JP4648684B2 - Dispersion and method for producing colored organic solid particles - Google Patents

Description

  The present invention relates to colored organic solid particles (resin particles, etc.) useful as cosmetics, image recording materials such as ink and colored particles used in inkjet printers, paints such as powder paints, and colorants for printing inks. ) And a method for producing the same, and a dispersion used for producing the organic solid particles.

  Conventionally, as a method of obtaining colored thermoplastic resin fine particles, a mechanical pulverization method, for example, a colored resin composition obtained by melt kneading a colored component with a resin is roughly pulverized with a crusher or the like. Thereafter, a method of finely pulverizing with a jet mill or the like and then classifying with an air classifier or the like is used.

  However, in such a method, in addition to the expensive manufacturing equipment, the obtained particles are also indeterminate and the particle size varies. In order to equalize the size of the resin particles, it is necessary to classify the resin particles. Since the classification produces a large amount of resin particles that cannot be used, it is economically disadvantageous. In addition, spherical particles are preferable from the viewpoint of blocking between particles, dispersibility, fluidity, and the like, but it is impossible to obtain spherical fine particles by a mechanical pulverization method.

  Japanese Patent Application Laid-Open No. 2002-275272 (Patent Document 1) describes a colored resin in which a pigment is uniformly dispersed or dissolved in a thermoplastic resin as a molten state, and the molten colored resin is insoluble in which the colored resin does not dissolve. Disclosed is a method for producing a particulate colored resin in which droplets are formed into fine particles in a medium and the droplets are cooled and solidified. However, in this method, the process is complicated, and in the droplet forming process, it is necessary to raise the temperature of the insoluble medium in order to dissolve the thermoplastic resin. Therefore, the type of the insoluble medium is an organic solvent having a high boiling point. Limited to. Further, in the cooling process, in order to avoid the fusion of droplets, it is necessary to cool to near 0 ° C., and it is impossible to obtain particles having a uniform and uniform particle size.

In JP-A-10-176065 (Patent Document 2), a resin (a) is obtained by melt-kneading one or more other thermoplastic resins (b) with a thermoplastic resin (a) to be finely powdered. Forms a dispersed phase, and a resin (b) forms a continuous resin composition. The resin (a) is not dissolved, and the resin composition is washed with a solvent and conditions in which the resin (b) is dissolved. A method for obtaining spherical fine particles of the resin (a) is disclosed. This document also proposes a method of adding various additives including pigments and dyes to the resin (a). However, in this method, since additives such as pigments and dyes are also distributed to the resin (b) side constituting the continuous phase, the additives such as pigments cannot be effectively used as a functional agent of the resin, and the economy It is also disadvantageous. In this method, the resin to be pulverized must be a resin having excellent solvent resistance, and the dispersed phase and the continuous phase must be incompatible with each other. It is necessary to appropriately select a combination of a continuous phase resin and a solvent depending on the type. Therefore, not only the combination of resins is limited, but also the combination of resin and solvent is limited. Further, in the process of cooling the dispersion, incompatible resins easily cause large phase separation, so that once the dispersed phase is formed, the dispersed phases once again cannot be obtained to obtain fine particles having a predetermined shape. Furthermore, since the resin forming the continuous phase is not involved in the resin fine particles as a product, it is finally collected or discarded in a dissolved state. However, recovery of the resin in the solution is not only very difficult, but also increases the production cost of the resin fine particles. Further, when the resin solution is discarded as a waste liquid, there is a concern about an adverse effect on the environment.
JP 2002-275272 A (Claim 1) JP 10-176065 A (Claim 1, paragraph number [0042])

  Therefore, the object of the present invention is to provide colored particles (such as colored resin particles) corresponding to the dispersed phase by a simple method regardless of the compatibility or incompatibility between the dispersed phase and the matrix and the solvent resistance. An object of the present invention is to provide a dispersion capable of industrially advantageously producing organic solid particles), a method for producing colored particles from the dispersion, and colored particles.

  Another object of the present invention is to provide a dispersion, a method for producing colored particles, and colored particles that can efficiently color the dispersed phase and can be effectively used by increasing the use efficiency of the colorant.

  Still another object of the present invention is to provide a dispersion capable of reducing the particle size of the colored particles, narrowing the particle size distribution width, and making the particles spherical, a method for producing the colored particles, and the colored particles.

  Another object of the present invention is to provide a dispersion capable of reducing the environmental burden due to waste liquid and the like, and a method for producing colored particles.

  As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that when forming a dispersion by combining a water-soluble auxiliary component composed of at least an oligosaccharide with a meltable organic solid component, an organic solid When a colorant with high affinity is selected, the colorant can be selectively distributed to the dispersed phase side of the dispersion, and the water-soluble auxiliary component that is the matrix of the dispersion is eluted using an aqueous medium. Or, when extracted, the eluate was found to contain almost no colorant, and the present invention was completed.

  That is, the dispersion of the present invention is a water-soluble solution containing a particulate dispersed phase composed of a meltable organic solid component (such as a resin component) (A) and a colorant (B) and at least an oligosaccharide (C1). And a matrix composed of the sex assistant component (C), and the dispersed phase is dispersed in the matrix. The colorant (B) may be at least one selected from water-insoluble (or hardly soluble) dyes (such as oil-soluble dyes) and organic or inorganic pigments. The proportion of the colorant (B) may be about 0.001 to 200 parts by weight (for example, 0.001 to 100 parts by weight) with respect to 100 parts by weight of the organic solid component (A).

  The average particle size of the dispersed phase may be about 0.1 to 100 μm, and the average particle size of the colorant (B) may be 50% or less of the average particle size of the dispersed phase. The dispersed phase may be a spherical dispersed phase having a coefficient of variation of an average particle diameter of 60 or less and a length ratio between a major axis and a minor axis (major axis / minor axis) = 1.5 / 1 to 1/1. The organic solid component (A) may be composed of a thermoplastic resin having a weight average molecular weight of 500,000 or less.

  The oligosaccharide (C1) may be composed of at least a tetrasaccharide. The oligosaccharide (C1) may be composed of at least one selected from starch sugar, galactooligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide and chitosan oligosaccharide. The viscosity of a 50% by weight aqueous solution of the oligosaccharide (C1) may be 1 Pa · s or higher when measured with a B-type viscometer at a temperature of 25 ° C.

  The auxiliary component (C) may be composed of an oligosaccharide (C1) and a water-soluble plasticizing component (C2) for plasticizing the oligosaccharide (C1). The oligosaccharide (C1) exhibits a melting point or softening point at a temperature higher than the heat distortion temperature of the organic solid component (resin component, etc.) (A), or decomposes to melt or soften the plasticizing component (C2). The point may be equal to or lower than the heat distortion temperature of the organic solid component (resin component or the like) (A). The plasticizing component (C2) may be composed of at least one selected from saccharides and sugar alcohols (erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol, mannitol, etc.). The ratio (weight ratio) between the oligosaccharide (C1) and the plasticizing component (C2) may be oligosaccharide (C1) / plasticizing component (C2) = 99/1 to 50/50.

  In the dispersion, the ratio (weight ratio) between the organic solid component (A) and the auxiliary component (C) was organic solid component (A) / auxiliary component (C) = 55/45 to 1/99. May be.

  In the present invention, the auxiliary component (C) is eluted from the dispersion to produce particles composed of an organic solid component (A) and a colorant (B), and obtained by this method. Particles are also included. These particles have an average particle diameter of 0.1 to 100 μm and an average particle diameter variation coefficient of 60 or less, and the length ratio between the major axis and minor axis of the particle is major axis / minor axis = 1.5 / 1 to 1. / 1 spherical particles may be used.

  In this specification, the dispersion may be an organic solid component (resin component, etc.), a colorant and an auxiliary component, and a composition (resin composition, etc.) that forms a dispersion system. Sometimes used interchangeably. In the present specification, the colored organic solid component may be simply referred to as “organic solid component”, the colored resin component may be simply referred to as “resin component”, and the water-soluble auxiliary component may be referred to as “auxiliary component”. The spherical shape is not limited to a true sphere, and the ratio of the length of the major axis to the minor axis is major axis / minor axis = 1.5 / 1 to 1/1 (preferably 1.2 / 1 to 1/1). More preferably, the shape is about 1.1 / 1 to 1/1).

  In the present specification, the “organic solid component” is not limited to a carbon-based organic compound as long as it is solid, and is used to include a silicon compound (such as a silicone resin).

  In the present invention, a dispersed phase composed of an organic solid component (resin component, etc.) and a colorant is dispersed in the form of particles in a matrix composed of a specific water-soluble auxiliary component. Regardless of the affinity (compatible or incompatible) and solvent resistance, colored particles (colored resin particles and the like) corresponding to the dispersed phase can be industrially advantageously produced by a simple method. Further, since a colorant having a high affinity for the organic solid component is used as the colorant, the dispersed phase can be colored efficiently, and the use efficiency of the colorant can be enhanced and effectively used. The colorant can be selectively distributed to the dispersed phase side, and the auxiliary component is composed of a naturally derived component, so that the burden on the environment due to waste liquid or the like can be reduced. Furthermore, the particle size of the colored particles can be reduced, the particle size distribution width can be narrowed, and the particles can be made spherical.

