JP2008239638A - Resin particle and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing crystalline thermoplastic elastomer resin particles having excellent heat resistance. <P>SOLUTION: A water-soluble auxiliary, that is composed of at least a water-soluble polysaccharide (A1) and can be melted and kneaded, is melted and kneaded with a crystalline thermoplastic elastomer (a crystalline polyamide elastomer, crystalline polyester elastomer or the like) satisfying all conditions of (i) a flexural modulus of ≤500 MPa, (ii) compression set of ≥30% and (iii) a melting point of ≥150°C to form a dispersion having a dispersed thermoplastic elastomer phase, and eluting the dispersion with an aqueous solvent to produce resin particles (spherical thermoplastic elastomer resin particles) composed of the thermoplastic elastomer. The water-soluble auxiliary comprises the water-soluble polysaccharide (A1) such as an oligosaccharide, a polysaccharide having a cyclic structure etc., and a water-soluble plasticized component (A2) such as a sugar alcohol etc. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to resin particles that are easily deformed by compression and easily deformed permanently, and are excellent in heat resistance and chemical resistance, and thermoplastic elastomers (particularly block copolymerization) for forming such resin particles. It is related with the method which can manufacture a resin particle even if it is a body polymer).

In recent years, it has been easily deformed by loading due to changes in the usage method and development of new joining methods for laminated circuit board members, various spacers, and cosmetics, etc., and the deformation can be recovered even if the weight is removed. There is a demand for soft particles that do not.
Conventional fine polymer particles have been formed by a method in which polymerization of monomers is involved in the generation of resin particles. The soft resin particles obtained by such a method are deformed by a load, and particles having a small compression set that recover from the deformation after removing the load are used. Such a property is expressed because deformation due to stress is caused by a decrease in morphological entropy of the polymer chain. In other words, those exhibiting rubber elasticity are in a low entropy state when the molecular chain is stretched, but generate an elastic force to return to the original state due to the thermal motion of the molecular chain. Therefore, when a crosslinked structure is formed by bond formation (crosslinking) between polymer chains, resin particles exhibiting rubber elasticity are obtained.

  When soft resin particles are obtained by a method in which the polymerization of conventional monomers is involved in the formation of resin particles, due to the limitation of the polymerization method, when the obtained resin particles are soft, I had to do it. For this reason, as described above, rubber elasticity inevitably occurs because of the crosslinked polymer. .

  On the other hand, in recent years, there has been a demand for particles that can be easily deformed by a load, such as a member for a laminated circuit board, various spacers, or cosmetics, and remain a certain amount of permanent deformation even after the load is removed. That is, resin fine particles made of a polymer having a large stress relaxation are suitable for such applications. However, such fine particles have not been provided.

One reason for this is the use of these particles. That is, these resin particles are generally used in combination with other materials forming a matrix as a binder. Specifically, for example, it is used in a state where resin particles are dispersed in an adhesive binder. Therefore, resistance to various chemical substances used in these binders, particularly solvents and monomers (including crosslinkable monomers) is required. And, in order to impart insolubility to such a solvent, a method of making the polymer a crosslinked polymer is taken. There are various types of polymers, and there are various types of polymers that satisfy insolubility and solvent resistance in solvents, but such fine particles have not been provided.
Furthermore, spherical particles having various particle diameters are required depending on the application, but there is no means for providing resin particles that satisfy all of these.
Conventionally, a mechanical pulverization method has been used as a method for producing resin particles. However, in the case of a soft resin, it cannot be pulverized by such a mechanical pulverization method, and it is difficult to obtain spherical resin particles. In addition, it is impossible to obtain spherical particles. There are also significant limitations in control.

As a method of making a thermoplastic resin into substantially spherical fine particles without depending on mechanical pulverization, for example, in JP-A-60-13816 (Patent Document 1), polyethylene glycol and a thermoplastic resin are melted and stirred. Later, a method for producing thermoplastic resin particles has been proposed in which both polymers are coagulated by being poured into water, and then polyethylene glycol is removed using water.
Japanese Patent Application Laid-Open No. 61-9433 (Patent Document 2) 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. Is disclosed. Japanese Patent Laid-Open No. 9-165457 (Patent Document 3) discloses a melt-molded product obtained by mixing a melt-formable water-soluble polymer such as polyvinyl alcohol resin, modified starch, and polyethylene oxide with a thermoplastic resin. After obtaining the above, a method for producing resin fine particles is disclosed in which water is used to remove the water-soluble polymer from the molded product.

However, even in these methods, since the combination of the resin and the water-soluble polymer is used, it is difficult to collect the particles even if the soft resin is made into particles. That is, in these techniques, a thermoplastic water-soluble polymer is used as the continuous phase. Such a water-soluble polymer exhibits a large viscosity even in an extremely low concentration aqueous solution. (The viscosity of the aqueous solution increases even at extremely low concentrations.) And, filtration of an aqueous solution exhibiting such a large viscosity requires a large filtration pressure.
For this reason, in the production of the resin particles obtained by these methods, a great filtration pressure is required for separating the water-soluble polymer forming the continuous phase from the resin fine particles. Furthermore, the soft resin particles are soft, the cake effect is excessive in the filtration process, the filtration efficiency is remarkably lowered, and the water-soluble polymer and the fine particles made of the soft resin are virtually impossible to be separated. . In particular, since polyethylene oxide lacks heat resistance, it is difficult to form a high melting point resin that requires processing at a high temperature for particle formation, that is, high heat resistance resin.

  On the other hand, in Japanese Patent Application Laid-Open No. 2003-023536 (Patent Document 4) and Japanese Patent Application Laid-Open No. 2005-162841 (Patent Document 5), a water-soluble auxiliary component containing an oligosaccharide as an essential component is melt-stirred with a thermoplastic resin. A method is disclosed in which a dispersion having a thermoplastic resin as a dispersed phase and a water-soluble auxiliary component as a continuous phase is obtained, and then the water-soluble auxiliary component is removed with water to obtain thermoplastic resin particles. . In this method, since a saccharide component is used for the continuous phase, a liquid medium is used even when a resin composition is recovered by treating a molten mixed resin composition of a saccharide component and a soft resin with water to dissolve the saccharide component in water. This is useful for collecting fine particles made of a soft resin.

