JP2005162840A - Organic composition containing oligosaccharide and manufacturing method for organic solid particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture resin particles (such as spherical resin particles) having the same particle size by a simple method. <P>SOLUTION: A resin composition is comprised of a meltable organic solid component (such as a resin component) (A) and a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1). The organic solid component (A) and the auxiliary component (B) have a different surface tension and/or the same or different melt viscosity at the melt-kneading temperature of the resin composition. The resin composition is melt-kneaded to form a dispersion comprising a dispersed phase of the granular organic solid component (A) and a matrix of the auxiliary component (B), and the auxiliary component (B) is caused to be eluted from the dispersion to give particles (such as spherical resin particles) comprising the organic solid component (A). The variation coefficient of the average particle size of the dispersed phase or the particles (such as resin particles) can be 60% or less. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an organic composition (resin composition etc.) and dispersion useful for producing organic solid particles (resin particles etc.) having a small particle size distribution by a simple method, a method of producing organic solid particles, and organic Relates to solid particles. More specifically, organic compositions (resin compositions, etc.) and dispersions that are also useful in fields such as cosmetics, image recording materials such as ink and colored particles used in ink jet printers, paints such as powder paints, etc. The present invention relates to a method for producing organic solid particles, and organic solid particles.

  Conventionally, as a method for producing resin particles, a mechanical pulverization method, for example, a resin or a resin composition is coarsely pulverized with a crusher or the like, then finely pulverized with a jet mill or the like, and then with an air classifier or the like. A classification method is used. However, in such a method, in addition to the expensive manufacturing equipment, the obtained particles are also indefinite 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 Laid-Open No. 10-176065 (Patent Document 1) discloses that a resin (a resin (b)) is melt-kneaded with one or more other thermoplastic resins (b) into a finely divided thermoplastic resin (a). A resin composition in which a) is a dispersed phase and resin (b) constitutes a continuous phase is obtained, and the resin composition is washed with a solvent that does not dissolve resin (a) but dissolves resin (b). Thus, a method for obtaining spherical fine particles of the resin (a) is disclosed. However, in this method, not only the dispersed phase and the continuous phase need to be incompatible with each other, but also an appropriate combination of the continuous phase resin and the solvent must be selected depending on the type of the dispersed phase resin. Therefore, not only the combination of resins is limited, but also the combination of resin and solvent is limited. Further, since the resin forming the continuous phase is not involved in the resin fine particles as a product, it is finally recovered 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.

  In JP-A-60-13816 (Patent Document 2), polyethylene glycol and a thermoplastic resin are melted and stirred, and then poured into water to coagulate both polymers. A method for producing thermoplastic resin particles to be removed has been proposed. Japanese Patent Laid-Open No. 61-9433 (Patent Document 3) discloses a method for producing thermoplastic resin particles in which a thermoplastic resin and polyethylene oxide are melted and stirred and then cooled, and water is used to remove the polyethylene oxide. Has been. In JP-A-9-165457 (Patent Document 4), a melt-formable water-soluble polymer such as polyvinyl alcohol resin, modified starch, and polyethylene oxide is mixed with a thermoplastic resin to obtain a melt-molded product. After that, a method for producing resin fine particles in which water is used to remove a water-soluble polymer from a molded product is disclosed.

However, even in these methods, since the incompatibility between the resin and the water-soluble polymer is necessary, not only the combination of resins that can be selected is limited, but also the uniformity of the particle size distribution of the obtained resin particles is Not enough. Moreover, since these water-soluble polymers have low solubility in water, a large amount of water is required for dissolution, and the dissolution rate is slow, so that productivity is remarkably reduced. Furthermore, since such a water-soluble polymer is often derived from a non-natural product, a waste liquid in which such a water-soluble polymer is dissolved adversely affects the environment.
JP 10-176065 A (Claim 1) Japanese Patent Laid-Open No. 60-13816 JP 61-9433 A JP-A-9-165457

  Accordingly, an object of the present invention is to provide an organic composition and dispersion useful for industrially advantageously producing organic solid particles (resin particles, etc.) having a uniform particle size, a method for producing organic solid particles, and an organic solid. To provide particles.

  Another object of the present invention is to provide an organic composition and dispersion useful for producing spherical organic solid particles (such as resin particles) by a simple method, a method for producing organic solid particles, and organic solid particles. There is.

  Another object of the present invention is to provide a method for producing organic solid particles, an organic composition, and a dispersion capable of reducing the environmental load due to waste liquid or the like.

  As a result of intensive studies to solve the above problems, the present inventor has found that a meltable organic solid component (resin component or the like) having the same or different viscosity and an auxiliary component (a water-soluble auxiliary composed of at least an oligosaccharide). Component) (especially, the viscosity ratio between the organic solid component and the auxiliary component is reduced), the organic solid component can be efficiently dispersed in the matrix of the auxiliary component, and the size of the dispersed phase can be controlled. With the removal of, organic solid particles (resin particles, etc.) having a uniform particle diameter can be obtained, and when the specific auxiliary component is used, the surface tension of the organic solid component (resin component, etc.) The present inventors have found that the surface tension can be made different (particularly greatly different) and the shape of the organic solid particles can be made spherical, and the present invention has been completed.

