenizer 15M-8TB]. went. Dispersion pressure is 51 MPa, processing speed is 1,000
ml / min, the number of passes was once, the temperature of the mixed solution at the time of charging the disperser was 16 ° C., the temperature of the discharged dispersion was 55 ° C., and the particle diameter d50 of the pigment was 0.39 μm. Dispersion 2
While stirring 5 parts at room temperature, high molecular weight polyester (A
-1) A solution prepared by dissolving 30 parts and 65 parts of low molecular weight polyester (A-2) in 36 parts of ethyl acetate and a dispersion liquid prepared by dispersing 5 parts of carnauba wax in 45 parts of ethyl acetate were added over 30 minutes to be solid. A mixed dispersion (1) of a resin and a colorant having a concentration of 50% was obtained. Ion-exchanged water 200 in the beaker
Parts, 35 parts of a hydroxyapatite 10% suspension (Supatite 10 manufactured by Nippon Kagaku Kogyo Co., Ltd.) and 0.1 part of sodium dodecylbenzenesulfonate were added and uniformly dissolved.
Then, adjust the temperature to 20 ° C and use a TK homomixer for 5000
With stirring at 100 rpm, 100 parts of the mixed dispersion liquid of the above resin and colorant was added and stirred for 10 minutes. Then, the mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, the temperature was raised to 50 ° C., the solvent was removed under reduced pressure, and the cake was separated by 5% after filtration.
The dispersion was washed with 450 parts of hydrochloric acid and filtered again. This operation was further performed once with 200 parts of 5% hydrochloric acid and 1% sodium hydroxide 2
After repeating once with 00 parts and three times with 250 parts of ion-exchanged water, it is dried with a normal air dryer and subjected to air classification to obtain a particle size d50 of 20.
μm [colored resin particles (1)] were obtained. In addition, 50 parts of ethyl acetate dispersion of carnauba wax was prepared by adding 50 parts of zirconia beads (particle size: 0.8) and performing dispersion for 2 hours with a Glen mill (manufactured by Asada Iron Works Co., Ltd.).

Example 2 [Synthesis of Colored Resin Particles (2)] Permanent Red 4R
20 parts, ethyl acetate 74 parts, pigment dispersant (Disper
byk-111: manufactured by Big Chemie Japan) was mixed and dispersed using a high pressure jet nozzle type disperser [Gorlin type homogenizer 15M-8TA]. The pressure during dispersion was 51 MPa, the processing speed was 1,000 ml / min, the number of passes was three times, the temperature of the mixed liquid when the dispersion machine was charged was 20 ° C., and the temperature of the discharged dispersion liquid was 52 to 61 ° C. It was The dispersion was cooled to 20 ° C. with ice water for each pass, and then treated with a disperser. The particle diameter d50 of the pigment was 0.41 μm. While stirring 25 parts of the dispersion at room temperature, the isocyanate group-containing prepolymer (A-1) described in Production Example 3 was used.
133 parts of the ethyl acetate solution of -1) and 52 parts of ethyl acetate were continuously added over 30 minutes to obtain a mixed dispersion liquid (2) of a resin and a colorant having a solid content concentration of 50%. The same operation as in Example 1 was carried out except that the mixed dispersion liquid of the resin and the colorant described above was used to obtain [colored resin particles (2)] having a particle diameter d50 of 20 μm. In this case, water is the extender.

Example 3 [Synthesis of Colored Resin Particles (3)] Benzidine Yellow 10
Parts, 85 parts of ethyl acetate and 5 parts of a pigment dispersant (Texahol: manufactured by San Nopco Co., Ltd.) were mixed and dispersed by a high pressure jet nozzle type disperser [Gorlin type homogenizer 15M-8TA]. The pressure during dispersion was 51 MPa, the processing speed was 1,000 ml / min, the number of passes was 5 times, the temperature of the mixed solution when the disperser was charged was 20 ° C., and the temperature of the discharged dispersion was 55-63 ° C. It was Disperse 20 times with ice water for each pass.
After cooling to 0 ° C., a dispersion machine was used for treatment. The particle diameter d50 of the pigment was 0.28 μm. Dispersion 70
90 parts of the low molecular weight polyester (A-2) described in Production Example 2 and 13 parts of an ethyl acetate solution of the isocyanate group-containing prepolymer (A-1-1) described in Production Example 3 and ethyl acetate with stirring at room temperature. 47 parts was added and dissolved over 30 minutes, and 0.15 parts of the ketimine compound was further mixed to obtain a mixed dispersion liquid (3) of a resin and a colorant having a solid content concentration of 50%. The same operation as in Example 1 was carried out except that this mixed dispersion liquid was used to obtain [colored resin particles (3)] having a particle diameter d50 of 20 μm.