[Dispersion]
In the dispersion of the present invention, the particulate dispersed phase composed of the meltable organic solid component (A) and the colorant (B) contains at least an oligosaccharide (C1) as a water-soluble auxiliary component (C). Is distributed in a matrix composed of

(A) Meltable organic solid component As the meltable organic solid component (A), an incompatible or hydrophobic component (water-insoluble component) can usually be used for the water-soluble auxiliary component (C). . The organic solid component (A) is usually solid at room temperature (about 15 to 25 ° C.), and may be a low molecular compound or a high molecular compound (or resin). The melting point of the low molecular weight organic solid component (A) may be about 40 to 280 ° C. (preferably 50 to 270 ° C., more preferably 70 to 260 ° C.), and has a relatively high melting point of about 100 to 260 ° C. The compound which has can also be used. The organic solid component (A) can be used alone or in combination of two or more.

  Examples of the low-molecular organic solid component (A) include waxes or lipids, stabilizers (hindered phenol-based, hindered amine-based, phosphorus-based antioxidants, benzophenone-based, salicylic acid-based UV absorbers, hindered amines). UV absorbers such as light stabilizers and light stabilizers), antistatic agents, flame retardants, lubricants, crystal nucleating agents, vulcanization accelerators, antiaging agents, vulcanizing agents, and the like. Examples of the waxes or lipids include aliphatic hydrocarbon waxes (polyolefin waxes such as polyethylene wax and polypropylene wax, paraffin waxes, microcrystalline waxes, etc.), vegetable or animal waxes (carnauba wax, beeswax, Shellac wax, montan wax, etc.), higher fatty acid esters (glycerin fatty acid esters, diglycerin fatty acid esters, polyglycerin fatty acid esters, etc.), fatty acid amides (stearic amide, erucic acid amide, etc.), alkylene bis fatty acid amides (methylene bis stearic acid) Amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide), fatty acid metal salt (barium laurate, zinc laurate, calcium stearate) Arm, zinc stearate, higher fatty acid polyvalent metal salts such as magnesium stearate), and others. The above waxes or lipids can also be used as a lubricant. These components can be used alone or in combination of two or more.

  In the present invention, even such a low molecular organic solid component can be obtained as particles (particularly true spherical particles) by combining with the water-soluble auxiliary component (C). The handleability of the component (A) can be improved.

  As the organic solid component (A), a polymer compound (resin) is often used. Examples of the resin include thermoplastic resins [polyester resins (for example, aromatic polyester resins and aliphatic polyester resins), polyamide resins, polyurethane resins, poly (thio) ether resins (for example, polyacetal resins). , Polyphenylene ether resins, polysulfide resins, polyether ketone resins, etc.), polycarbonate resins, polysulfone resins, polyimide resins and other condensation thermoplastic resins; polyolefin resins, (meth) acrylic resins, styrene resins Resins, vinyl resins (for example, halogen-containing resins, vinyl ester resins, vinyl alcohol resins, etc.), vinyl polymerization thermoplastic resins; cellulose-derived and other natural product-derived resins; thermoplastic silicone resins, etc.], and heat Curable resin (eg Epoxy Resin, unsaturated polyester resin, diallyl phthalate resin, a silicone resin (silicone rubber, silicone varnish), etc.) and the like. These resins can be used alone or in combination of two or more. As the resin component (A), a thermoplastic resin or a water-insoluble resin (such as a water-insoluble thermoplastic resin) is usually used.

(Thermoplastic resin)
(1) Polyester resin Examples of polyester resins include homopolyester or copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component; homopolyester or copolyester obtained by polycondensation of oxycarboxylic acid; lactone And homopolyester or copolyester obtained by ring-opening polymerization. These polyester resins can be used alone or in combination of two or more.

  Examples of the dicarboxylic acid component include aromatic dicarboxylic acids [e.g., terephthalic acid, isophthalic acid, phthalic acid; alkyl-substituted phthalic acids such as methyl terephthalic acid and methyl isophthalic acid; naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, etc.); 4,4'-diphenyldicarboxylic acid, diphenyldicarboxylic acid such as 3,4'-diphenyldicarboxylic acid; 4,4'-diphenoxyethanedicarboxylic acid Diphenoxyethane dicarboxylic acid such as acid; diphenyl ether dicarboxylic acid such as diphenyl ether-4,4′-dicarboxylic acid; diphenylalkane dicarboxylic acid such as diphenylmethane dicarboxylic acid and diphenylethane dicarboxylic acid; An aromatic dicarboxylic acid having about 8 to 20 carbon atoms such as an acid], an aliphatic dicarboxylic acid (for example, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedicarboxylic acid, dimer acid, etc. Of aliphatic dicarboxylic acid having about 2 to 40 carbon atoms), alicyclic dicarboxylic acid (for example, cyclohexanedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, highmic acid, etc. And about 12 alicyclic dicarboxylic acids). These dicarboxylic acid components can be used alone or in combination of two or more.

  The dicarboxylic acid component includes derivatives capable of forming an ester, for example, lower alkyl esters such as dimethyl ester, acid halides such as acid anhydride and acid chloride, and the like.

Examples of the diol component include aliphatic C _2-12 diols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, poly C _2-4 alkylene). Glycol (diethylene glycol, dipropylene glycol, etc.), alicyclic C _6-12 diol (eg, cyclohexanediol, cyclohexanedimethanol, etc.), aromatic C _6-20 diol (eg, resorcinol, hydroquinone, naphthalenediol, bisphenol) Bisphenols such as A, F, and AD, and alkylene oxide adducts of bisphenols). These diol components can be used alone or in combination of two or more.

Examples of the oxycarboxylic acid include aliphatic C _2-6 oxycarboxylic acids such as glycolic acid, lactic acid, oxypropionic acid, oxybutyric acid, glyceric acid, and tartronic acid; and aromatic oxycarboxylic acids such as hydroxybenzoic acid and oxynaphthoic acid. An acid etc. are mentioned. These oxycarboxylic acids can be used alone or in combination of two or more.

Examples of the lactone include C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, and caprolactone. These lactones can be used alone or in combination of two or more. Of these lactones, C _4-10 lactones, particularly caprolactone (eg, ε-caprolactone, etc.) are preferred.

  Polyester resins include aromatic polyester resins and aliphatic polyester resins.

Examples of the aromatic polyester resin include the aromatic dicarboxylic acid (preferably an aromatic dicarboxylic acid having about 8 to 20 carbon atoms such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.) and the fat. Group diols (preferably, aliphatic C _2-12 diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, etc.) or the alicyclic diols (preferably cyclohexanedimethanol, etc.) Homopolyester or copolyester obtained by polycondensation with an alicyclic C _6-20 diol, etc., preferably an alkylene arylate unit such as alkylene terephthalate or alkylene naphthalate as the main component (for example, 50 Homopolyester or copoly) Examples include esters. Examples of the copolymer component include poly C _2-4 alkylene glycol having an oxyalkylene unit having a number of repetitions of about 2 to 4 [such as a glycol containing a poly (oxy-C _2-4 alkylene) unit such as diethylene glycol] and 6 carbon atoms. About ˜12 aliphatic dicarboxylic acids (such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) may be contained.

Specifically, examples of the aromatic polyester-based resin include polyalkylene terephthalate [for example, polycycloalkanedi C _1-4 alkylene terephthalate such as poly (1,4-cyclohexanedimethylene terephthalate) (PCT); polyethylene terephthalate. (PET), poly C _2-4 alkylene terephthalate such as polybutylene terephthalate (PBT)], poly C _2-4 alkylene naphthalate (for example, polyethylene naphthalate) corresponding to this polyalkylene terephthalate, mainly ethylene terephthalate unit Examples thereof include polyethylene terephthalate copolyester contained as a component and polybutylene terephthalate copolyester containing a butylene terephthalate unit as a main component. The aromatic polyester resin may be a liquid crystalline polyester.

Examples of the aliphatic polyester resin include aliphatic dicarboxylic acid components (for example, aliphatic dicarboxylic acids having about 2 to 6 carbon atoms such as oxalic acid, succinic acid, and adipic acid, preferably oxalic acid and succinic acid. About 2 to 4 aliphatic dicarboxylic acids and the like, and the aliphatic diol components (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, etc.) Group C _2-6 diol (C _2-6 alkane diol), preferably aliphatic C _2-4 diol (C _2-4 alkane diol) such as ethylene glycol, 1,4-butanediol, neopentyl glycol) Homopolyester or copolyester obtained by polycondensation or the above aliphatic oxycarboxylic acid (for example Homopolyesters or copolyesters of aliphatic C _2-6 oxycarboxylic acids such as oxalic acid, lactic acid, oxypropionic acid, oxybutyric acid, preferably aliphatic C _2-4 oxycarboxylic acids such as glycolic acid and lactic acid Homopolylactone obtained by ring-opening polymerization of the lactone (preferably C _4-10 lactone such as caprolactone) using an agent (bifunctional or trifunctional initiator, for example, an active hydrogen compound such as alcohol) Copolylactone is mentioned. Examples of the copolymer component include poly C _2-4 alkylene glycols having a number of repeating oxyalkylene units of about 2 to 4 [such as glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol], and the number of carbon atoms. About 6 to 12 aliphatic dicarboxylic acids (such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) may be contained.