That is, the composition (organic composition) of the present invention is a composition comprising a meltable organic solid component (A) and a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1). The organic solid component (A) and the auxiliary component (B) have the same or different melt viscosities at the melt kneading temperature of the composition. In the melt-kneading temperature of the composition, the ratio eta _A / eta _B of the shear viscosity eta _B of the shear viscosity eta _A and auxiliary components of the organic solid components was measured at a shear rate of 126sec ^-1 (A) (B) is 20 / It may be 1 or less.

The composition of the present invention is a composition comprising a meltable organic solid component (A) and a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1). The component (A) and the auxiliary component (B) have different surface tensions. In 25 ° C., and the contact angle theta _A with water of the organic solid component (A), the ratio of the contact angle theta _B with water auxiliary component _{(B) (θ A / θ} B) is a 2 or more Also good.

  In the dispersion of the present invention, a particulate dispersed phase composed of a meltable organic solid component (A) is dispersed in a matrix composed of a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1). The organic solid component (A) and the auxiliary component (B) have the same or different melt viscosities at the melt kneading temperature. The variation coefficient of the average particle diameter of the dispersed phase may be 60% or less. The dispersed phase may be a spherical dispersed phase having an average particle diameter of 0.05 to 100 μm and a length ratio of major axis to minor axis (major axis / minor axis) = 1.5 / 1 to 1/1.

  The oligosaccharide (B1) may be composed of at least a tetrasaccharide. The oligosaccharide (B1) 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 auxiliary component (B) may be composed of an oligosaccharide (B1) and a water-soluble plasticizing component (B2) (sugar, sugar alcohol, etc.) for plasticizing the oligosaccharide (B1). The oligosaccharide (B1) exhibits a melting point or softening point at a temperature higher than the thermal deformation temperature of the organic solid component (resin component, etc.) (A) or decomposes, and the melting point or softening of the plasticizing component (B2) 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 oligosaccharide (B1) may exhibit a melting point or softening point at a temperature higher than the melting point or softening point of the plasticizing component (B2) or decompose. The ratio (weight ratio) between the oligosaccharide (B1) and the plasticizing component (B2) may be about oligosaccharide (B1) / plasticizing component (B2) = 99/1 to 50/50.

  In the composition or dispersion, the ratio (weight ratio) between the organic solid component (A) and the auxiliary component (B) is: organic solid component (A) / auxiliary component (B) = 55 / 45-1 It may be about / 99.

  In the present invention, the meltable organic solid component (A) constituting the particulate dispersed phase and the water-soluble auxiliary component (B) comprising at least the oligosaccharide (B1) and constituting the matrix are melt-kneaded, In the method for producing the organic solid particles composed of the organic solid component (A) by eluting the auxiliary component (B) from the produced dispersion, the organic solid component (A) and the auxiliary component As (B), components having the same or different melt viscosities at the melt kneading temperature are used.

  The present invention includes particles (organic solid particles) obtained by the production method. The particles (resin particles and the like) have an average particle diameter of 0.05 to 100 μm, a coefficient of variation of the 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. Spherical particles having ~ 1/1 may also be used.

  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, in the preparation of the dispersion, the dispersion is formed using an organic solid component having the same or different melt viscosity and an auxiliary component (a water-soluble auxiliary component composed of at least an oligosaccharide). The organic solid component can be efficiently dispersed in the matrix of the auxiliary component to control the size of the dispersed phase. As the matrix is removed, organic solid particles with uniform particle size (resin particles, etc.) are industrially advantageous. Can be manufactured. In the present invention, since the organic solid component and the auxiliary component can have different surface tensions, spherical organic solid particles can be produced by a simple method. Furthermore, in the present invention, since the matrix is composed of naturally derived components, it is possible to reduce the environmental burden due to waste liquids and the like.

[Composition]
The composition (organic composition) of the present invention comprises a meltable organic solid component (A) and a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1). Such a composition produces a dispersion composed of a disperse phase containing a meltable organic solid component (A) and a matrix containing the auxiliary component (B) by kneading (melt kneading) or the like. It is useful for obtaining particles by eluting the auxiliary component (B) from this dispersion. The organic solid components can be used alone or in combination of two or more.

(A) Organic solid component that can be melted As the solid organic component (A) that can be melted, an incompatible or hydrophobic component (water-insoluble component) can be usually used for the water-soluble auxiliary agent (B). 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.

  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 system 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 agent (B). The handleability of (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 Resin, vinyl resins (for example, halogen-containing resins, vinyl ester resins, vinyl alcohol resins, etc.) vinyl polymerization (addition polymerization) thermoplastic resins; cellulose-derived and other natural product-derived resins; thermoplastic silicone resins, etc. ), And thermosetting resins (eg Examples include epoxy resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins (including silicone rubber, silicone varnish, etc.) These resins can be used alone or in combination of two or more. As (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) oxy C _{2 -4} alkylene glycol, etc.), alicyclic C _6-12 diol (eg cyclohexanediol, cyclohexanedimethanol etc.), aromatic C _6-20 diol (eg resorcinol, hydroquinone, naphthalenediol, bisphenol A, F, AD) Bisphenols, alkylene oxide adducts of bisphenols, etc.). 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 polyoxy C _2-4 alkylene glycol having a repeating number of about 2 to 4 oxyalkylene units [such as glycols containing poly (oxy-C _2-4 alkylene) units 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-cyclohexyldimethylene 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.) Homopolyesters or copolyesters obtained by polycondensation with group C _2-6 diols, preferably aliphatic C _2-4 diols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, etc. Carboxylic acid (for example, glycolic acid, lactic acid, oxypropionic acid, oxybutyric acid, etc. Aliphatic C _2-6 hydroxycarboxylic acid, preferably homo- polyesters or copolyesters, initiator aliphatic C _2-4 hydroxycarboxylic acid such as glycolic acid or lactic acid) (bifunctional or trifunctional initiators, for example, an alcohol Homopolylactone or copolylactone obtained by ring-opening polymerization of the lactone (preferably C _4-10 lactone such as caprolactone) using an active hydrogen compound). Examples of the copolymer component include polyoxy C _2-4 alkylene glycol 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), copolyesters obtained from a dicarboxylic acid component, a diol component, and a lactone (for example, polycaprolactone-polybutylene succinate copolymer resin).