However, in this method, the particle size of the thermoplastic elastomer having a high melting point (high heat resistance) that requires a particularly high processing temperature is uniform due to the heat resistance problem of the water-soluble auxiliary component containing the oligosaccharide used as an essential component. Production of fine particles (that is, low Dw / Dn and CV values) was difficult.
Japanese Patent Laid-Open No. 60-13816 JP 61-9433 A JP-A-9-165457 JP 2003-023536 A JP 2005-162841 A

Accordingly, an object of the present invention is to provide crystalline resin particles having excellent heat resistance and chemical resistance, and a method for efficiently producing the resin particles.
Another object of the present invention is to provide a method capable of producing spherical resin particles having a predetermined particle diameter with high reproducibility by melt kneading.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have melt-stirred a water-soluble auxiliary component having an oligosaccharide as an essential component with a thermoplastic resin, and the thermoplastic resin has been dispersed in a phase, a water-soluble auxiliary component. After obtaining a dispersion having a continuous phase, water-soluble auxiliary components are removed with water to obtain thermoplastic resin particles (in some cases, abbreviated as “forced emulsification method” for simplification described below) In this case, the pressure during filtration does not become unnecessarily high even when the dispersed phase composed of the thermoplastic elastomer is extracted with an aqueous solvent using a water-soluble auxiliary component and filtered. The present invention was completed by finding that the molecules can be easily made into fine particles.

That is, the present invention
A) The flexural modulus obtained by the method according to JIS K7171 is 500 MPa or less; b) the compression set measured at 70 ° C. obtained by the method according to JIS K6262 is 30% or more;
C) Melting and kneading a crystalline thermoplastic elastomer having a melting point measured by DSC method of 150 ° C. or more, a water-soluble polysaccharide (A1), and a water-soluble plasticizing component (A2) The soluble polysaccharide (A1) and the water-soluble plasticizing component (A2) are eluted. When the thermoplastic elastomer is granulated by this method, the resin is soft and has high heat resistance without involving the polymerization of the monomer and the liquid medium (aqueous or oily liquid medium) at room temperature in the formation of the resin particles. Even (that is, even if it has a high melting point), it has been found that spherical resin particles can be obtained within a processing temperature range in which the water-soluble polysaccharide (A1) can be suitably used, and the present invention has been completed.

  Further, the present inventors have found that when a crystalline thermoplastic elastomer is used, although it is an elastomer, the stress relaxation becomes large, the particles have a large compression set, are easily deformed by weighting, and are subjected to weighting. The present invention was completed by finding that the particles are soft particles whose deformation does not recover even after removal.

  The resin particles of the present invention are in a matrix of a water-soluble auxiliary agent composed of at least the water-soluble polysaccharide (A1) without the polymerization of monomers (and aqueous or oily medium that is liquid at room temperature) participating in particle formation. It is obtained by eluting the dispersion in which the resin is dispersed in an aqueous solvent. The volume elastic modulus of the resin particles can be 20 MPa or less. The resin particles are solid at room temperature (15 to 25 ° C.). The polymer constituting the resin particles is a thermoplastic elastomer, may be a block copolymer polymer, and may be a crystalline polyamide elastomer or a crystalline polyester elastomer.

The average particle size and particle size distribution of the resin particles can be controlled and are not particularly limited. For example, the number average particle size Dn is 0.1 to 20 μm, and the ratio Dw of the volume average particle size Dw to the number average particle size Dn is / Dn may be 2.0 or less.
The resin particles of the present invention comprise a melt-kneaded water-soluble auxiliary agent composed of at least a water-soluble polysaccharide (A1), and a) a flexural modulus obtained by a method according to JIS K7171, 500 MPa or less, JIS A crystalline thermoplastic elastomer (crystalline crystalline elastomer) satisfying all the conditions, in which the compression set measured at 70 ° C. obtained by the method according to K6262 is 30% or more and the melting point measured by DSC method is 150 ° C. or more. Polyamide elastomer or crystalline polyester elastomer) is melt-kneaded to produce a dispersion in which a soft resin phase is dispersed, and the dispersion is eluted with an aqueous solvent to obtain resin particles composed of the soft resin. Can be manufactured. The water-soluble auxiliary agent may contain a water-soluble plasticizing component (A2) that can plasticize the water-soluble polysaccharide (A1).
The water-soluble polysaccharide (A1) may be a production method comprising at least one selected from oligosaccharides and polysaccharides having at least one cyclic structure.

In this specification, the terms “polymer”, “water-soluble polymer”, “plastic”, and “thermoplastic resin” are “new edition polymer dictionary” (published by Asakura Shoten, Society of Polymer Science: November 25, 1999, first edition). ) Definition. However, when the term “polymer” is used as the polymer fine particle or the constituent material of the polymer fine particle, it is synonymous with the term “plastic” in the above-mentioned “New Edition Polymer Dictionary”. It means the main raw material added with additives such as fillers, plasticizers, stabilizers and pigments.
The meaning of the term “resin” in the terms “resin particles” and “resin fine particles” is synonymous with the term “plastic” in the above-mentioned “New Edition Polymer Dictionary”. Therefore, in the present invention, the term “polymer fine particles” and the terms “resin fine particles” or “resin particles” have the same meaning.
The term “resin” has the broad meaning of the JIS Industrial Dictionary (published and edited by the Japanese Standards Association, published on October 20, 1996, third print), that is, “several base materials for plastics” This is the same meaning as “used to specify a polymer”.
The term “soft resin” is synonymous with the term “elastomer” in the second term in the “new edition polymer dictionary” (published by Asakura Shoten, edited by the Society of Polymer Science, November 25, 19998). That is, “an elastic body that is crosslinked by physical bonds (microcrystals, ionic bonds, hydrogen bonds), not covalent bonds. A high block in which a soft block as a rubber component and a hard block as a resin component are appropriately arranged in one molecule. It consists of molecules ".

  In the present invention, a water-soluble polysaccharide (A1) and preferably a melt-kneadable water-soluble auxiliary agent containing at least one selected from polysaccharides having at least one cyclic structure as the water-soluble polysaccharide (A1) are dispersed. Since resin particles can be dispersed as a dispersion phase as a medium, spherical resin particles can be efficiently produced even if the resin is highly heat resistant and soft. Also, resin particles having predetermined characteristics (particle diameter and particle size distribution) can be produced with high reproducibility by melt kneading.