Specifically, as the aliphatic polyester-based resin, for example, a polyester-based resin obtained by polycondensation of a dicarboxylic acid component and a diol component (for example, polyethylene oxalate, polybutylene oxalate, polyneopentylene olefin). Poly C _2-6 alkylene oxalate such as gizarate; Poly C _2-6 alkylene succinate such as polyethylene succinate, polybutylene succinate, polyneopentylene succinate; polyethylene adipate, polybutylene adipate, polyneopenty Poly C _2-6 alkylene adipate such as len adipate), polyoxycarboxylic acid resin (for example, polyglycolic acid and polylactic acid), polylactone resin [for example, polycaprolactone (manufactured by Daicel Chemical Industries, Ltd., PCLH7) , PCLH4, PC H1, etc.) and poly C _3-12 lactone resins], and others. Specific examples of the copolyester include, for example, a copolyester using two kinds of dicarboxylic acid components (for example, poly C _2-4 alkylene such as polyethylene succinate-adipate copolymer resin and polybutylene succinate-adipate copolymer resin). Succinate-adipate copolymer resin, etc.), a copolyester obtained from a dicarboxylic acid component, a diol component, and a lactone (eg, polycaprolactone-polybutylene succinate copolymer resin (butanediol-succinic acid-caprolactone terpolymer) Etc.) etc.).

  The polyester resin used in the present invention may be a polyester resin containing a urethane bond (for example, an aliphatic polyester resin containing a urethane bond). The polyester resin containing a urethane bond is preferably a resin obtained by increasing the molecular weight of the polyester resin (such as low molecular weight polyester diol) with a diisocyanate (for example, aliphatic diisocyanate).

  Examples of the diisocyanate include aromatic diisocyanates (for example, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate), araliphatic diisocyanates (for example, xylylene diisocyanate), alicyclic diisocyanates (for example, isophorone diisocyanate). Etc.), aliphatic diisocyanates (for example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate methyl ester, trimethylhexamethylene diisocyanate, etc.). These diisocyanates can be used alone or in combination of two or more. Of these diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate can be used.

  Examples of the polyester resin containing a urethane bond (for example, aliphatic polyester resin) include “Bionore # 1000”, “Bionore # 3000”, and “Bionore # 6000” series manufactured by Showa Polymer Co., Ltd. .

(2) Polyamide-based resin Examples of the polyamide-based resin include aliphatic polyamide-based resins, alicyclic polyamide-based resins, and aromatic polyamide-based resins. Usually, aliphatic polyamide-based resins are used. These polyamide resins can be used alone or in combination of two or more.

Aliphatic polyamide resins include aliphatic diamine components (C _4-10 alkylenediamines such as tetramethylenediamine and hexamethylenediamine) and aliphatic dicarboxylic acid components (C ₄₋ such as adipic acid, sebacic acid and dodecanedioic acid). ₂₀ such alkylene dicarboxylic acids) and condensates of (e.g., polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, or polyamide 1212), lactams (.epsilon.-caprolactam, such as ω- laurolactam C _{4 -20} lactam etc.) or aminocarboxylic acid (carbon number _C4-20 amino carboxylic acid etc. such as ω-aminoundecanoic acid) homopolymer or copolymer (eg polyamide 6, polyamide 11, polyamide 12, polyamide 6/11) , Polyamide 6/12 etc.), these Copolyamide polyamide components copolymerized (e.g., a polyamide 66/11, a polyamide 66/12) and the like.

Furthermore, the polyamide-based resin may have biodegradability. Examples of the biodegradable polyamide resin include the aliphatic diamine component (C _4-10 alkylene diamine such as tetramethylene diamine and hexamethylene diamine) and the aliphatic dicarboxylic acid component (adipic acid, sebacic acid, dodecanedioic acid and the like). C _4-20 alkylene dicarboxylic acid), and polyester amides which are condensates with the above aliphatic diol components (C _2-12 alkylene glycol such as ethylene glycol, propylene glycol, butane diol, etc.).

(3) Polyurethane resin A polyurethane resin can be obtained by reaction of diisocyanates and polyols (for example, diols) and, if necessary, a chain extender. Diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, phenylene diisocyanate, tolylene diisocyanate, Examples thereof include aromatic diisocyanates such as diphenylmethane-4,4′-diisocyanate and 1,5-naphthalene diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate.

  Examples of the polyols include polyester polyols, polyether polyols, and polycarbonate polyols. Of the polyols, diols (polyester diol, polyether diol, polycarbonate diol, etc.) are particularly preferable. These polyol components can be used alone or in combination of two or more.

Examples of diols include polyester diols (C _4-12 aliphatic dicarboxylic acid components such as succinic acid, adipic acid, and azelaic acid, and C _2-12 aliphatic diols such as ethylene glycol, propylene glycol, butanediol, and neopentyl glycol. A polyester diol obtained from a C _4-12 lactone component such as ε-caprolactone, a polyester diol obtained from the aliphatic dicarboxylic acid component and / or the aliphatic diol component and the lactone component, etc. ), Polyether diol (polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polytetramethylene glycol, bisphenol A-alkylene oxide adduct, etc.) Etc. can be used (the polyether diol polyester diols used as a part of the diol component) esters ether diols.

Furthermore, as chain extenders, in addition to C _2-10 alkylene glycols such as ethylene glycol and propylene glycol, diamines [aliphatic diamines (linear or branched alkylene diamines such as ethylene diamine, trimethylene diamine and tetramethylene diamine) Linear or branched polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylenetriamine), alicyclic diamines (such as isophorone diamine), aromatic diamines (phenylenediamine, xylylene) Amine etc.) can also be used. These polyurethane resins can be used alone or in combination of two or more.

(4) Poly (thio) ether-based resin The poly (thio) ether-based resin includes polyalkylene glycol, polyphenylene ether-based resin, and polysulfide-based resin (polythioether-based resin). Examples of the polyalkylene glycol include polypropylene glycol, polytetramethylene ether glycol, and alkylene glycols such as polyoxyethylene-polyoxypropylene block copolymers, or copolymers (poly C _2-4 alkylene glycol, etc.). . These poly (thio) ether resins can be used alone or in combination of two or more.

(5) Polycarbonate resin Polycarbonate resins include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate. These polycarbonate resins can be used alone or in combination of two or more.

(6) Polysulfone resin Polysulfone resins include polysulfone resins obtained by polycondensation of dihalogenodiphenylsulfone (such as dichlorodiphenylsulfone) and bisphenols (such as bisphenol A or metal salts thereof), polyethersulfone resins, and polysulfones. Examples include allyl sulfone resin (trade name: RADEL). These polysulfone resins can be used alone or in combination of two or more.

(7) Polyolefin resin Polyolefin resins include α-C _2-6 olefin homo- or copolymers, such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (methylpentene-1) and other olefins. Homopolymer or copolymer of olefin and copolymerizable monomer (ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer) Etc.). These polyolefin resins can be used alone or in combination of two or more.

(8) (Meth) acrylic resin As (meth) acrylic resin, (meth) acrylic monomer ((meth) acrylic acid, (meth) acrylic acid C _1-18 alkyl ester, (meth) acrylic acid Hydroxyalkyl, glycidyl (meth) acrylate, (meth) acrylonitrile, etc.) or a copolymer, for example, poly (meth) acrylate such as poly (meth) acrylate, methyl methacrylate- (meth) acryl Acid copolymer, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester-styrene copolymer (MS resin) Etc.). Preferred (meth) acrylic resins include poly (meth) acrylic acid C _1-5 alkyl, methyl methacrylate-acrylic acid ester copolymer, (meth) acrylic acid ester-styrene copolymer (MS resin, etc.), etc. Is included. These (meth) acrylic resins can be used alone or in combination of two or more.

(9) Styrenic resin As the styrene resin, a styrene monomer (styrene, α-methylstyrene, vinyltoluene, etc.) or a copolymer (polystyrene, styrene-vinyltoluene copolymer, styrene-α-) is used. Methyl styrene copolymer), copolymer of styrene monomer and copolymerizable monomer (styrene-acrylonitrile copolymer (AS resin), (meth) acrylate ester-styrene copolymer (MS) Resin), styrene-maleic anhydride copolymer, copolymer such as styrene-butadiene block copolymer, etc .; acrylonitrile-acrylic ester-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer Polymer (ACS resin), acrylonitrile-vinyl acetate-styrene copolymer (AXS tree) ) And the like; Graft polymers obtained by graft polymerization of at least a styrene monomer in the presence of a rubber component, such as impact-resistant polystyrene (HIPS or rubber-grafted polystyrene resin), acrylonitrile-butadiene -Styrene copolymer (ABS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), etc.). These styrenic resins can be used alone or in combination of two or more.

(10) Vinyl-based resin The vinyl-based resin includes a vinyl-based monomer alone or a copolymer, or a copolymer with another copolymerizable monomer. Examples of vinyl monomers include halogen-containing vinyl monomers [eg, chlorine-containing vinyl monomers (eg, vinyl chloride, vinylidene chloride, chloroprene, etc.), fluorine-containing vinyl monomers (eg, fluoroethylene, etc.) Etc.], and carboxylic acid vinyl esters [vinyl esters such as vinyl acetate, vinyl propionate, vinyl crotonate, vinyl benzoate, etc.]. These vinyl resins can be used alone or in combination of two or more.

  Examples of vinyl resins include vinyl chloride resins (for example, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride-vinyl acetate copolymers, etc.), fluororesins (for example, polyfluoride). Vinyl, polyvinylidene fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, etc.), vinyl ester resin (For example, polyvinyl acetate, vinyl acetate-ethylene copolymer, ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate- (meth) acrylic acid ester copolymer, etc.). .