  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 Al such as dicarboxylic acid) and a condensate 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 C _4-20 aminocarboxylic acid etc. such as ω-aminoundecanoic acid) homopolymer or copolymer (eg polyamide 6, polyamide 11, polyamide 12 etc.), these Copolyamide (polyamide component copolymerized) In example, polyamide 6/11, polyamide 6/12, polyamide 66/11, and 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 alkanedicarboxylic acid and the like) and polyester amides which are condensates of the aliphatic diol component (C _2-12 alkylene glycol such as ethylene glycol, propylene glycol and butanediol).

(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, polyoxytetramethylene glycol, bisphenol A-alkylene oxide adduct, etc. (A polyester diol with a polyether diol as a part of the diol component) polyester ether diols, such as can be utilized.

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), and 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 resins 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 copolymers, for example, poly (meth) acrylates 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, 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 polystyrene (HIPS or rubber graft 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 using a saponified vinyl acetate copolymer as a hydrophilic resin, the proportion of the hydrophobic comonomer unit is adjusted to, for example, about 10 to 40% by weight from the viewpoint of the affinity for the auxiliary component (B). 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, about 0.1 to 2), and more preferably 1.5. The following (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 (B), 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.

  Further, in the present invention, not limited to the type of resin polymerization method, a dispersion or resin particles can be obtained even using a resin using a monomer capable of addition polymerization reaction, but emulsion polymerization or suspension polymerization can be obtained. Resin particles (particularly spherical resin particles) can be obtained even with a resin obtained by a non-addition polymerization reaction that cannot be obtained by the above method.

  The average molecular weight of a resin component (such as a thermoplastic resin) is a polystyrene-reduced weight average molecular weight or viscosity average molecular weight by gel permeation chromatography, 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) Water-soluble auxiliary component The water-soluble auxiliary component contains at least an oligosaccharide (B1). Further, in order to adjust the heat melting property of the oligosaccharide, the water-soluble auxiliary component may further contain a plasticizing component (B2) for plasticizing the oligosaccharide. When the oligosaccharide (B1) and the water-soluble plasticizing component (B2) are combined, the viscosity of the water-soluble auxiliary component (B) can be adjusted in kneading with the organic solid component (A). The water-soluble auxiliary component can form organic solid particles (resin particles and the like) by appropriately eluting or washing after forming a dispersion in combination with the organic solid component.

(B1) Oligosaccharide The oligosaccharide (B1) comprises 2 to 10 molecules of a 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 (B1) 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 (particularly tetrasaccharides) in the oligosaccharide composition is, for example, 60% by weight or more (for example, , 60 to 100% by weight), preferably 70% by weight or more (for example, about 70 to 100% by weight), more preferably 80% by weight or more (for example, about 80 to 100% by weight), particularly 90% by weight or more ( For example, it may be about 90 to 100% by weight.

  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; 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 (B1) 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 (B1).

  The temperature difference between the melting point or softening point of the oligosaccharide (B1) 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 (B1) can be selected in the range of 70 to 300 ° C. depending on the type of the organic solid component (A), for example, 90 to 290 ° C., preferably 100 to 280 ° C. (for example, 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.

(B2) Water-soluble plasticizing component The water-soluble plasticizing component (B2) is not particularly limited as long as the oligosaccharide (B1) is capable of expressing the phenomenon of being hydrated to be in a syrup state, such as sugars and sugar alcohols. 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 (B1). 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, xylopentod 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 (especially 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 (B1). For example, among the disaccharides, a disaccharide having a low melting point or a low softening point (for example, gentibiose, 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, and as such saccharides, free monosaccharides as well as disaccharides having a low melting point or a low softening point (for example, gentibiose, 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 (gamma Lactitol), allosulfitol (allitol), arsitol, etc.], 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 (B2) may be liquid (syrup-like) 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 (B) is composed of the oligosaccharide (B1) and the plasticizing component (B2), the oligosaccharide (B1) is effective even if it 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 (B2) 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 K 7206). 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, etc.), the temperature at which the plasticizing effect is exerted on oligosaccharides is changed to the plasticizing component (B2). The “melting point or softening point” may be used.

  Further, the oligosaccharide (B1) may exhibit a melting point or softening point at a temperature higher than the melting point or softening point of the plasticizing component (B2), or may be decomposed.