[Thermoplastic elastomer]
The thermoplastic elastomer of the present invention is solid at room temperature (15 to 25 ° C.) and is substantially incompatible with the water-soluble auxiliary agent. Further, the thermoplastic elastomer is a thermoplastic resin.
As the thermoplastic elastomer, a water-insoluble resin (or hydrophobic resin, water-insoluble thermoplastic resin, etc.) is usually used.

In general, thermoplastic elastomers have the characteristics of rubber at room temperature, but at high temperatures, they can be easily molded by plastic processing machines such as softening, compression, extrusion, and injection, just like thermoplastic resins. Is a high polymer. Collectively called TPE (thermo-plastic elastomer). That is, the thermoplastic elastomer shares both components, a rubber component having an entropy elasticity (soft segment) and a molecular constraint component (hard segment) for preventing plastic deformation in the molecule.
The elastic body is not crosslinked by a covalent bond but is crosslinked by a physical bond (microcrystal, ionic bond, hydrogen bond). Therefore, the factor that develops elasticity is a higher-order structure such as a physical bond (microcrystal, ionic bond, hydrogen bond), and when the higher-order structure disappears, it does not exhibit the properties as an elastic body. There are many types of thermoplastic elastomers such as styrene (SBC), olefin (TPO), vinyl chloride (TPVC), urethane (PU), ester (TPEE), and amide (TPAE). Yes. Some thermoplastic elastomers exhibit a melting point and others do not. That is, some have a crystal structure and some do not.

  The thermoplastic elastomer in the present invention has a melting point. That is, it has a crystal structure. That is, when the thermoplastic elastomer has a crystal structure, it is used in a state where resin particles are dispersed in an adhesive binder, and various chemical substances used in the binder, particularly solvents and monomers (cross-linking). Even when resistance to a resin (including a functional monomer) is required, solvent resistance can be achieved.

  The thermoplastic elastomer in the present invention is a) The flexural modulus obtained by a method according to JIS K7171 is 500 MPa or less. B) The compression set measured at 70 ° C. obtained by a method according to JIS K6262 is 30% or more. C) Melting point (Tm) measured by DSC method is 150 ° C. or higher. As long as these three conditions are satisfied, the synthesis method is not particularly limited. That is, it may be a radical polymerization resin, an addition polymerization resin, or a ring-opening polymerization resin.

  A thermoplastic elastomer suitable for the present invention is a block copolymer. The block copolymer may be an α-olefin type. For example, an ethylene-α-olefin-based block copolymer can be used as long as it has a melting point and satisfies the requirements (a) to (c). Such a block copolymer may be a-(AB) n type or a-(ABA) n type. The A segment may be composed of ether, ester, amide, vinyl, or carbonate. Further, the A segment may be ether and the B segment may be composed of an ester. Particularly preferred are ether-esters and amides.

From the viewpoint of heat resistance, the preferred thermoplastic elastomer is preferably a polymer in which the hard segment portion is composed of an amide segment, an ethylene terephthalate segment, a butylene terephthalate segment, or the like.
In general, a thermoplastic elastomer has low heat resistance, but it can also have heat resistance by using a polymer containing these components having a high melting point as a hard segment.
Specific examples of these products include a VESTAMELT (trademark) elastomer manufactured by Daicel Degussa Co., Ltd. as a polyamide elastomer, and a perprene (trademark) series manufactured by Toyobo Co., Ltd. as a polyester elastomer.
As described above, the thermoplastic elastomer of the present invention has a crystal structure. The melting point of the thermoplastic elastomer measured by a differential scanning calorimeter (DSC) is 150 ° C. or higher, for example, 150 to 230 ° C., preferably 155 to 220 ° C., more preferably 170 to 215 ° C. (for example, 173 to 215 ° C.). It may be a degree. When a plurality of melting point peaks are shown, the melting point can be determined with the peak top value of the largest melting peak.

  In the thermoplastic elastomer of the block copolymer, the melting point of the segment having a crystal structure determines the melting point of the thermoplastic elastomer. The segment having a crystal structure may be a hard segment. In order to set the melting point of the hard segment to 150 ° C. or higher, the hard segment may be a polymer having a rigid structure. For example, a thermoplastic elastomer having polycarbonate as a hard segment may have a melting point of 205 ° C. It is known that a thermoplastic elastomer having a butylene terephthalate segment has a melting point exceeding 200 ° C.

The molecular weight of the hard segment also affects the melting point. In the same hard segment, the higher the molecular weight, the closer to the melting point of the homopolymer of the hard segment, that is, the higher the molecular weight of the hard segment, the higher the melting point. Of course, the crystallinity also increases.
In order to obtain a material having a melting point close to 150 ° C., a hard segment having a random copolymer may be selected. For example, if two types of dicarboxylic acids of terephthalic acid and isophthalic acid are used in the butylene terephthalate segment, the melting point of the hard segment can be adjusted in a wide range, and if the isophthalic acid component is increased, the melting point can be lowered. In the case of a thermoplastic elastomer whose hard segment is an amide segment, the melting point can be lowered by lowering the amide group concentration of the amide segment (that is, by increasing the number of carbon atoms between the amide groups). As a result, an amide-based thermoplastic elastomer having a high melting point can be obtained. As described above, the melting point can be lowered by lowering the molecular weight of the hard segment.

As described above, in order to obtain a thermoplastic elastomer having a melting point in the range described in the present invention, it can be obtained by adjusting the type of hard segment, the copolymerization ratio therein, and the molecular weight.
The thermoplastic elastomer having these crystal structures is a block copolymer as described above. As a manufacturing method thereof, generally, a hard segment and a soft segment are polymerized in advance, and these segments are condensed. Or the like can be used. For example, a-(AB) n type amide segment (amide-amide block copolymer) can be prepared by polymerizing each amide segment and then performing an amide exchange reaction by melt polymerization. The ether-ester block copolymer can be obtained, for example, by subjecting dimethyl terephthalate and ethylene glycol to melt-condensation polymerization using tin and magnesium catalysts in the presence of polyethylene oxide.