  The vinyl resin may be a derivative of the vinyl ester resin, for example, a vinyl alcohol resin (for example, polyvinyl acetal such as polyvinyl formal or polyvinyl butyral; a saponified product of the vinyl acetate copolymer, for example, ethylene- Vinyl alcohol copolymer, etc.). Of these vinyl alcohol resins, saponified vinyl acetate copolymers, particularly ethylene-vinyl alcohol copolymers are preferred. In the saponified vinyl acetate copolymer, the degree of hydrophilicity may be adjusted by adjusting the proportion of hydrophobic comonomer units (for example, ethylene units in an ethylene-vinyl alcohol copolymer). When a saponified vinyl acetate copolymer is used as the hydrophilic resin, the proportion of the hydrophobic comonomer unit is adjusted to, for example, about 10 to 40% by weight from the viewpoint of affinity for the auxiliary component (C). May be.

(11) Cellulose derivative Examples of the cellulose derivative include cellulose esters (such as cellulose acetate and cellulose phthalate), cellulose carbamates (such as cellulose phenyl carbamate), and cellulose ethers (such as cyanoethyl cellulose). These cellulose derivatives can be used alone or in combination of two or more.

  Examples of the cellulose ester include cellulose acetate (cellulose acetate) such as cellulose diacetate and cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and other organic acid esters (or acylcellulose). ); Inorganic acid esters such as cellulose nitrate, cellulose sulfate and cellulose phosphate; and mixed acid esters such as cellulose nitrate acetate.

Examples of the cellulose ether include alkyl cellulose (for example, C _2-6 alkyl cellulose such as ethyl cellulose, isopropyl cellulose, and butyl cellulose), aralkyl cellulose (for example, benzyl cellulose), cyanoethyl cellulose, and the like.

  In terms of biodegradability, the degree of substitution of the cellulose derivative is preferably low. For example, the average degree of substitution is 2.5 or less, preferably 2 or less (for example, 0.1 to 2), and more preferably 1.5 or less. (For example, about 0.1 to 1.5).

(12) Thermoplastic elastomer Examples of the thermoplastic elastomer include polyamide elastomers, polyester elastomers, polyurethane elastomers, polystyrene elastomers, polyolefin elastomers, polyvinyl chloride elastomers, and fluorine thermoplastic elastomers. These thermoplastic elastomers can be used alone or in combination of two or more.

  When the thermoplastic elastomer is a block copolymer, the block structure is not particularly limited, and may be a triblock structure, a multiblock structure, a star block structure, or the like.

  The heat distortion temperature (for example, Vicat softening point specified by JIS K 7206) of the resin component can be selected from the range of 60 to 300 ° C., for example, 80 to 260 ° C., preferably 100 to 240 ° C. (for example, 110 to 240). ° C), more preferably about 120 to 230 ° C (eg 130 to 220 ° C).

Preferred resins include water-insoluble thermoplastic resins (or hydrophobic thermoplastic resins), such as polyamide resins, polyolefin resins, styrene resins, vinyl resins (for example, halogen-containing resins, vinyl ester resins, vinyl alcohols). Resin), biodegradable resins [for example, aliphatic polyester resins (for example, polylactic acid resins and poly C _3-12 lactone resins), biodegradable polyester resins such as polyester amide, vinyl alcohol Resin, the cellulose derivative] and the like. In order to facilitate melt-kneading with the auxiliary component (C), a resin having a hydrophilic group such as an amino group, a hydroxyl group or a carboxyl group may be used. Moreover, when the organic solid component (A) is composed of the biodegradable resin, resin particles having excellent biodegradability can be obtained.

  The average molecular weight of a resin component (such as a thermoplastic resin) is a weight average molecular weight or viscosity average molecular weight in terms of polystyrene by gel permeation chromatography, and is, for example, 500,000 or less (for example, about 10,000 to 500,000). , Preferably about 50,000 to 400,000, more preferably about 10,000 to 350,000. In addition, a viscosity average molecular weight is employable about thermoplastic resins, such as a cellulose derivative, whose molecular weight is difficult to measure by gel permeation chromatography. The weight average molecular weight of the resin component can also be adjusted by the kneading time and kneading temperature of the resin component.

(B) Colorant The colorant (B) is not particularly limited as long as it is a pigment used for coloring a resin or plastic, but the colorant is efficiently distributed to the dispersed phase, and the auxiliary component (C) is added. In order to prevent the colorant from being extracted into the solvent for elution or extraction, for example, water-insoluble (or poorly soluble) dyes or pigments [oil-soluble dyes (solvent dyes, etc.), disperse dyes, vat dyes, sulfides Dyes, azoic dyes (naphthol dyes), pigments (inorganic pigments, organic pigments, etc.)] and the like can be used. Further, since the colorant (B) is distributed to the dispersed phase, the dispersed phase can be colored chromatic (yellow, orange, red, purple, blue, green, etc.) or achromatic by the colorant (B). is there.

  Examples of the water-insoluble dyes (oil-soluble dyes, disperse dyes, vat dyes) include azo dyes (yellow dyes such as Disperse Yellow 3); dyes obtained by diazotizing fast orange GC base and coupling to naphthol AS; Disperse Orange Orange dyes such as 3; red dyes such as Disperse Red 1; black dyes such as Disperse Black 1), anthraquinone dyes (yellow dyes such as Vat Yellow 2 and 3; red dyes such as Disper Red 11 and 15; disperse Purple dyes such as violet 1; blue dyes such as bat blue 1, 3, 14 and solvent blue 11), condensed polycyclic quinone dyes (yellow dyes such as bat yellow 4; orange dyes such as bat orange 3; bat blue Blue dyes such as 4; Bat Green 1, Dispersing Green dyes such as dye 1), selenium dyes (red dyes such as vat red 23), indigoid dyes (purple dyes such as vat violet 2; blue dyes such as vat blue 1), phthalocyanine dyes, carbonium Examples include ionic dyes, nitro dyes, quinoline dyes, and naphthoquinone dyes.

  Examples of the inorganic pigment include white pigments (such as titanium dioxide (hydrophobized titanium dioxide), zinc oxide, zinc sulfide), extender pigments (calcium carbonate, barium sulfate, silica, aluminum hydroxide, kaolin clay, talc, bentonite, etc.) , Black pigments (channel black, furnace black, thermal black, lamp black, ketjen black and other carbon blacks), red pigments (iron oxide such as bengara, red lead, molybdenum red, cadmium red, etc.), yellow pigments (resurge) , Yellow lead, yellow iron oxide, cadmium yellow, etc.), blue pigments (such as bitumen, ultramarine blue, etc.). Further, a ferromagnetic material may be used as an inorganic pigment. Examples of such ferromagnetic materials include ferromagnetic metals (powder) such as iron, cobalt, and nickel; ferromagnetic alloys (powder) such as magnetite and ferrite; and ferromagnetic metal oxides (powder) such as magnetic iron oxide. Etc. can be exemplified.

  Examples of organic pigments include azo pigments [insoluble azo pigments or azo lake pigments such as yellow, orange or red pigments (for example, pigment red 1,3,4,6,48,57: 1 (red 202)) -Naphthol azo pigments; pyrazolone azo pigments such as pigment red 37 and pigment orange 13), green pigments (metal complex salts of azo compounds such as pigment green 10), condensed azo compounds, high molecular weight azo pigments, Azo pigments containing azomethine groups, azomethine pigments, etc.), phthalocyanine pigments [copper phthalocyanine, blue pigments such as pigment blue 15,15: 3 (phthalocyanine blue), pigment green 7 (phthalocyanine green), etc.], quinacridone pigments (Purple pigments such as Pigment Violet 19 ), Isoindolinone pigments (yellow pigments such as Pigment Yellow 110), perinone / perylene pigments (red pigments such as Pigment Red 179 and 190), selenium pigments (blue pigments such as Pigment Blue 60) , Dioxazine pigments (purple pigments such as pigment violet 23), anthraquinone pigments (yellow, orange or red pigments such as pigment yellow 108, 123, pigment red 83, 177), indigo or thioindigo pigments (indigo, indigo white) Blue pigments such as indirubin; red pigments such as thioindigo and pigment red 88), black pigments such as aniline black, diketopyrrolopyrrole pigments, benzimidazolone compounds, diarylide yellow (pigmen) To yellow 83).

  The colorant may be a fluorescent pigment or dye, a phosphorescent pigment, or the like. The colorants can be used alone or in combination of two or more.

  When a colorant (water-insoluble dye or pigment) having a higher affinity for the organic solid component (resin component, etc.) (A) than the water-soluble auxiliary component (C) is used as the colorant, the dispersion is colored. The agent can be distributed to the dispersed phase (organic solid component (A)) side, and the utilization efficiency of the colorant can be improved. Of the colorants, chromatic or black water-insoluble dyes (such as oil-soluble dyes), inorganic pigments (white pigments such as titanium oxide, black pigments such as carbon black), and chromatic organic pigments are preferable.