  The melting point or softening point of the auxiliary component (B) 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 (B) 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 (B) and the heat distortion 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 (B) 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 dispersed form can be fixed in a short time by the auxiliary component (B) (for example, sugar component) having a high solidification rate.

  Further, the melt flow rate of the auxiliary component (B) (for example, the auxiliary component including the oligosaccharide (B1) and the plasticizing component (B2)) 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 (B), the proportion (weight ratio) of the plasticizing component (B2) is not localized due to agglomeration or the like with the melt kneading, and the oligosaccharide (B1) is efficiently Amount that can be plasticized, for example, oligosaccharide (B1) / plasticizing component (B2) = 99/1 to 50/50, preferably 95/5 to 60/40, more preferably 90/10 to 70 / About 30. In addition, according to the melt-kneading temperature (processing temperature), the ratio of the oligosaccharide (B1) and the plasticizing component (B2) is appropriately adjusted so that the organic solid component (A) and the auxiliary component (B) are mixed. The efficiency of kneading may be controlled. For example, when melt-kneading at a relatively low temperature (for example, about 90 to 180 ° C.), the components (A) and (B) can be efficiently kneaded by increasing the proportion of the plasticizing component.

  The water-soluble auxiliary component (B) has the following properties (I-1) to (I-3).

(I-1) When measured at a temperature of 180 ° C. and a shear rate of 126 sec ⁻¹ using a capillary having a pore diameter of 1 mm and a length of 40 mm, the shear viscosity of the water-soluble auxiliary component (B) is, for example, 5 Pa · s or more. (For example, about 5 to 250 Pa · s), usually 8 Pa · s or more (for example, about 8 to 200 Pa · s), preferably 10 Pa · s or more (for example, about 10 to 150 Pa · s), More preferably, it is 12 Pa · s or more (for example, about 15 to 150 Pa · s), and may be about 20 to 150 Pa · s (for example, 40 to 130 Pa · s). When the water-soluble auxiliary component (B) having such melt viscosity characteristics is used, the composition with the organic solid component (A) such as a resin component is uniformly melted while preventing the auxiliary component (B) from being separated. The organic solid component (A) can be formed into particles. Furthermore, in the molding apparatus, the water-soluble auxiliary component (B) does not flow out from the joints such as the vent part, the feed block, and the die, and the kneading force is effectively applied to the composition while preventing the idling of the screw. Can act. In addition, the molding processing temperature of resin or the like is usually 140 to 240 ° C., and the shear rate of a typical processing machine such as an extruder is usually about 50 to 200 sec ⁻¹ . Therefore, in the present invention, the temperature of 180 ° C. and the shear rate of 126 sec ⁻¹ are adopted as typical conditions.

(I-2) When a plate-like molded body of 25 mm × 25 mm × 3 mm was immersed in 500 ml of distilled water at 25 ° C. for 600 seconds, the following formula W ₁ / (W ₁ −W ₂ ) × 600 × 0.5
(W ₁ represents the weight of the plate-shaped molded body before immersion, and W ₂ represents the weight of the plate-shaped molded body after dipping for 600 seconds and then removing moisture by drying.)
The half-life time in water represented by is 1500 seconds or less (for example, 10 to 1500 seconds), preferably 1200 seconds or less (for example, 20 to 1200 seconds), more preferably 1000 seconds or less (for example, 20 to 1000). Second). In a preferred embodiment, the half-life time of the water-soluble auxiliary component (B) is 800 seconds or less (for example, 10 to 800 seconds), preferably 780 seconds or less (for example, 10 to 750 seconds), particularly 720 seconds or less (for example, 10 to 720 seconds). Since it has such characteristics, the water-soluble auxiliary component (B) has a high dissolution rate in water and high solubility or elution. Therefore, unlike the method of eluting the water-soluble polymer, the water-soluble component (B) can be eluted with the minimum amount of water while reducing the energy load for stirring without using a large amount of water. The productivity of the molded body (particles, porous body, etc.) composed of the component (A) can be greatly improved.

  Further, (I-3) the water-soluble auxiliary component (B) is 10 mPa · sec or less (for example, 2 to 10 mPa · sec) at 25 ° C. in a 10 wt% aqueous solution measured with a B-type viscometer, preferably 7 mPa · sec or less (for example, 2 to 7 mPa · sec), more preferably 5 mPa · sec or less (for example, 2 to 5 mPa · sec), and usually about 3 to 7 mPa · sec. Thus, since the aqueous solution viscosity of water-soluble auxiliary component (B) is small, the separation efficiency (or filtration efficiency) with the particle | grains comprised with the organic solid component (A) can be improved greatly by elution operation with water. Therefore, unlike the method of eluting the water-soluble polymer, the viscosity of the aqueous solution can be reduced, and in centrifugation, particles composed of the organic solid component (A) can be separated within a short time without increasing the number of rotations. In the filtration separation, particles composed of the organic solid component (A) can be separated in a low pressure within a short time. Therefore, it is advantageous in terms of energy and the productivity of particles composed of the organic solid component (A) can be improved.

  As described above, the water-soluble auxiliary component (B) having the characteristics (I-1) to (I-3) has high solubility in water and low aqueous solution viscosity despite its high melt viscosity. Moreover, it can be melt-molded by various methods such as injection molding and extrusion molding by melt-kneading with an organic solid component (A) such as a resin component.