In general, in order to obtain a block copolymer from a mixture of a plurality of types of monomers in one step, a considerable selectivity is required in the chain extension reaction during polymerization. That is, when the selectivity is low, a random copolymer is obtained. Since combinations of monomers that can produce such highly selective reactions are limited, in general, either segment is created and polymerized as a prepolymer, or all segments are prepared as prepolymers and polymerized. This method is used as a conventional technique.
For this reason, when particles are obtained by a method in which monomer polymerization (and an aqueous or oily medium which is liquid at room temperature) is involved in particle formation, it is difficult to form various polymers as particles as in the present invention. In the present invention, by using a forced emulsification method, even such a block copolymer can be made into fine particles.

  The bending elastic modulus of the thermoplastic elastomer measured by a method according to JIS K7171 is 500 MPa or less (for example, about 10 to 450 MPa), preferably 400 MPa or less (for example, about 20 to 380 MPa), and more preferably 300 MPa or less (for example, About 50 to 250 MPa), and most preferably 200 MPa or less (for example, about 70 to 150 MPa).

That is, if the above-described thermoplastic elastomer having a flexural modulus of 500 MPa or less has less entropy elasticity, stress relaxation is increased, particles having a large compression set, easily deformed by weight, and the weight is removed. However, it becomes a soft particle that does not recover from deformation. A low flexural modulus means that the entropy elasticity is strong, the properties as an elastomer are strong, and the compression set is small. It has been found that the plastic elastomer produces compression set even at lower stresses.
This seems to be an intrinsic property of the crystalline thermoplastic elastomer used in the present invention, and is a characteristic because it is crystalline. That is, the crystalline thermoplastic elastomer of the present invention has a structure in which the crystalline region formed by the hard segment is dispersed in the non-crystalline region formed by the soft segment, so that the non-crystalline region of the soft segment is displaced. It is thought that plastic deformation is caused by this. For this reason, a low flexural elasticity is a guideline for plastic deformation, and is an important requirement for obtaining fine particles having a large permanent compression strain in the present invention. That is, fine particles formed from a thermoplastic elastomer having a low flexural modulus cause plastic deformation even with a small stress.

In order to obtain a thermoplastic elastomer having a flexural modulus of 500 MPa or less, it can be obtained by adjusting the ratio of the soft segment and the ratio of the hard segment. That is, by increasing the ratio of the soft segment to the hard segment, the crystalline thermoplastic elastomer having a low bending elasticity can be easily obtained.
In consideration of the above melting point requirements, a thermoplastic elastomer having a rigid hard segment, a high average molecular weight of the hard segment, and a small ratio of the hard segment to the soft segment is preferable. . That is, a thermoplastic elastomer having a large crystal diameter formed by the hard segment but a small crystal region (that is, a small number of crystals) is suitable.

  When the above-mentioned points are discussed from the soft segment, a thermoplastic elastomer having a large average molecular weight of the soft segment and a large ratio of the soft segment to the hard segment is preferable. Such a thermoplastic elastomer can be obtained by arbitrarily selecting from conventionally known crystalline thermoplastic elastomers.

The compression set of the thermoplastic elastomer of the present invention measured by a method according to JIS K6262 is 30% or more (for example, 32 to 100%), preferably 40% or more (for example, 42 to 100). %), More preferably 45% or more (for example, 47 to 100%), and most preferably 50% or more (for example, 55 to 100%).
Since the permanent compression strain of the thermoplastic elastomer is large, the permanent strain of the formed fine particles can be increased. And when it uses for the resin particle of this invention, it becomes suitable. A thermoplastic elastomer having a large permanent compression strain is preferably a thermoplastic elastomer having a large average molecular weight of the soft segment and a large ratio of the soft segment to the hard segment. Moreover, what is necessary is just to select such a thermoplastic elastomer. When the permanent compression strain is small, the properties as an elastomer are strong, and even when fine particles are used, the permanent compression strain cannot be secured.

  The resin particles need only have a particulate form, and are preferably in a form having a smooth surface (spherical or ellipsoidal shape), particularly spherical.

  By using the thermoplastic elastomer as described above, it is possible to obtain resin particles having a low volume elastic modulus of the fine particles by making them into fine particles by the forced emulsification method. The volume modulus of elasticity of the resin particles of the present invention is 20 MPa or less, for example, 0.5 to 18 MPa, preferably 1 to 15 MPa, and more preferably 1.5 to 13 MPa (for example, 2 to 12 MPa). The volume modulus of elasticity of the resin particles is based on the relationship between the load and the compression amount by compressing and molding the resin particles at a pressure of 60 MPa to form a tablet (thickness 3 mm × 25 mmφ) and compressing the tablet to shear deformation. Thus, it can be obtained by calculating the bulk modulus in the elastic deformation region.

  The number average particle diameter Dn of the resin particles is not particularly limited and can be selected from the range of about 0.05 to 100 μm depending on the application, and is 0.1 to 20 μm, preferably 0.3 to 15 μm (for example, 0.5 10 to 10 μm), more preferably about 1 to 10 μm (for example, 1.5 to 8 μm), and usually about 2 to 10 μm (for example, 2 to 6 μm).

  The resin particles of the present invention have a particle size distribution, for example, a distribution represented by a ratio Dw / Dn of the volume average particle size Dw and the number average particle size Dn of 2.0 or less (for example, 1-1. 9, preferably 1 to 1.8, more preferably 1 to 1.5, particularly about 1 to 1.3). Alternatively, when the CV value (value obtained by dividing the standard deviation of the measured particle diameter by the average particle diameter (in this case, the number average particle diameter) and multiplying it by 100) is used as the particle size distribution, the CV value is 60% or less (for example, 0 to 50%, preferably 0 to 40%, more preferably 0 to 25%, and most preferably 0 to 15%). The particle diameter of the resin particles can be obtained by measuring the particle diameter of about 200 to 300 particles based on a scanning electron micrograph. Alternatively, a known particle diameter measuring device or method such as a laser scattering method (solvent dispersion method, gas phase method, etc.) may be used.

  The spherical resin particles are not limited to a true spherical shape, and include, for example, a shape in which the length ratio between the major axis and the minor axis is, for example, major axis / minor axis = 1.5 / 1 to 1/1. It is. 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.