  In order to efficiently contain (or include) the colorant in the dispersed phase and color the dispersed phase, the particle size of the colorant (B) needs to be smaller than the particle size of the dispersed phase. The average particle diameter of the colorant (B) may be, for example, 50% or less, preferably 30% or less, more preferably 20% or less, of the average particle diameter of the dispersed phase (or the obtained colored particles). A water-insoluble dye such as an oil-soluble dye may be dispersed in the organic solid component (A) with a molecular size. The average particle diameter of the pigment can be selected from a wide range of about 2 nm to 10 μm, and may be, for example, 3 nm to 1 μm, preferably 5 to 500 nm, and more preferably about 10 to 300 nm. Since the oil-soluble dye has a molecular size, it is advantageous to select an oil-soluble dye when reducing the size of the particles (or dispersed phase).

  Since the colorant (B) is uniformly dispersed in the organic solid component (A), the colorant is dispersed in a thermoplastic resin [an organic solid component (A) or an organic solid component (A) compatible with the organic solid component (A). May be diluted in advance with a thermoplastic resin or the like] and used in a masterbatch state. The master batch is a mixture of an organic solid component [for example, a thermoplastic resin (for example, the same type of resin as the resin component), etc.] and a colorant using a conventional kneader (such as the kneader illustrated above). Can be produced. The concentration of the colorant in the masterbatch is not particularly limited, and may be a conventional concentration, for example, about 5 to 20% by weight.

  In the dispersed phase, the ratio of the colorant (B) is selected from a wide range of about 0.001 to 200 parts by weight (for example, 0.001 to 100 parts by weight) with respect to 100 parts by weight of the organic solid component (A). For example, 0.001 to 70 parts by weight (for example, 0.001 to 50 parts by weight), preferably 0.01 to 45 parts by weight (for example, 0.02 to 30 parts by weight), and more preferably 0.05. About 20 parts by weight may be used.

(C) Water-soluble auxiliary component The water-soluble auxiliary component contains at least an oligosaccharide (C1). Further, in order to adjust the heat melting property of the oligosaccharide, the water-soluble auxiliary component may further contain a water-soluble plasticizing component (C2) for plasticizing the oligosaccharide. When the oligosaccharide (C1) and the water-soluble plasticizing component (C2) are combined, the viscosity of the water-soluble auxiliary component (C) can be adjusted in kneading with the organic solid component (A). The water-soluble auxiliary component can form colored organic solid particles (resin particles and the like) by forming a dispersion in combination with an organic solid component and a colorant and then eluting or washing as appropriate.

(C1) Oligosaccharide The oligosaccharide (C1) is composed of 2 to 10 molecules of mono-oligosaccharide dehydrated and condensed via a glycosidic bond, and at least two or more types of monosaccharide and / or sugar alcohol. They are broadly classified into heterooligosaccharides dehydrated and condensed via molecular glycosidic bonds. Examples of the oligosaccharide (C1) include disaccharides to decasaccharides, and disaccharides to hexasaccharides are usually used. Oligosaccharides are usually solid at room temperature. These oligosaccharides may be anhydrides. In the oligosaccharide, a monosaccharide and a sugar alcohol may be bonded. The oligosaccharide may be an oligosaccharide composition composed of a plurality of sugar components. Even such an oligosaccharide composition may be simply referred to as an oligosaccharide. Oligosaccharides (or oligosaccharide compositions) can be used alone or in combination of two or more.

  Examples of disaccharides include trehalose (eg, α, α-trehalose, β, β-trehalose, α, β-trehalose, etc.), Cozybiose, Nigerose, maltose, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, etc. Homo-oligosaccharides such as lactose, sucrose, palatinose, melibiose, rutinose, primeverose, and turanose.

  Trisaccharides include homo-oligosaccharides such as maltotriose, isomaltotriose, panose and cellotriose; hetero-oligosaccharides such as manninotriose, solatriose, melezitose, planteose, gentianose, umbelliferose, lactosucrose and raffinose It is done.

  Examples of tetrasaccharides include homo-oligosaccharides such as maltotetraose and isomalttetraose; and hetero-oligosaccharides such as tetraose in which sugar or sugar alcohol is bonded to the reducing end of stachyose, cellotetraose, scorodose, liquinose, or panose.

  Among these tetrasaccharides, tetraose in which a monosaccharide or a sugar alcohol is bonded to the reducing end of panose is disclosed, for example, in JP-A-10-215892, and glucose, fructose, mannose, Examples include tetraose to which monosaccharides such as xylose and arabinose and sugar alcohols such as sorbitol, xylitol and erythritol are bonded.

  Examples of the pentasaccharide include homooligosaccharides such as maltopentaose and isomaltopentaose; and heterooligosaccharides such as pentaose in which a disaccharide is bonded to the reducing end of panose. Pentaose in which a disaccharide is bonded to the reducing end of panose is disclosed, for example, in JP-A-10-215892, and pentaose in which a disaccharide such as sucrose, lactose, cellobiose or trehalose is bonded to the reducing end of panose. It can be illustrated.

  Examples of hexasaccharides include homo-oligosaccharides such as maltohexaose and isomalthexaose.

  The oligosaccharide is preferably composed of at least a tetrasaccharide from the viewpoint of melt kneading with an organic solid component.

  The oligosaccharide may be an oligosaccharide composition produced by degradation of a polysaccharide. The oligosaccharide composition usually contains a tetrasaccharide. Examples of the oligosaccharide composition include starch sugar (starch saccharified product), galactooligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide, chitosan oligosaccharide and the like.

  For example, the starch sugar is an oligosaccharide composition obtained by allowing an acid or glucoamylase to act on starch, and may be a mixture of oligosaccharides to which a plurality of glucoses are bonded. Examples of starch sugar include reduced starch saccharified product (trade name: PO-10, tetrasaccharide content of 90% by weight or more) manufactured by Towa Kasei Kogyo Co., Ltd.

The galactooligosaccharide is an oligosaccharide composition obtained by allowing β-galactosidase or the like to act on lactose, and may be a mixture of galactosyl lactose and galactose- (glucose) _n (n is an integer of 1 to 4).

Coupling sugar is an oligosaccharide composition obtained by allowing cyclodextrin synthase (CGTase) to act on starch and sucrose. Even if it is a mixture of (glucose) _n -sucrose (n is an integer of 1 to 4) Good.

Fructooligosaccharide (fructo-oligosaccharide) is an oligosaccharide composition obtained by allowing fructofuranosidase to act on sugar, and may be a mixture of sucrose- (fructose) _n (n is an integer of 1 to 4).

  In these oligosaccharide compositions, the content of trisaccharides and tetrasaccharides (especially tetrasaccharides) in the oligosaccharide composition is, for example, 60% by weight or more (60%) in order to prevent a sudden decrease in viscosity during melt kneading. -100 wt%), preferably 70 wt% or more (70-100 wt%), more preferably 80 wt% or more (80-100 wt%), especially 90 wt% or more (90-100 wt%), Also good.

  The oligosaccharide may be a reduced type (maltose type) or a non-reduced type (trehalose type), but a reduced oligosaccharide is preferable because of its excellent heat resistance.

  The reduced oligosaccharide is not particularly limited as long as it has a free aldehyde group or a ketone group and exhibits reducibility. For example, Cozy biose, nigerose, maltose, isomaltose, sophorose, laminaribio. , Cellobiose, gentiobiose, lactose, palatinose, melibiose, rutinose, primebellose, turanose and other disaccharides; maltotriose, isomaltotriose, panose, cellotriose, manninotriose, soratriose and other trisaccharides; maltotetraose, Examples thereof include tetrasaccharides such as isomalttetraose, cellotetraose, and liquinose; pentasaccharides such as maltopentaose and isomaltopentaose; and hexasaccharides such as maltohexaose and isomalthexaose.

  Generally, since the oligosaccharide is a derivative of a polysaccharide that is a natural product or a product derived from a natural product that is produced by reduction thereof, the burden on the environment can be reduced.

  In order to effectively disperse the organic solid component and the auxiliary component by kneading, it is desirable that the oligosaccharide has a high viscosity. Specifically, when measured at a temperature of 25 ° C. using a B-type viscometer, the viscosity of a 50 wt% aqueous solution of oligosaccharide is 1 Pa · s or more (for example, about 1 to 500 Pa · s), preferably 2 Pa · s. s or more (for example, 2 to 250 Pa · s, particularly about 3 to 100 Pa · s), more preferably 4 Pa · s or more (for example, about 4 to 50 Pa · s), particularly 6 Pa · s or more (for example, 6 to 50 Pa · s). It is desirable to use a high viscosity oligosaccharide.

  The melting point or softening point of the oligosaccharide (C1) is defined by the heat distortion temperature of the organic solid component (resin component, etc.) (A) (for example, the melting point or softening point of the organic solid component (A), JIS K 7206). Higher than the Vicat softening point). In addition, depending on the type of oligosaccharide [for example, starch sugar such as reduced starch saccharified product], it does not show melting point or softening point and may be decomposed (thermally decomposed). In such a case, the decomposition temperature may be the “melting point or softening point” of the oligosaccharide (C1).

  The temperature difference between the melting point or softening point of the oligosaccharide (C1) and the heat distortion temperature of the organic solid component (resin component, etc.) (A) is, for example, 1 ° C. or more (for example, about 1 to 80 ° C.), preferably It is 10 ° C or higher (for example, about 10 to 70 ° C), more preferably 15 ° C or higher (for example, about 15 to 60 ° C). The melting point or softening point of the oligosaccharide (C1) can be selected in the range of 70 to 300 ° C. depending on the type of the organic solid component (A) and the like, for example, 90 to 290 ° C., preferably 100 to 280 ° C. 110 to 270 ° C.), more preferably about 120 to 260 ° C. (for example, 130 to 260 ° C.). In general, an oligosaccharide anhydride exhibits a high melting point or softening point. For example, in the case of trehalose, the melting point of dihydrate is 97 ° C, while the melting point of anhydride is 203 ° C. When the melting point or softening point of the oligosaccharide is higher than the heat distortion temperature of the organic solid component (resin component, etc.) (A), not only can the viscosity decrease of the oligosaccharide during melt-kneading be prevented, but also the oligosaccharide may be thermally deteriorated. Can be suppressed.