  The ratio (weight ratio) between the organic solid component (A) and the auxiliary component (B) 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 it is not particularly limited, it is usually an amount that does not impair the moldability, for example, organic solid component (A) / auxiliary component (B) = 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 organic solid component (A) and the auxiliary component (B) have the same or different melt viscosity (shear viscosity). In particular, when the viscosity of the oligosaccharide (or the auxiliary component (B) containing the oligosaccharide) is close to the melt viscosity of the organic solid component (A), the dispersibility of the organic solid component (A) can be improved, and the dispersed phase ( In addition, the particle size of the resulting resin particles can be reduced and the particle size distribution can be narrowed.

Difference in melt viscosity, for example, can be expressed as the ratio η _A / η _B of the shear viscosity eta _B of the organic solid shear viscosity eta _A and the auxiliary component of the component (A) (B), the shear viscosity By reducing the ratio, the coefficient of variation in average particle diameter can be reduced, and the particle diameter of organic solid particles (resin particles and the like) can be controlled.

The shear viscosity ratio η _A / η _B is usually 20/1 or less (for example, about 0.05 / 1 to 20/1), preferably 0.06 / 1 to 15/1, more preferably 0.1. / 1 to about 10/1 may be sufficient. The coefficient of variation of the average particle diameter can be controlled by adjusting the combination of the organic solid component (A) and the auxiliary component (B) and the processing temperature (such as mixing temperature or kneading temperature).

In the shear viscosity ratio, the shear viscosity of each component is the pore size at the melt kneading temperature (typically 180 ° C.) of the organic solid component (A) and the auxiliary component (B) accompanying the preparation of the dispersion. The shear viscosity measured using a capillary with a length of 1 mm and a length of 40 mm at a shear rate of 126 sec ⁻¹ is shown.

When measured using a capillary having a pore diameter of 1 mm and a length of 40 mm under the conditions of a temperature of 180 ° C. and a shear rate of 126 sec ⁻¹ , the shear viscosity η _A of the organic solid component (A) is the shear of the auxiliary component (B). The viscosity can be appropriately selected according to the viscosity η _B, and may be, for example, about 50 to 1000 Pa · sec, preferably about 100 to 900 Pa · sec, and more preferably about 150 to 800 Pa · sec. The shear viscosity η _B of the auxiliary component (B) is as described above, and is, for example, 5 to 250 Pa · sec, preferably 10 to 150 Pa · sec (for example, 20 to 150 Pa · sec), and more preferably 40. It may be about 130 Pa · sec.

  In the present invention, the organic solid component (A) and the auxiliary component (B) have different surface tensions. In particular, since the auxiliary component (B) contains at least the oligosaccharide (B1) and the water-soluble plasticizing component (B2), the surface tension is usually smaller than that of the organic solid component (A). Thus, in the present invention, the difference or ratio of the surface tension between the organic solid component (A) and the auxiliary component (B) can be increased, and the dispersed phase is composed of the organic solid component having a large surface tension. The shape of (or organic solid particles) can be made spherical.

The difference between the surface tension of the organic solid component (A) and the surface tension of the auxiliary component (B) can be expressed, for example, by the ratio of the contact angle between the two. In 25 ° C., and the contact angle theta _A with water of the organic solid component (A), the ratio of the contact angle theta _B with water auxiliary component _{(B) (θ A / θ} B) is 2 or more (e.g., θ _A / θ _B = about 2/1 to 10/1), preferably 2.5 or more (for example, θ _A / θ _B = about 2.5 / 1 to 9/1), more preferably 3 or more (for example, , Θ _A / θ _B = about 3/1 to 8/1). The contact angle refers to the surface of the water droplet and the organic solid component (or auxiliary component) when the water droplet spreads on the surface of the organic solid component or auxiliary component at room temperature (25 ° C.) and stops spreading. Of the angles formed between the tangent to the water droplet and the surface of the organic solid component (or auxiliary component) at the intersection with the surface, it refers to the angle on the water droplet side.

The contact angle θ _A of the organic solid component (A) may be, for example, about 40 to 110 °, preferably 50 to 105 °, and more preferably about 60 to 105 °. Further, the contact angle θ _B of the auxiliary component (B) may be, for example, 10 to 25 °, preferably 10 to 20 ° (for example, 12 to 20 °), and more preferably about 15 to 20 °. .

  In the present invention, the composition (or dispersion) contains various additives, for example, fillers (such as fibrous fillers such as granular fillers and glass fibers), plasticizers or softeners, and light as necessary. Degradability-imparting agent (anatase type titanium oxide, etc.), lubricant, stabilizer (heat stabilizer, antioxidant, UV absorber, weather resistance (light) stabilizer, etc.), UV scattering agent (titanium oxide, zirconium oxide, zinc oxide) , Powders of metal oxides such as iron oxide), dispersants, flame retardants, antistatic agents, colorants [dyes such as oil-soluble organic dyes; inorganic or organic pigments (for example, ferromagnetic such as iron, cobalt, nickel) Metal (powder); ferromagnetic alloys such as magnetite and ferrite (powder); including ferromagnetic materials such as ferromagnetic metal oxides (powder) such as magnetic iron oxide)], charge control agents (nigrosine dye, trif Positive charge control agents such as nylmethane dyes, quaternary ammonium salts, guanidine compounds, imidazole compounds, amine compounds; negative charge control agents such as salicylic acid metal complexes, azo dye metal complexes, copper phthalocyanine dyes, nitroimidazole derivatives, urea derivatives Etc.), fluidizing agents, waxes [olefin waxes such as polyethylene wax, ethylene copolymer wax, polypropylene wax; paraffin wax; higher fatty acids or derivatives thereof (salts, polyhydric alcohol esters, amides, etc.); ester waxes Etc.], and may contain other additives such as a crosslinking agent. In the dispersion, the additive may be contained in any of the dispersed phase and the matrix constituting the dispersion. Moreover, as said additive, the component different from the said organic solid component can be normally used.