[Production method of resin particles]
In the method of the present invention, resin particles are produced without emulsion polymerization and suspension polymerization (a polymerization method involving polymerization of monomers) or phase inversion emulsification using an oily medium and an aqueous medium. That is, through a step of melt-kneading the water-soluble auxiliary agent capable of being melt-kneaded and the soft resin, and a step of eluting with a water-based solvent a dispersion in which the thermoplastic elastomer phase is dispersed by the aqueous solvent, Resin particles can be produced. The water-soluble auxiliary agent may be composed of the water-soluble polysaccharide (A1) alone, but is usually water-soluble polysaccharide (A1) and water-soluble for plasticizing the water-soluble polysaccharide (A1). It is often composed of a plasticizing component (A2).

[Water-soluble polysaccharide (A1)]
The water-soluble polysaccharide (A1) can be composed of at least one selected from oligosaccharides and polysaccharides having at least one cyclic structure (water-soluble polysaccharide having a cyclic structure), and may be used in combination. . When the oligosaccharide and the polysaccharide having a cyclic structure are combined, the melt viscosity can be adjusted, and the particle diameter of the resin particles can be widely controlled by combining with the resin.

[oligosaccharide]
Oligosaccharides are roughly classified into homo-oligosaccharides and hetero-oligosaccharides, and 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. Oligosaccharides include disaccharides to decasaccharides.
Examples of the disaccharide include homo-oligosaccharides such as trehalose, maltose, isomaltose, and cellobiose; and hetero-oligosaccharides such as lactose, sucrose, and palatinose.

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 may be an oligosaccharide composition produced by degradation of a polysaccharide. Examples of the oligosaccharide composition include starch sugar (starch saccharified product), galacto-oligosaccharide, coupling sugar, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, chitin oligosaccharide, chitosan oligosaccharide and the like. It can be used alone or in combination of two or more. For example, the starch sugar may be a mixture of oligosaccharides having a plurality of glucose bound thereto. 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.
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, about 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, about 90 to 100% by weight). Good.

The oligosaccharide may be a non-reducing type (trehalose type), but a reducing type (maltose type) oligosaccharide is preferred because of its excellent heat resistance. The reduced oligosaccharide is not particularly limited as long as it is a sugar (such as a disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, or hexasaccharide) that has a free aldehyde group or a ketone group and exhibits reducibility.
In addition, depending on the type of oligosaccharide (for example, starch sugar such as reduced starch saccharified product), it does not show a melting point or a 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.

The temperature difference between the melting point or softening point of the oligosaccharide and the heat distortion temperature of the resin component is, for example, 1 ° C. or higher (for example, about 1 to 80 ° C.), preferably 10 ° C. or higher (for example, about 10 to 70 ° C.). More preferably, it is 15 ° C. or higher (for example, about 15 to 60 ° C.). The melting point or softening point of the oligosaccharide can be selected in the range of 70 to 300 ° C. depending on the type of the resin component, for example, 90 to 290 ° C., preferably 100 to 280 ° C. (for example, 110 to 270 ° C.), More preferably, it may be about 120 to 260 ° C (for example, 130 to 260 ° C).
The water-soluble auxiliary agent (or water-soluble medium) may be composed of oligosaccharides, but in order to increase the melt viscosity, a polysaccharide having a cyclic structure (water-soluble polysaccharide) is used alone or in combination with oligosaccharides. It is advantageous to do so.

[Cyclic polysaccharide]
In a water-soluble polysaccharide having a cyclic structure (sometimes simply referred to as a cyclic polysaccharide), the cyclic structure (cyclic skeleton, cyclic unit, cyclic portion) is composed of a plurality of glycolose units [usually glucose units (particularly, D-glucose)] may be a ring formed by a glucoside bond (or glucosylation). That is, in this specification, the cyclic structure means a ring formed of a plurality of glycolose units (and glucoside bonds), and does not mean a monosaccharide ring such as a glucose ring.
Such a cyclic polysaccharide has a relatively high molecular weight and a high melt viscosity as compared with an oligosaccharide and the like, and also exhibits water solubility because of its cyclic structure. When a cyclic polysaccharide is used, a high shear viscosity can be maintained in melt-kneading, so melt-kneading can be performed without impairing melt-kneading properties, and water-soluble, so that it can be easily removed with water or the like.
In the polysaccharide, the cyclic structure may be composed of a plurality of glucoside bonds, may be composed of α-glucoside bonds or β-glucoside bonds, and may be generally composed of α-glucoside bonds. Good.

The average degree of polymerization of the cyclic structure (per one cyclic structure) (number average degree of polymerization, average number of glucoside bonds forming the cyclic structure, average degree of polymerization of the glycose unit forming the cyclic structure) is, for example, 10 or more (for example, 10 or more), preferably 12 or more (for example, about 12 to 300), more preferably 14 or more (for example, about 14 to 100).
Further, the glucoside bond constituting the cyclic structure is usually a ring formed of at least 1,4-glucoside bond (particularly α-1,4-glucoside bond), and 1,4-glucoside bond (particularly, , Α-1,4-glucoside bond) and 1,6-glucoside bond (particularly α-1,6-glucoside bond).

In such a ring containing 1,6-glucoside bond, the average number of 1,6-glucoside bonds in the cyclic structure (per one cyclic structure) may be 1 or more (for example, about 1 to 700), For example, it may be 1 to 300 (for example, 1 to 200), preferably 1 to 100 (for example, 1 to 50), more preferably 1 to 20 (for example, 1 to 10).
Moreover, the cyclic polysaccharide should just have at least 1 cyclic structure (cyclic unit), and may have a some cyclic structure.
The average degree of polymerization of the cyclic polysaccharide (number average degree of polymerization, total average degree of polymerization, average degree of polymerization of the whole polysaccharide) is, for example, 14 or more (for example, 14 to 15000), preferably 17 or more (for example, 17 -10000), more preferably 20 or more (for example, 20-8000).

The cyclic polysaccharide may be derivatized (or modified). For example, a cyclic polysaccharide has a hydroxyl group (alcoholic hydroxyl group) derivatized [eg, etherification (eg, alkyl etherification such as methyl etherification; hydroxyalkyl etherification such as hydroxyethyl etherification, hydroxypropyl etherification, etc.) Glycerylated, esterified, grafted, cross-linked, etc.] derivatives.
These cyclic polysaccharides may be used alone or in combination of two or more.
The water-soluble polysaccharide having a typical cyclic structure has (1) a cyclic structure (or a cyclic unit) and an acyclic structure (acyclic skeleton, acyclic unit acyclic part) bonded to the cyclic structure. And a polysaccharide having an average degree of polymerization of 50 or more, and (2) a polysaccharide having one cyclic structure formed of 14 or more α-1,4-glucoside bonds in the molecule.