(C2) Water-soluble plasticizing component The water-soluble plasticizing component (C2) may be any one that can express the phenomenon that the oligosaccharide (C1) is hydrated to become a chickenpox state. Can be used. These plasticizing components can be used alone or in combination of two or more.

(a) Saccharides As the saccharides, monosaccharides and / or disaccharides are usually used in order to effectively plasticize the oligosaccharide (C1). These saccharides can be used alone or in combination of two or more.

Examples of monosaccharides include triose, tetrose, pentose, hexose, heptose, octose, nonose, and decourse. These compounds may be aldoses and ketoses, and dialdoses (compounds that are sugar derivatives and aldehyde groups at both ends of the carbon chain, such as tetraacetylgalactohexodialdose, idhexodialdose, xylopentodi Aldose, etc.), monosaccharides having a plurality of carbonyl groups (such as aldoalcoketoses such as osone and onose), monosaccharides having methyl groups (such as methyl sugars such as altromethylose), acyl groups (particularly C such as acetyl group) _2-4 acyl group etc.) monosaccharides (acetylated aldoses of the above-mentioned aldose, for example, aldehydes such as aldehyde glucose pentaacetyl compound), saccharides introduced with carboxyl groups (sugar acid or uronic acid etc.), thiosugars , Amino sugar, deoxy sugar and the like.

  Specific examples of such monosaccharides include, for example, tetrose (erythrose, threllose, etc.), pentose (arabinose, ribose, lyxose, deoxyribose, xylose, etc.), hexose (allose, altrose, glucose, mannose, gulose, idose). Galactose, fructose, sorbose, fucose, rhamnose, talose, galacturonic acid, glucuronic acid, mannuronic acid, glucosamine and the like.

  The monosaccharide may be a cyclic isomer in which a cyclic structure is formed by a hemiacetal bond. The monosaccharide does not need to have optical rotation, but may be any of D form, L form, and DL form. These monosaccharides can be used alone or in combination of two or more.

  The disaccharide is not particularly limited as long as it can plasticize the oligosaccharide (C1). For example, among the disaccharides, disaccharides having a low melting point or a low softening point (for example, gentiobiose, melibiose, trehalose). (Dihydrate) and the like, and disaccharides corresponding to the monosaccharide homo and hetero disaccharides (for example, aldobiouronic acid such as glucuronoglucose in which glucuronic acid and glucose are α-1,6 glycosidic bonded) it can.

  Since saccharides are excellent in thermal stability, reducing sugars are preferable. Examples of such saccharides include free monosaccharides as well as disaccharides having a low melting point or a low softening point (for example, gentiobiose, melibiose). Etc.).

(b) Sugar alcohol The sugar alcohol may be a chain sugar alcohol such as alditol (glycitol) or a cyclic sugar alcohol such as inosit. Usually, a chain sugar alcohol is used. The These sugar alcohols can be used alone or in combination of two or more.

  Examples of chain sugar alcohols include tetritol (threitol, erythritol, etc.), pentitol [pentaerythritol, arabitol, ribitol (adonitol), xylitol, lyxitol, etc.], hexitol [sorbitol, mannitol, iditol, glitol, tallitol, dulcitol (g Lactitol), allozulcitol (aritol), arsitol], heptitol, octitol, nonitol, dexitol, dodecitol and the like.

  Of these sugar alcohols, erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol and mannitol are preferred. The sugar alcohol often contains at least one sugar alcohol selected from erythritol, pentaerythritol, and xylitol.

  The plasticizing component (C2) may be a liquid (syrup) at normal temperature (for example, about 15 to 20 ° C.), but it is usually a solid from the viewpoint of handleability. When the auxiliary component (C) is composed of an oligosaccharide (C1) and a plasticizing component (C2), it is effective even if the oligosaccharide (C1) is a thermally decomposable oligosaccharide that does not show a clear melting point or softening point. Can be plasticized or softened.

  The melting point or softening point of the plasticizing component (C2) is usually defined by the heat distortion temperature of the organic solid component (resin component, etc.) (A) (for example, the melting point or softening point of the organic solid component (A), JIS K7206. Vicat softening point) or less. Note that some plasticizing components have a high melting point (for example, 200 ° C. or higher) and melt at a temperature lower than the actual melting point when coexisting with the oligosaccharide. For example, pentaerythritol exhibits a plasticizing effect on oligosaccharides at a temperature lower than the actual melting point (260 ° C.) (for example, about 160 to 180 ° C.), and itself is in a molten state. Such a high melting point plasticizing component cannot be used alone because it does not melt at the heat distortion temperature of an organic solid component (such as a resin component), but can be effectively used in combination with an oligosaccharide. In addition, in plasticizing components that exhibit a plasticizing effect on oligosaccharides at a temperature lower than the actual melting point (for example, pentaerythritol), the temperature at which the plasticizing effect is exerted on oligosaccharides is set to the plasticizing component (C2). The “melting point or softening point” may be used.

  The melting point or softening point of the auxiliary component (C) may be equal to or higher than the heat distortion temperature of the organic solid component (resin component or the like) (A), or may be equal to or lower than the heat distortion temperature. The organic solid component (A) and the auxiliary component (C) may be melted or softened at least at the kneading temperature (or molding processing temperature). For example, the temperature difference between the melting point or softening point of the auxiliary component (C) and the thermal deformation temperature of the organic solid component (resin component etc.) (A) may be selected in the range of 0 to 100 ° C., for example 3-80 degreeC (for example, 3-55 degreeC), Preferably it is 5-60 degreeC (for example, 5-45 degreeC), More preferably, about 5-40 degreeC (for example, 10-35 degreeC) may be sufficient. When the temperature difference between the melting point or softening point of the auxiliary component (C) and the heat distortion temperature of the organic solid component (resin component, etc.) (A) is small (for example, the temperature difference is about 0 to 20 ° C. In the case), there is an advantage that the dispersion form can be fixed in a short time by the auxiliary component (C) (for example, sugar component) having a high solidification rate.

  Further, the melt flow rate of the auxiliary component (C) (for example, the auxiliary component containing the oligosaccharide (C1) and the plasticizing component (C2)) is, for example, that of the organic solid component (resin component, etc.) (A). When the melt flow rate defined by JIS K 7210 is measured at a temperature 30 ° C. higher than the heat distortion temperature (for example, the melting point or softening point of the organic solid component (A), the Vicat softening point), one or more (for example, 1 ˜40), preferably 5 or more (for example, about 5 to 30), more preferably 10 or more (for example, about 10 to 20).

  In the auxiliary component (C), the proportion (weight ratio) of the plasticizing component (C2) is such that the plasticizing component does not localize due to aggregation or the like with melt kneading, and the oligosaccharide (C1) is efficiently contained. Amount that can be plasticized, for example, oligosaccharide (C1) / plasticizing component (C2) = 99/1 to 50/50, preferably 95/5 to 60/40, more preferably 90/10 to 70 / About 30.

  The ratio (weight ratio) between the organic solid component (A) and the auxiliary component (C) is selected according to the type and viscosity of the organic solid component and auxiliary component, the compatibility between the organic solid component and auxiliary component, etc. Although not particularly limited, it is usually an amount that does not impair the moldability, for example, organic solid component (A) / auxiliary component (C) = 55/45 to 1/99, preferably 50/50 to 5/95, More preferably, it is about 45/55 to 10/90.

  In the present invention, the dispersion or composition may be provided with various additives, for example, fillers (powder fillers, fibrous fillers such as glass fibers), plasticizers or softeners, and imparting photodegradability. Agents (anatase type titanium oxide, etc.), lubricants, stabilizers (heat stabilizer, antioxidant, UV absorber, weathering (light) stabilizer, etc.), UV scattering agents (titanium oxide, zirconium oxide, zinc oxide, iron oxide) Metal oxide powders, etc.), dispersants, flame retardants, antistatic agents, charge control agents (nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidine compounds, imidazole compounds, amine compounds, etc.) Charge control agents; salicylic acid metal complexes, azo dye metal complexes, copper phthalocyanine dyes, nitroimidazole derivatives, urea derivative and other negative charge control agents), flow Agent, wax [olefin wax such as polyethylene wax, ethylene copolymer wax, polypropylene wax; paraffin wax; higher fatty acid or derivative thereof (salt, polyhydric alcohol ester, amide, etc.); ester wax, etc.], crosslinking agent And other additives may be included. The additive may be contained in either the dispersed phase or the matrix constituting the dispersion.

  The other additives can be selected depending on the use of the colored fine particles. For example, in applications such as cosmetics (foundation, white powder, blusher, etc.), UV absorbers (benzophenone-based absorbers, cinnamic acid-based absorbers, p-aminobenzoic acid-based absorbents, salicylic acid-based absorbents, dibenzoylmethane-based absorbents, urocanic acid or esters thereof, β-isopropylfuranone, β-carotene, etc.), the aforementioned ultraviolet scattering agent, and the like may be used. For image recording material applications such as toner, for example, a charge control agent, a fluidizing agent, waxes, and the like may be used. In applications such as paints, for example, a crosslinking agent, a weather resistance (light) stabilizer, an ultraviolet absorber, a fluidizing agent, and the like may be used.