  The additive can be selected depending on the application of the particles. For example, in applications such as cosmetics (foundation, white powder, blusher, etc.), an ultraviolet absorber (benzophenone-based absorbent, cinnamic acid-based absorbent, p-amino, etc. Benzoic acid-based absorbents, salicylic acid-based absorbents, dibenzoylmethane-based absorbents, urocanic acid or esters thereof, β-isopropylfuranone, β-carotene and the like), the above-described ultraviolet light scattering agents, coloring agents, and the like may be used. For image recording material applications such as toner, for example, a charge control agent, a fluidizing agent, waxes, a colorant, 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, a colorant, 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 with respect to 100 parts by weight of the organic solid component (resin etc.). 0 to 50 parts by weight (for example, 0 to 30 parts by weight), preferably about 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, It may be about 0.5 to 10 parts by weight).

[Dispersion]
In the dispersion of the present invention, the particulate dispersed phase composed of the organic solid component (A) is dispersed in the matrix composed of the water-soluble auxiliary component (B) containing at least the oligosaccharide (B1). .

  In the dispersion of the present invention, the average particle size of the dispersed phase is not particularly limited, and can be selected from the range of about 0.05 μm to 1 mm depending on the application, and is 0.1 to 800 μm, preferably 0.1 to 100 μm. More preferably, it may be about 0.2 to 50 μm, particularly about 1 to 40 μm. Moreover, the average particle diameter of the organic solid particles is, for example, 0.05 to 100 μm, preferably 0.05 to 10 μm, by appropriately selecting the type of the organic solid component (A) and the auxiliary component (B). Preferably, it can be as small as 0.05 to 5 μm, particularly 0.1 to 3 μm.

  In the present invention, the particle size distribution (coefficient of variation) can be reduced by making the particle size of the dispersed phase uniform. The variation coefficient (%) of the average particle size of the dispersed phase ([standard deviation of particle size / average particle size] × 100) is, for example, 60 or less (for example, about 5 to 60), preferably 50 or less (for example, 10 to 10). About 50), more preferably 40 or less (for example, about 10 to 40).

  In the dispersion of the present invention, the shape of the dispersed phase may be in the form of particles, and may be, for example, spherical, ellipsoidal, polygonal, prismatic, cylindrical, rod-like, or indefinite. The spherical dispersion (or spherical particles) is not limited to a true sphere, and for example, the length ratio between the major axis and the minor axis is, for example, major axis / minor axis = about 1.5 / 1 to 1/1. Certain shapes are 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.

[Method for producing organic solid particles]
In the present invention, the organic solid component (A) constituting the granular dispersed phase and the water-soluble auxiliary component (B) comprising at least the oligosaccharide (B1) and constituting the matrix are kneaded (melt kneaded) to form From the dispersion, the water-soluble auxiliary component (B) is eluted to produce particles composed of the organic solid component (A).

  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.

  The water-soluble auxiliary component may be eluted from the kneaded product (melt kneaded product), or the kneaded composition may be molded and eluted from the obtained preform. Examples of the molding method for the preform include extrusion molding, injection molding, blow molding, calendar molding, and the like. 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.

  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, even if the organic solid component (A) and the auxiliary component (B) are compatible in the molten state, the surface tension, crystallization, etc. are accompanied by cooling. A dispersed phase can be formed by the difference in the solidification rate of the resin, 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 (B). The temperature at which the organic solid component (resin component or the like) is heat-deformed or the melting point or softening point of the auxiliary component is about 10 to 100 ° C., preferably about 15 to 80 ° C., more preferably the temperature. The temperature may be lower by about 20 to 60 ° C. 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 kneading conditions (for example, kneading time, kneading temperature, etc.) and cooling conditions (for example, cooling time, cooling temperature, etc.), the average particle size of the dispersed phase (or organic solid particles) can be changed, The particle size distribution width can be further narrowed.

  The dispersion obtained in this manner is a phase in which the auxiliary component (B) forms a continuous phase in the sea-island structure and the dispersed phase composed of the organic solid component (A) forms an independent dispersed phase. Since it has a separation structure, the auxiliary component can be eluted or extracted quickly, and the dispersed phase (organic solid phase such as resin phase) can be obtained as particles.

  The elution (or washing) of the water-soluble auxiliary component (B) is carried out using an aqueous solvent such as water, a water-soluble solvent (for example, 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 (B), 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). ) Can be done. 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.

  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 is easily soluble in water, a large amount of water is not required.

  The organic solid particles can be recovered from the dispersion liquid in which the particles are dispersed using a conventional separation (recovery) method such as filtration or centrifugation.