(Cyclic polysaccharide (1))
In the polysaccharide (1), the cyclic structure may be a ring formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond. Further, the average degree of polymerization (number average degree of polymerization) of the cyclic structure (per one cyclic structure) may be, for example, about 10 to 500, preferably about 12 to 300, and more preferably about 14 to 100. When the cyclic structure has an α-1,6-glucoside bond, the average number of α-1,6-glucoside bonds in the cyclic structure (per one cyclic structure) is, for example, 1 or more (for example, 1 to 200), Preferably it may be about 1-100, more preferably about 1-50.
In addition, the average degree of polymerization (number average degree of polymerization) of polysaccharide (1) should just be 50 or more, for example, 50-10000, Preferably it is about 60-7000, More preferably, about 70-5000 may be sufficient. .

The polysaccharide (1) may have one or a plurality of acyclic structures, and usually has a plurality of (for example, about 2 to 1000, preferably about 3 to 500) acyclic structures. Also good. The average degree of polymerization (number average degree of polymerization) per such acyclic part (or part other than the cyclic structure of the polysaccharide (1)) is, for example, 10 or more (for example, about 10 to 30), preferably About 10-20 may be sufficient.
Moreover, the average degree of polymerization (number average degree of polymerization) of the whole non-cyclic part should just be 10 or more, for example, 40 or more (for example, about 50-5000), Preferably about 100-3000 may be sufficient. In particular, the acyclic moiety is often branched from an α-1,6-glucoside-bonded glycose (particularly glucose) unit.

In the polysaccharide (1), the hydroxyl group (alcoholic hydroxyl group) may be derivatized (for example, etherified, esterified, grafted, etc.).
Such a polysaccharide (1) includes a so-called “cluster dextrin”. Such polysaccharides (1) are synthesized by, for example, saccharides (for example, starch, partially decomposed starch, amylopectin, glycogen, waxy starch, high amylose starch, soluble starch, dextrin, starch hydrolyzate, and phosphorylase). It may be obtained by reacting an enzyme (branching enzyme, D enzyme, cyclodextrin glucanotransferase, etc.) capable of forming a cyclic structure by acting on a saccharide with at least one substrate selected from amylopectin. . JP-A-8-134104 and the like can be referred to for details of such cluster dextrins BR> X and a method for producing the same.

(Cyclic polysaccharide (2))
In the polysaccharide (2), the cyclic structure may be a ring formed of at least an α-1,4-glucoside bond, and includes an α-1,4-glucoside bond and an α-1,6-glucoside bond. It may be a ring formed. In the polysaccharide (2), the average degree of polymerization (number average degree of polymerization) of the cyclic structure may be 14 or more, for example, 14 to 5000, preferably 15 or more (for example, about 15 to 3000), It may be 17 or more (for example, about 17 to 1000). When the cyclic structure has an α-1,6-glucoside bond, the average number of α-1,6-glucoside bonds in the cyclic structure is, for example, 1 to 500, preferably 1 to 300, more preferably about 1 to 100. It may be.
The polysaccharide (2) may have an acyclic structure (for example, a linear structure) as long as it has the cyclic structure, but is usually composed (or formed) of only the cyclic structure. It may be a cyclic polysaccharide.
In the polysaccharide (2), the hydroxyl group (alcoholic hydroxyl group) may be derivatized (for example, etherified, esterified, grafted, crosslinked).

  Such a polysaccharide (2) includes a so-called “cycloamylose (or cycloamylose)” polysaccharide. Such a polysaccharide (2) is, for example, linear α-1,4-glucan or a saccharide containing this glucan (for example, maltooligosaccharide, amylose, amylopectin, glycogen, starch, waxy starch, high amylose starch, An enzyme capable of forming a polysaccharide (2) with soluble starch, dextrin, starch debranch, partially hydrolyzed starch, amylose synthesized with morpholylase, and at least one selected from derivatives thereof (for example, D enzyme etc.) can be obtained by reacting in the presence of phosphorylase and glucose 1-phosphate, if necessary. In the reaction, when a substrate having an α-1,6-glucoside bond is used as a substrate, an enzyme capable of cleaving the α-1,6-glucoside bond (for example, isoamylase, pullulanase, etc.) is present. You may go on. JP-A-8-311103 and the like can be referred to for details on such cycloamylose and its production method.

  These polysaccharides may be used alone or in combination of two or more. For example, the polysaccharide (1) and the polysaccharide (2) can be used in combination, and in particular, at least the cyclic polysaccharide (1) (or cluster dextrin) can be preferably used.

  The ratio between the cyclic polysaccharide and the oligosaccharide is, for example, the former / the latter (weight ratio) = 99/1 to 5/95, preferably 95/5 to 10/90, more preferably 90/10 to 20/80. (E.g., 85/15 to 25/75), particularly 80/20 to 30/70 (e.g., 70/30 to 40/60), and usually about 99/1 to 50/50. Also good.

  The viscosity of a 50% by weight aqueous solution of the water-soluble polysaccharide (A1) is, for example, about 5 Pa · sec or less (eg, 1 to 5 Pa · sec), preferably (eg, 2 to 4 Pa · sec) at a temperature of 25 ° C. is there. Thus, since aqueous solution viscosity is low, when water-soluble polysaccharide (A1) is used, the elution efficiency by water can be improved combined with the high solubility with respect to water.

[Water-soluble plasticizing component (A2)]
The water-soluble plasticizing component is not particularly limited as long as it is a component that plasticizes the polysaccharide (that is, develops a phenomenon in which an oligosaccharide is hydrated to form a chickenpox state), and examples thereof include sugars and sugar alcohols. Can be used. These plasticizing components can be used alone or in combination of two or more.