  These additives only need to be effective amounts, for example, the total amount of the additives can be selected from a range of about 0 to 100 parts by weight, for example, 0 to 50 parts by weight with respect to 100 parts by weight of the organic solid component. Parts (for example, 0 to 30 parts by weight), preferably 0.05 to 20 parts by weight (for example, 0.1 to 20 parts by weight), more preferably 0.1 to 10 parts by weight (for example, 0.5 to 10 parts by weight). Part by weight).

  In the dispersion of the present invention, the average particle size of the dispersed phase is not particularly limited, and can be selected from a range of about 0.1 μm to 1 mm (for example, 0.1 to 800 μm) depending on the application. ˜500 μm, preferably 0.1 to 100 μm (for example, 0.5 to 80 μm), more preferably 0.2 to 50 μm (for example, 0.5 to 50 μm), particularly about 1 to 40 μm (for example, 1 to 20 μm). It may be. The average particle size of the dispersed phase may be, for example, about 0.1 to 10 μm (for example, 0.2 to 5 μm), preferably about 0.5 to 3 μm (for example, 0.5 to 2 μm).

  In the present invention, the particle size distribution can be reduced by making the particle size of the dispersed phase uniform. The variation coefficient (%) of the average particle diameter of the dispersed phase ([standard deviation of particle diameter / average particle diameter] × 100) is, for example, 60 or less (for example, about 5 to 60), preferably 55 or less (for example, 5 to 5). About 55), more preferably 50 or less (for example, about 10 to 50).

  In the dispersion or composition of the present invention, the dispersed phase may be in the form of particles, and may be, for example, spherical, ellipsoidal, polygonal, prismatic, cylindrical, rod-shaped, indefinite or the like. Good. A preferable dispersed phase has a spherical shape. The spherical dispersion (or spherical particle) is not limited to a true sphere, and for example, a shape in which the length ratio of the major axis to the minor axis is, for example, about major axis / minor axis = 1.5 / 1 to 1/1. Is also included. The length ratio between the major axis and the minor axis is preferably major axis / minor axis = 1.3 / 1 to 1/1 (for example, 1.2 / 1 to 1/1), more preferably 1.1 / 1 to 1. It may be about 1/1.

  The dispersion can be prepared by kneading an organic solid component (A), a colorant (B) (including a masterbatch containing a colorant, etc.) and an auxiliary component (C), and is usually a kneaded composition. In many cases, a preform is prepared by molding. The kneading can be performed using a conventional kneader (for example, a single or twin screw extruder, a kneader, a calender roll, etc.). Prior to kneading, each component may be preliminarily processed into a powder form with a freeze pulverizer or the like, or premixed with a Henschel mixer, a tumble mixer, a ball mill, or the like.

  Examples of the molding method include extrusion molding, injection molding, blow molding, calendar molding, and the like, and usually extrusion molding or injection molding is used from the viewpoint of productivity and ease of processing. The shape of the preform (or dispersion) is not particularly limited, and is a zero-dimensional shape (granular, pellet-like, etc.), a one-dimensional shape (strand-like, rod-like, etc.), or a two-dimensional shape (plate-like, sheet-like) Or a three-dimensional shape (such as a tube or a block). Considering the elution property of the auxiliary component, it is desirable to process it into a strand shape, a rod shape, a sheet shape, or a film shape.

  Although the water-soluble auxiliary component may be eluted from the kneaded product, it is usually molded after kneading to elute the water-soluble auxiliary component.

  In addition, kneading | mixing temperature and shaping | molding processing temperature can be suitably set according to the raw material (for example, organic solid component and auxiliary agent component) to be used, for example, 90-300 degreeC, Preferably it is 110-260 degreeC. (For example, 170 to 250 ° C.), more preferably 140 to 240 ° C. (for example, 170 to 240 ° C.), particularly about 170 to 230 ° C. (for example, 180 to 220 ° C.). In order to avoid thermal decomposition of the auxiliary components (oligosaccharide and plasticizing component), the kneading temperature and the molding processing temperature may be 230 ° C. or lower. The kneading time may be selected from the range of, for example, 10 seconds to 1 hour, and is usually about 30 seconds to 45 minutes, preferably about 1 to 30 minutes (for example, 1 to 10 minutes).

  The melt obtained by kneading and / or molding (for example, a kneaded product or a preformed product) may be appropriately cooled as necessary. Thus, by cooling the melt, in the molten state, even if the organic solid component (A) and the colorant (B) and the auxiliary component (C) are compatible, with cooling, A dispersed phase can be formed by a difference in solidification speed such as surface tension and crystallization, and a dispersion can also be obtained.

  The cooling temperature may be at least about 10 ° C. lower than the heat distortion temperature of the organic solid component (resin component, etc.) (A), or the melting point or softening point of the auxiliary component (C). 10 to 100 ° C. lower than the heat distortion temperature of the organic solid component or the melting point or softening point of the auxiliary component), preferably 15 to 80 ° C. lower than the above temperature, more preferably 20 to 60 ° C. lower than the above temperature. The temperature may be as low as possible. Specifically, for example, the cooling temperature can be selected from the range of 5 to 150 ° C. according to the type of organic solid component or auxiliary component, for example, 10 to 120 ° C. (for example, 10 to 60 ° C.), preferably It may be about 15 to 100 ° C. (for example, 15 to 50 ° C.), more preferably about 20 to 80 ° C. (for example, 20 to 40 ° C.). The cooling time can be appropriately set according to the type of organic solid component and auxiliary component, the cooling temperature, etc., and may be selected from a wide range of 30 seconds to 20 hours, for example, 45 seconds to 10 hours, preferably May be 1 minute to 5 hours (for example, 1 minute to 1 hour), more preferably about 1.5 to 30 minutes.

  Further, by adjusting the compatibility between the organic solid component and the auxiliary component, kneading conditions (for example, kneading time, kneading temperature, etc.), molding processing temperature and cooling conditions (for example, cooling time, cooling temperature, etc.), dispersion The average particle diameter of the phase (or particles) can be changed, and the particle size distribution width can be further narrowed.

  In the dispersion thus obtained, the auxiliary component (C) forms a continuous phase in the sea-island structure, and the dispersed phase composed of the organic solid component (A) and the colorant (B) is independent. Thus, the auxiliary component can be quickly eluted or extracted, and the dispersed phase (colored organic solid phase) can be obtained as particles.

[Method for producing colored particles]
In the present invention, the water-soluble auxiliary component (C) is eluted from the dispersion to produce particles composed of the organic solid component (A) and the colorant (B).

  Elution (or washing) of the water-soluble auxiliary component (C) is carried out by using an aqueous solvent such as water, a water-soluble solvent (eg, alcohols (methanol, ethanol, propanol, isopropanol, butanol, etc.), ethers (cellosolve, butylcellosolve). Etc.)) and the like. These aqueous solvents can be used alone or in combination of two or more. It is preferable to use water as an elution solvent because it has a low environmental burden and can reduce industrial costs.

  For elution of the auxiliary component (C), for example, the dispersion (or preform) is immersed and dispersed in the aqueous medium, and the auxiliary component is eluted or washed (transferred to an aqueous solvent). ). When the dispersion (or preform) is immersed in an aqueous medium, the water-soluble auxiliary component that forms the matrix of the dispersion is gradually eluted, and the dispersed phase (particles) is dispersed in the eluate. In order to promote dispersion and elution of the auxiliary component, stirring or the like may be appropriately performed.

  In the present invention, as the colorant (B), a colorant having a higher affinity for the organic solid component (A) than the auxiliary component (C) such as an oil-soluble organic dye or pigment is used. , Because it can be distributed to the dispersed phase (dispersed particles) without being substantially distributed to the aqueous phase (water-soluble auxiliary component (C) and aqueous medium) side, and the utilization efficiency of the colorant can be improved. This is also industrially advantageous. When a dye or pigment having a higher degree of affinity for the organic solid component (A) than the affinity for the water-soluble auxiliary component (C) is used as the colorant, the distribution ratio of the colorant to the dispersed phase The colorant content in the eluate can be greatly reduced (substantially to 0), and the environmental load can be reduced.

  The auxiliary component may be eluted, for example, under pressure, but can usually be eluted under normal pressure (for example, about 100,000 Pa) or under reduced pressure. The elution temperature of the auxiliary component can be appropriately set according to the organic solid component and the auxiliary component, and is usually a temperature below the melting point or softening point of the organic solid component, for example, 10 to 100 ° C., preferably It is about 25-90 degreeC, More preferably, it is about 30-80 degreeC (for example, 40-80 degreeC). Since the water-soluble auxiliary component of the present invention is easily soluble in water, a large amount of water is not required. Further, since the auxiliary component has a low molecular weight, the viscosity of the obtained eluate is low and can be easily recovered.

  The colored particles can be recovered from the dispersion in which the particles are dispersed using a conventional separation (recovery) method such as filtration or centrifugation. In the obtained colored particles, it is desirable that the auxiliary component does not substantially remain. However, for example, from the viewpoint of cost reduction in the washing process, the auxiliary component may remain in the colored particles in a small amount. Since the auxiliary component is a compound derived from a natural product (including food or food additives), the adverse effect on the obtained particles is small and the safety is high. The proportion of the auxiliary component (C) in the colored particles may be 3% by weight or less, for example.