  In particular, since the viscosity of the eluate obtained by elution of the auxiliary component is low, the eluate and the organic solid particles can be easily separated, and the organic solid particles can be easily recovered. If the viscosity of the eluate is too high, for example, when organic solid particles are separated by centrifugation, it may be necessary to rotate at high speed or increase the rotation time. Moreover, in the separation by filtration, it may be necessary to perform filtration at a high pressure, or the filtration time may be prolonged, which may be disadvantageous in terms of energy load and production speed. In order to reduce the viscosity of the eluate, it is necessary to elute using a large amount of water.

  In the obtained organic solid particles, it is desirable that the auxiliary component does not substantially remain. However, for example, a small amount of the auxiliary component remains in the organic solid particles from the viewpoint of cost reduction of the washing process. However, 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 (B) in the organic solid particles is, for example, 3% by weight or less (for example, about 0 to 3% by weight), preferably 1% by weight or less (for example, about 0 to 1% by weight), Preferably, it may be 0.5% by weight or less (for example, about 0.001 to 0.5% by weight). When the matrix of the dispersion is composed of a highly soluble water-soluble auxiliary component and an auxiliary component having a low affinity for the organic solid component is used, the content of the auxiliary component (B) in the organic solid particles is reduced. Can be reduced. For example, the proportion of the auxiliary component (B) in the organic solid particles is, for example, 0.1% by weight or less (for example, about 0.001 to 0.1% by weight), preferably 0.05% by weight with respect to the whole particles. % Or less (for example, about 0.001 to 0.05% by weight), more preferably 0.01% by weight or less (for example, about 0.001 to 0.1% by weight). In many cases, the following concentrations are used.

  The content of the auxiliary component (B) in the organic solid particles can also be reduced by washing the organic solid particles with an aqueous medium (such as water). For example, the content of the auxiliary component (B) is 10,000 ppm or less (for example, about 0.1 to 10,000 ppm), preferably 3,000 ppm or less (for example, 0.5 to 3, based on weight). 000 ppm), more preferably 1,000 ppm or less (for example, about 1 to 1,000 ppm), and further preferably 300 ppm or less (for example, about 1 to 300 ppm).

  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 organic solid particles obtained by the production method. The shape of the organic solid particles, the average particle size, and the variation coefficient of the average particle size can be selected from the same range as the dispersed phase. Further, the ratio of the major axis to the minor axis of the organic solid particles can be selected from the same range as that of the dispersed phase. The shape and size of the organic solid particles are maintained as they are unless the organic solid component (A) is eluted in the elution solvent (aqueous solvent). The organic solid particles may have the same particle size by means such as classification as required.

  Since the organic solid particles (resin particles, etc.) obtained by the method of the present invention have a uniform particle size, ink (for example, foundations, white powder, blushers, eye shadows, etc.), inks used for inkjet printing, etc. It is useful for image recording materials such as polymer inks) and colored toners, paints and coating agents (such as powder coating or slurry coating), and printing ink colorants. Further, the organic solid particles may be used for improving 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.), additives for sheets or films, abrasives for chemical mechanical polishing (CMP) of semiconductors, and the like.

  In addition, since biodegradable resin particles obtained using biodegradable resin components are excellent in biodegradability, agricultural chemicals, pharmaceuticals, paints (for example, powder paints, ship bottom paints, etc.), coating agents, adhesives 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 1-3
A resin composition composed of a resin component having the composition shown in Table 1 and a water-soluble auxiliary component is prepared at a processing temperature shown in Table 1 at 50 rpm with a Brabender (Toyo Seiki Co., Ltd., Lab Plast Mill). After melt-kneading for a minute, it was immersed in hot water at 60 ° C. to obtain a suspension of resin particles. Resin particles were recovered by separating insolubles from this suspension using a membrane membrane made of polyvinylidene fluoride having a pore diameter of 0.45 μm. A scanning electron micrograph of the resin particles obtained in Example 1 is shown in FIG.

  In the examples, the following components were used, and the shear viscosity of the resin and auxiliary components, the average particle size and particle size distribution of the resin particles, and the contact angles of the resin and auxiliary components were measured by the following methods.

(Resin component)
Resin 1: Polyamide 12 resin (Daicel Degussa Co., Ltd., Daiamide L1600)
Resin 2: Polycaprolactone-polybutylene succinate copolymer resin (Daicel Chemical Industries, Cell Green CBS178)
Resin 3: Polycaprolactone-polybutylene succinate copolymer resin (Daicel Chemical Industries, Cell Green CBS17X)
(Water-soluble auxiliary ingredient)
(B1) oligosaccharide
(B1-1): Starch sugar (manufactured by Nippon Shokuhin Kako Co., Ltd., starch saccharified product Fujioligo 450P)
(B1-2): Starch sugar (manufactured by Towa Kasei Kogyo Co., Ltd., reduced starch saccharified product PO-10)
(B2) Plasticizing component Sugar alcohol: Sorbitol (Sorbit, manufactured by Towa Kasei Kogyo Co., Ltd.).