(a) Sugar
As sugars, monosaccharides and / or disaccharides are usually used. In addition, although disaccharides are classified into oligosaccharides, when combined with oligosaccharides, they can be used as long as they are combined with oligosaccharides of trisaccharides or higher. 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, dialdoses, monosaccharides having a plurality of carbonyl groups, monosaccharides having a methyl group, monosaccharides having an acyl group, saccharides introduced with a carboxyl group, thiosaccharides, An amino sugar, a deoxy sugar, etc. may be sufficient.
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.
As the disaccharide, for example, among the disaccharides, disaccharides having a low melting point or a low softening point (for example, gentiobiose, melibiose, trehalose (dihydrate), etc.), equivalent to the monosaccharide homo and hetero disaccharides (For example, aldobiouronic acid such as glucuronoglucose in which glucuronic acid and glucose are α-1,6-glycosidically bonded).
Since saccharides are excellent in thermal stability, reducing sugars are preferable. Examples of such saccharides include free monosaccharides as well as disaccharides having a low melting point or a low softening point (for example, gentiobiose, melibiose). Etc.).

(b) Sugar alcohol The sugar alcohol may be a chain sugar alcohol such as alditol (glycitol) or a cyclic sugar alcohol such as inosit. Usually, a chain sugar alcohol is used. . These sugar alcohols can be used alone or in combination of two or more.
Examples of chain sugar alcohols include tetritol (threitol, erythritol, etc.), pentitol [pentaerythritol, arabitol, ribitol (adonitol), xylitol, lyxitol, etc.], hexitol [sorbitol, mannitol, iditol, glitol, tallitol, dulcitol (g Lactitol), 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 melting point of the water-soluble plasticizing component (A2) is usually 140 ° C. or lower (for example, 50 to 135 ° C., preferably 70 to 130 ° C., more preferably about 80 to 125 ° C.).
In the water-soluble auxiliary agent or the water-soluble medium, the ratio (weight ratio) between the polysaccharide (A1) and the plasticizing component (A2) is not particularly limited as long as the polysaccharide can be efficiently plasticized. , (A1) / (A2) = 99/1 to 50/50, preferably 90/10 to 60/40 (for example, 85/15 to 65/35), and more preferably 80/20 to 65/35 (for example, 80/20 to 70/30), and usually about 85/15 to 75/25.

When the water-soluble plasticizing component and the oligosaccharide are used in combination, the ratio between the oligosaccharide and the water-soluble plasticizing component is, for example, the former / the latter (weight ratio) = 99/1 to 60/40, preferably 90. / 10 to 65/35, more preferably about 80/20 to 70/30.
Further, when the cyclic polysaccharide and the oligosaccharide are used in combination, the ratio between the total amount of the polysaccharide and the oligosaccharide and the water-soluble plasticizing component is, for example, the former / the latter (weight ratio) = 99/1 to 50/50, Preferably, it may be about 90/10 to 55/45, more preferably about 85/15 to 60/40 (for example, 80/20 to 65/35).

A water-soluble auxiliary agent is used for obtaining a dispersion in which a thermoplastic elastomer is molded and dispersed in a particulate form in a medium (matrix) of a water-soluble auxiliary agent or a resin particle by kneading in combination with a resin. Useful as an aid. Therefore, the present invention also includes a melt moldable composition (or melt moldable composition) containing the water-soluble auxiliary agent and a meltable thermoplastic elastomer. Further, it is composed of a matrix (meltable medium) composed of the water-soluble auxiliary agent and a dispersed phase (particulate dispersed phase) composed of a thermoplastic elastomer dispersed in the matrix and meltable. Including dispersions.
The ratio (weight ratio) between the water-soluble auxiliary agent and the thermoplastic elastomer is water-soluble auxiliary agent / thermoplastic elastomer = 99/1 to 45/55, preferably 95/5 to 50/50, more preferably 90/10. About 55/45 may be sufficient.

[Modifier]
In the present invention, the kneading system (or dispersion) may further contain a modifier (or additive) as necessary. Examples of the modifier (or additive) include components capable of modifying the resin, such as a plasticizer (or softener), a filler (such as a granular filler), and a photodegradability imparting agent (such as anatase-type titanium oxide). ), Lubricants [higher fatty acids or derivatives thereof (fatty acid salts, fatty acid esters, fatty acid amides, alkylene bis (saturated fatty acid amides), etc.), waxes such as olefinic waxes, hydrocarbon oils or mineral oils, silicone oils (polydimethylsiloxanes) (Or polydialkylsiloxanes such as dimethyl silicone oil), polyalkylaryl siloxanes such as polymethylphenylsiloxane, etc.], stabilizers (thermal stabilizers, antioxidants, UV absorbers, weathering (light) stabilizers, processing Stabilizers), UV scattering agents (titanium oxide, zirconium oxide, zinc oxide, iron oxide, etc.) Oxide powders), dispersants, flame retardants, antistatic agents (anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents and other low molecular weight antistatic agents, polymers Type antistatic agents), colorants [eg dyes or pigments [oil-soluble dyes (solvent dyes, etc.), disperse dyes, vat dyes, sulfur dyes, azoic dyes (naphthol dyes), inorganic pigments (white pigments such as titanium dioxide] Extender pigments such as calcium carbonate; black pigments such as carbon black; red pigments such as cadmium red; yellow pigments such as cadmium yellow; blue pigments such as ultramarine blue; ferromagnetic metal powders such as nickel and ferrite), organic pigments ( Azo pigment, phthalocyanine pigment, isoindolinone pigment, perinone / perylene pigment, selenium pigment, dioxazine Materials, anthraquinone pigments, indigo or thioindigo pigments, diketopyrrolopyrrole pigments, benzimidazolone compounds, fluorescent pigments or dyes, phosphorescent pigments, etc.], charge control agents (nigrosine dyes, triphenylmethane dyes, 4 Positive charge control agents such as 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.), mold release Agent, brightener, wettability improver, fluidizing agent, crosslinking agent [polymerizable compound, curing agent, polymerization initiator (eg, organic peroxide, azo compound, etc.), photopolymerization initiator, etc.], antibacterial agent, Preservatives, compounds having reactive groups [for example, compounds having an epoxy group, compounds having an acid group (for example, Examples thereof include compounds having a ruboxyl group, compounds having a sulfonic acid group, compounds having an acid anhydride group such as maleic anhydride, and the like. The kneading system (or dispersion) may contain these modifiers alone or in combination of two or more.