Comparative Example 1 [Synthesis of Colored Resin Particles (4)] 95 parts of the low molecular weight polyester described in Production Example 1, 5 parts of cyanine blue KRO (manufactured by Sanyo Dye), a pigment dispersant (Disper Byk-11).
1: 2 parts of Big Chemie Japan) and 5 parts of carnauba wax were mixed with a Henschel mixer (FM manufactured by Mitsui Miike Kakoki Co., Ltd.).
10B) and premixed, and then kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.). Then supersonic jet crusher Lab Jet (Japan Pneumatic Mfg. Co., Ltd.)
After finely pulverizing the mixture with 107 parts of ethyl acetate, the mixture was stirred at 35 ° C. for 3 hours to obtain a mixed dispersion liquid (4) of a resin and a colorant having a solid content concentration of 50%. The procedure of Example 1 was repeated except that this mixed dispersion liquid was used.
A comparative [colored resin particle (4)] having a particle diameter of 50 of 20 μm was obtained.

Comparative Example 2 [Synthesis of Colored Resin Particles (5)] The pigment described in Comparative Example 2 was used as Permanent Red 4R (5 parts), and the pigment dispersant was Disper.
(Byk-111: manufactured by Big Chemie Japan), except that the amount was changed to 2 parts, the same operation as in Comparative Example 1 was performed [mixed dispersion liquid (5) of resin and colorant] and particle size d50 was 20 μm.
m [colored resin particles (5)] were obtained.

Comparative Example 3 [Synthesis of Colored Resin Particles (6)] All except that the pigment described in Comparative Example 2 was changed to 7 parts of benzidine yellow and the pigment dispersant was changed to 2.1 parts of Texaphor (manufactured by San Nopco Ltd.). The same operation as in Comparative Example 1 was carried out to obtain [mixed dispersion liquid (6) of resin and colorant] and [colored resin particle (6)] having a particle size d50 of 20 μm.

Physical Property Measurement Example 1 Pigment particle size (particle size d) of [Pigment Dispersion (1)] to [Pigment Dispersion (6)] obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
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.). The evaluation results are shown in Table 1. The smaller the pigment particle size and the lower the aggregate content, the better the pigment dispersibility.

Performance Evaluation Example 2 Cutting samples of [colored resin particles (1) to [colored resin particles (6)] obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were prepared, and a transmission electron microscope ( The TEM) "H7100" (manufactured by Hitachi, Ltd.) was used to observe the pigment dispersion state of the cross section of the colored resin particles. (Magnification: 10,000 times) The dispersed state of the pigment was judged according to the following evaluation criteria. The results are shown in Table 3. ⊚: No pigment aggregate (0.5 μm or more). ◯: There are 1 to 3 pigment aggregates (0.5 μm or more). Δ: There are 3 to 9 pigment aggregates (0.5 μm or more). X: There are 10 or more pigment aggregates (0.5 μm or more). Performance Evaluation Example 3 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 2. 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.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

The method of the present invention has the following effects. 1. The pigment dispersion is dispersed very finely and the stability of the dispersed state over time is excellent. 2. The pigment dispersibility in the resin particles is good, 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 the front page (56) References JP-A-5-230225 (JP, A) JP-A-5-230226 (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 (7)

(57) [Claims] 1. A coloring agent (B) and an organic solvent (D) are mixed so as to have a solid content concentration of 1 to 50% by weight, and then the coloring is carried out by using a high pressure jet nozzle type disperser or an ultrasonic type disperser. The agent is dispersed in an organic solvent, and the reactive group-containing prepolymer (A-1), which is a precursor of the resin (A), is dissolved or dispersed in the dispersion so that the solid content concentration becomes 20 to 95% by weight. Then, the solution or dispersion is emulsified or dispersed in an aqueous medium, and (A-1) is extended and / or crosslinked by an extender and / or a crosslinking agent (A-2) to give a resin (A). A method for producing colored resin particles, which comprises forming and granulating. 2. The reactive group contained in the prepolymer (A-1) is a reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and the (A-2) is The production method according to claim 1, which is a compound (A-2-1) having or generating active hydrogen. 3. The method according to claim 2, wherein the (A-2-1) is water or a ketimine compound. 4. The production method according to claim 1, wherein the resin (A) is a resin selected from the group consisting of polyester resins, polyurethane resins, polyurea resins and epoxy resins. 5. The colorant (B) is a white pigment, a yellow pigment,
Orange pigment, red pigment, purple pigment, blue pigment, green pigment,
The manufacturing method according to claim 1, comprising a brown pigment or a black pigment. 6. The reactive group-containing prepolymer (A-
1), other resin (C) is used together with the elongation agent and / or the cross-linking agent (A-2), and the weight ratio of the (A-1) and the (C) is from 2:98 to 100: 0. It is a range, The manufacturing method in any one of Claims 1-5. 7. The method according to claim 6, wherein the resin (C) is a resin selected from the group consisting of vinyl resins, polyester resins, polyurethane resins, polyurea resins and epoxy resins.