  The auxiliary component eluted or extracted with the solvent can be recovered using a conventional separation means (eg, distillation, concentration, recrystallization, drying (freeze drying), etc.).

The present invention also includes colored organic solid particles (resin particles and the like) obtained by the production method. The shape of particles (resin particles, etc.), the average particle diameter, and the variation coefficient of the average particle diameter can be selected from the same ranges as in the dispersed phase. Further, the ratio of the major axis to the minor axis of the particles can be selected from the same range as that of the dispersed phase. In addition, as long as the organic solid component (A) is not eluted in the elution solvent (aqueous solvent), the shape and size of the particles are maintained as they are. The particles are
If necessary, the particle size may be aligned by means such as classification.

  When the colored particles (colored resin particles and the like) of the present invention are visually observed, they often exhibit a whiter color than the original color of the colorant (C) due to light scattering. Utilizing such a light scattering effect, it can be used in applications such as cosmetics (for example, foundation, white powder, blusher, eye shadow, etc.). It is also useful for image recording materials such as inks (including polymer inks) and colored toners used for inkjet printing, paints and coating agents (such as paints for powder coating or slurry coating), and colorants for printing inks. is there. The colored particles may be used to improve the mixing suitability with other fine particles (for example, inorganic fine particles), an anti-blocking agent (for example, an anti-blocking agent for a molded product), a spacer (liquid crystal spacer, etc.). ), An additive for sheets or films, and an abrasive for chemical mechanical polishing (CMP) of semiconductors.

  In addition, colored resin particles obtained using a biodegradable resin component are excellent in biodegradability, and therefore include agrochemicals, pharmaceuticals, paints (eg, powder paints, ship bottom paints, etc.), coating agents, adhesives, etc. It is also useful as a raw material or additive in the fine chemical field. In addition, additives for agriculture, forestry and fisheries, civil engineering and construction films and sheets, sanitary products such as disposable diapers, medical materials that require biodegradability and sustained release that require sustained release It can also be used as a functional material.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Examples 1-11 and Comparative Examples 1-3
A resin composition containing a resin component, a water-soluble auxiliary component, and a colorant component having the composition shown in Tables 1 and 2 is set at a set temperature (processing temperature) by Brabender (Toyo Seiki Co., Ltd., Labo Plast Mill). ) After melt-kneading at 200 ° C. for 5 minutes, the mixture was cooled to prepare a dispersion. The obtained dispersion was immersed in hot water at 60 ° C. to obtain a suspension solution of resin particles. Using a membrane membrane (pore size 0.45 μm, made of polyvinylidene fluoride), the insoluble matter is filtered from the suspension solution to collect resin fine particles, and an aqueous solution (extracted aqueous solution) in which the auxiliary component is dissolved is recovered. did. The color of the extracted aqueous solution containing the resin fine particles and auxiliary components obtained was visually observed.

  Further, after drying the resin fine particles, the shape of the particles was observed using a scanning electron microscope, and the weight average molecular weight and the average particle diameter of the resin particles were calculated by the following methods. FIG. 1 shows a scanning electron micrograph (magnification 3000 times) of the colored resin particles obtained in Example 2.

(Weight average molecular weight)
The weight average molecular weight was calculated in terms of standard polystyrene by gel permeation chromatography (GPC).

(Average particle size)
An appropriate amount of dried resin particles is re-dispersed in pure water to prepare a suspension, and the number average particle size is measured using a laser diffraction type particle size distribution analyzer (SALD-2000J, manufactured by Shimadzu Corporation). did. In addition, standard deviation and coefficient of variation were calculated for 100 resin particles extracted at random. The coefficient of variation was calculated according to the following formula.

Coefficient of variation (%) = standard deviation / average particle size × 100
In the examples and comparative examples, the following components were used.

(A) Resin component Resin 1: Polystyrene resin (Toyo Styrene Co., Ltd., GPPS HRM63C)
Resin 2: Nylon 12 resin (Daicel Degussa Co., Ltd., Daiamide L1640)
Resin 3: Butanediol-succinic acid-caprolactone terpolymer (manufactured by Daicel Chemical Industries, CBS-178, weight average molecular weight 170,000)
Resin 4: Butanediol-succinic acid-caprolactone terpolymer (Daicel Chemical Industries, CBS-17X, weight average molecular weight 140,000)
Resin 5: Polystyrene resin (Toyo Styrene Co., Ltd., GPPS G100C)
Resin 6: Polystyrene resin (manufactured by Aldrich, MI 12 g / 10 min).

(B) Colorant Colorant 1: Blue organic pigment (Blue 15: 3 (phthalocyanine blue))
Colorant 2: Red organic pigment (Red No. 202 (Pigment Red 57: 1))
Colorant 3: Green water-soluble colorant (aqueous food color green, food yellow No. 4 + food blue No. 1 + dextrin, manufactured by Kyoritsu Foods Co., Ltd.)
Colorant 4: Red dye for resin (manufactured by Orient Chemical Co., Ltd., OPLAS RED330)
Colorant 5: Black dye for resin (manufactured by Orient Chemical Industry Co., Ltd., NUBIAN BLACK PC-0850)
Colorant 6: Zinc oxide (manufactured by Sumitomo Osaka Cement Co., Ltd., ZnO-350Si (4) G)
Colorant 7: Hydrophobized titanium dioxide (manufactured by Nippon Aerosil Co., Ltd., TITANDIOXID T805).

(C) Water-soluble auxiliary component
(C1) oligosaccharide: starch sugar (manufactured by Towa Kasei Kogyo Co., Ltd., reduced starch saccharified product PO-10, viscosity of 50 wt% aqueous solution measured at 25 ° C. with a B-type viscometer: 6.5 Pa · s)
(C2) Water-soluble plasticizing component: sugar alcohol (manufactured by Towa Kasei Kogyo Co., Ltd., marine crystal D (-) mannitol).

  The results are shown in Tables 1 and 2.

  In any of the examples, the colored resin particles were colored in a hue derived from the used colorant, and no color was observed in the aqueous solution from which the auxiliary component was extracted. In addition, the shape of the particles was true spherical in any example, and the particle diameter variation coefficient was small, and particles having a uniform particle size were obtained.

  On the other hand, in Comparative Examples 1 to 3 using a water-soluble pigment as the colorant, the resin fine particles were not colored at all, and the aqueous solution from which the auxiliary component was extracted was colored in the color of the pigment.

1 is a scanning electron micrograph of the colored resin particles obtained in Example 2. FIG.

Claims (14)

A meltable thermoplastic resin (A), a colorant (B), and a water-soluble auxiliary component (C) containing at least an oligosaccharide (C1) are melt-kneaded, and from the resulting composition, the auxiliary component (C) is a method for producing particles composed of the thermoplastic resin (A) and the colorant (B) , wherein the colorant (B) comprises an oil-soluble dye and an organic or inorganic pigment. The ratio (weight ratio) between the thermoplastic resin (A) and the auxiliary component (C) is at least one selected, and the thermoplastic resin (A) / auxiliary component (C) = 55 / 45-1 / 99 .   The composition according to claim 1, wherein the composition is formed of a particulate dispersed phase composed of a thermoplastic resin (A) and a colorant (B) and a matrix composed of a water-soluble auxiliary component (C). Method.   The method according to claim 2, wherein the average particle size of the dispersed phase is 0.1 to 100 µm, and the average particle size of the colorant (B) is 50% or less of the average particle size of the dispersed phase.   The dispersed phase is a spherical dispersed phase having a coefficient of variation of an average particle diameter of 60 or less and a length ratio between a major axis and a minor axis (major axis / minor axis) = 1.5 / 1 to 1/1. Method.   The method according to claim 1, wherein the proportion of the colorant (B) is 0.001 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).   The method according to claim 1, wherein the oligosaccharide (C1) comprises at least a tetrasaccharide.   The oligosaccharide (C1) is composed of at least one selected from starch sugar, galactooligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide and chitosan oligosaccharide. Method.   The method according to claim 1, wherein the viscosity of the 50% by weight aqueous solution of the oligosaccharide (C1) is 1 Pa · s or more when measured with a B-type viscometer at a temperature of 25 ° C.   The method according to claim 1, wherein the auxiliary component (C) comprises an oligosaccharide (C1) and a water-soluble plasticizing component (C2) for plasticizing the oligosaccharide (C1). The oligosaccharide (C1) exhibits a melting point or softening point at a temperature higher than the thermal deformation temperature of the thermoplastic resin (A) or decomposes, and the melting point or softening point of the plasticizing component (C2) is the thermoplastic resin. The method according to claim 9, which is not higher than the heat distortion temperature of (A). The method according to claim 9 , wherein the plasticizing component (C2) is composed of at least one selected from saccharides and sugar alcohols. The method according to claim 11 , wherein the sugar alcohol is at least one selected from erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol and mannitol. The method according to claim 9 , wherein the ratio (weight ratio) between the oligosaccharide (C1) and the plasticizing component (C2) is oligosaccharide (C1) / plasticizing component (C2) = 99/1 to 50/50. The ratio (weight ratio) between the thermoplastic resin (A) and the auxiliary component (C) is thermoplastic resin (A) / auxiliary component (C) = 45/55 to 10/90. Method.