(Shear viscosity)
For each of the resin component (A) and the auxiliary component (B), the capillograph (manufactured by Toyo Seiki Co., Ltd., capillary diameter (D) 1 mm, length (L) 40 mm) was used to obtain the processing temperatures shown in Table 1. The shear viscosities η _A and η _B were measured under the condition of a shear rate of 126 sec ⁻¹ . In addition, when each component was comprised with several components, the sample was prepared by performing preliminary kneading | mixing suitably as needed.

(Average particle size and particle size distribution of resin particles)
After drying the resin particles, the shape of the fine particles was observed using a scanning electron microscope.

  The particle size of 100 particles randomly selected from an electron micrograph was measured, and the number average particle size and standard deviation were determined. Further, the coefficient of variation was calculated according to the following formula.

  Coefficient of variation (%) = standard deviation / number average particle size × 100.

(Contact angle)
About each of resin component (A) and auxiliary agent component (B), water (distillation) is used at 25 ° C. using a contact angle measuring machine (manufactured by Kyowa Interface Science Co., Ltd., FACE automatic contact angle meter CA-Z type). The contact angle with respect to water) was measured, the contact angle θ _A of the resin component (A) was divided by the contact angle θ _B of the auxiliary component (B), and the ratio θ _A / θ _B of both was obtained.

  The results of the examples are shown in Table 1.

  In Examples 1 to 3, resin particles having a small variation coefficient (less than 40%) and uniform particle diameters were obtained. The shape of the resin particles was also spherical.

1 is a scanning electron micrograph of the resin particles of Example 1. FIG.

Claims (20)

  A composition comprising a meltable organic solid component (A) and a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1), the organic solid component (A) and the auxiliary component The composition in which (B) has the same or different melt viscosity at the melt kneading temperature of the composition. In the melt-kneading temperature of the composition, the ratio eta _A / eta _B of the shear viscosity eta _B of the shear viscosity eta _A and auxiliary components of the organic solid components was measured at a shear rate of 126sec ^-1 (A) (B) is 20 / The composition according to claim 1, which is 1 or less.   A composition comprising a meltable organic solid component (A) and a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1), the organic solid component (A) and the auxiliary component (B) ) Have different surface tensions. In 25 ° C., wherein the contact angle theta _A with water of the organic solid component (A), the ratio of the contact angle theta _B with water auxiliary component _{(B) (θ A / θ} B) is 2 or more Item 4. The composition according to Item 3.   The composition according to claim 1 or 3, which is a resin composition comprising a resin component (A) and a water-soluble auxiliary component (B).   The composition according to claim 1 or 3, wherein the oligosaccharide (B1) comprises at least a tetrasaccharide.   The oligosaccharide (B1) is composed of at least one selected from starch sugar, galactooligosaccharide, coupling sugar, fructo-oligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide and chitosan oligosaccharide. Composition.   The composition according to claim 1 or 3, wherein the auxiliary component (B) comprises an oligosaccharide (B1) and a water-soluble plasticizing component (B2) for plasticizing the oligosaccharide (B1).   The oligosaccharide (B1) exhibits a melting point or softening point at a temperature higher than the heat distortion temperature of the organic solid component (A) or decomposes, and the melting point or softening point of the plasticizing component (B2) The composition according to claim 8, which is not higher than the heat distortion temperature of (A).   The composition according to claim 8, wherein the oligosaccharide (B1) exhibits a melting point or softening point at a temperature higher than the melting point or softening point of the plasticizing component (B2) or decomposes.   The composition according to claim 8, wherein the plasticizing component (B2) is composed of at least one selected from saccharides and sugar alcohols.   The composition according to claim 11, wherein the sugar alcohol is at least one selected from erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol, and mannitol.   The composition according to claim 8, wherein the ratio (weight ratio) between the oligosaccharide (B1) and the plasticizing component (B2) is oligosaccharide (B1) / plasticizing component (B2) = 99/1 to 50/50. .   The ratio (weight ratio) between the organic solid component (A) and the auxiliary component (B) is organic solid component (A) / auxiliary component (B) = 55/45 to 1/99. The composition as described.   A dispersion in which a particulate dispersed phase composed of a meltable organic solid component (A) is dispersed in a matrix composed of a water-soluble auxiliary component (B) containing at least an oligosaccharide (B1). A dispersion in which the organic solid component (A) and the auxiliary component (B) have the same or different melt viscosities at the melt kneading temperature.   The dispersion according to claim 15, wherein the variation coefficient of the average particle size of the dispersed phase is 60% or less.   The average particle diameter of the dispersed phase is 0.05 to 100 μm, and the dispersed phase is a spherical dispersed phase having a length ratio of a major axis to a minor axis (major axis / minor axis) = 1.5 / 1 to 1/1. The dispersion according to claim 15.   Dispersion produced by melt-kneading meltable organic solid component (A) constituting the particulate dispersed phase and water-soluble auxiliary component (B) comprising at least oligosaccharide (B1) and constituting the matrix The auxiliary component (B) is eluted to produce particles composed of the organic solid component (A), as the organic solid component (A) and the auxiliary component (B). A method for producing particles using components having the same or different melt viscosities at the melt kneading temperature.   Particles obtained by the production method according to claim 18.   Spherical particles having an average particle diameter of 0.05 to 100 μm, a coefficient of variation of the average particle diameter of 60% or less, and a length ratio of the major axis to the minor axis (major axis / minor axis) = 1.5 / 1 to 1/1. The particle according to claim 19.