The total amount of the additive can be selected, for example, from the range of about 0 to 100 parts by weight with respect to 100 parts by weight of the resin, for example, 0.01 to 50 parts by weight (for example, 0.03 to 30 parts by weight), preferably May be about 0.05 to 20 parts by weight (for example, 0.1 to 20 parts by weight), more preferably about 0.2 to 10 parts by weight (for example, 0.5 to 10 parts by weight).
Note that the modifier (additive) may be present in the kneading system, and may be contained in either the dispersed phase (thermoplastic elastomer phase) or the matrix (continuous phase) of the dispersion. In particular, a dispersion having a dispersed phase composed of a resin and a modifier can be efficiently obtained by mixing (in particular, melt-mixing or melt-kneading) a resin containing a modifier and a water-soluble auxiliary agent in advance. And it can be obtained reliably.

The dispersion can be usually prepared by kneading a melt-moldable composition (a composition that may contain a water-soluble auxiliary agent, a resin, and, if necessary, a modifier). The melt kneading temperature T ₀ is, for example, about 100 to 300 ° C., and is usually about 170 to 230 ° C. (for example, 180 to 220 ° C.). The kneading time can be selected from a range of 10 seconds to 1 hour, for example. Kneading can be performed using a conventional kneader (for example, a screw extruder, a kneader, a calender roll, etc.). Prior to kneading, each component may be premixed with a Henschel mixer, a tumble mixer, a ball mill, or the like. The kneaded composition may be preliminarily molded by, for example, extrusion molding, injection molding, calendar molding, or the like. The shape of the preform (or dispersion) is not particularly limited, and may be granular, pellet, strand, rod, plate, sheet, film, tubular, block or the like.

  By cooling the melt obtained by kneading and / or molding (for example, kneaded product, preformed product), a dispersed phase can be formed due to differences in solidification rate such as surface tension and crystallization. It can also be obtained. The cooling temperature is a heat distortion temperature of the resin, or a temperature that is at least about 10 ° C. lower than the melting point or softening point of the water-soluble auxiliary agent (for example, a temperature that is about 10 to 100 ° C., preferably about 15 to 80 ° C., The temperature may be preferably about 20 to 60 ° C.). Specifically, the cooling temperature can be selected from about 10 to 120 ° C., for example, and may be about 15 to 60 ° C. (for example, 20 to 50 ° C.). The cooling time can be selected from a wide range of 30 seconds to 20 hours.

When the water-soluble auxiliary agent is eluted from the dispersion thus obtained, a particulate molded body composed of the resin can be produced. In particular, since the water-soluble auxiliary agent has high solubility in water, the water-soluble auxiliary agent can be quickly eluted or extracted, and the resin particles can be obtained efficiently.
Elution (or washing) of a water-soluble auxiliary agent (water-soluble auxiliary agent) is carried out using an aqueous solvent such as water, a water-soluble solvent (eg, alcohols (ethanol, isopropanol, etc.), ethers (cellosolve, etc.)), etc. Can be used. These aqueous solvents can be used alone or in combination of two or more. It is preferable to use water as the eluting solvent.

  Elution of the water-soluble auxiliary agent is performed by a conventional method, for example, the dispersion (or preform) is immersed and dispersed in the aqueous medium, and the water-soluble auxiliary agent is eluted or washed (transferred to an aqueous solvent). Can be done to In addition, in order to accelerate | stimulate dispersion | distribution and elution of a water-soluble auxiliary agent, you may stir. The water-soluble auxiliary agent 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 water-soluble auxiliary agent is usually a temperature below the melting point or softening point of the resin component, for example, about 10 to 100 ° C., 25 to 80 ° C. (for example, 40 to 80 ° C.). The molded body composed of the resin can be recovered using a conventional separation (recovery) method such as filtration or centrifugation.

  The crystalline resin particles of the present invention can be suitably used for printed circuit board members, various spacers, and cosmetic applications. It can also be added to various thermosetting resins (such as epoxies), photo-curing resins (such as acrylic or urethane), or varnish, and used as a mechanical strength modifier.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the following materials were used.

[Matrix component]
(A1-1) Water-soluble polysaccharide Oligosaccharide Starch sugar (manufactured by Towa Kasei Kogyo Co., Ltd., reduced starch saccharified product PO-10, 50% aqueous solution viscosity 0.55 Pa · sec)
(A1-2) Water-soluble polysaccharide Polysaccharide having a cyclic structure (manufactured by Nippon Shokuhin Kako Co., Ltd., cluster dextrin)
(A2) Water-soluble plasticizing component Sugar alcohol sorbitol (manufactured by Towa Kasei Kogyo Co., Ltd., sorbit, melting point 103 ° C.).

[Crystalline thermoplastic elastomer]
(B1) Polyamide elastomer: VESTAMELT ™ E62,
Made by Daicel Degussa Co., Ltd.
Flexural modulus (JIS K7171) 370 MPa,
Melting point (DSC) 173 ° C.,
Compression set (JIS K6262, 70 ° C) 48%

(B2) Polyamide elastomer: VESTAMELT ™ E47,
Made by Daicel Degussa Co., Ltd.
Flexural modulus (JIS K7171) 120 MPa,
Melting point (DSC) 158 ° C.,
Compression set (JIS K6262, 70 ° C) 48%

(B3) Polyester elastomer: Perprene S ™ 1002
Toyobo Co., Ltd.
Flexural modulus (JIS K7171) 125 MPa,
Melting point (DSC) 200 ° C.,
Compression set (JIS K6262, 70 ° C) 60%

(B4) Polyester polyether elastomer: Perprene P (trademark) 150B,
Toyobo Co., Ltd.
Flexural modulus (JIS K7171) 289 MPa,
Melting point (DSC) 212 ° C.,
Compression set (JIS K6262, 70 ° C) 60%

(B5) Polyester polyether elastomer: Perprene P (trademark) 150M,
Toyobo Co., Ltd.
Flexural modulus (JIS K7171) 118 MPa,
Melting point (DSC) 170 ° C.,
Compression set (JIS K6262, 70 ° C) 60%

(B6) Polyester polyether elastomer: Perprene P ™ 40H,
Toyobo Co., Ltd.
Flexural modulus (JIS K7171) 51 MPa,
Melting point (DSC) 172 ° C.,
Compression set (JIS K6262, 70 ° C) 50%

(B7) Polyester polyether elastomer: Perprene P ™ 70B
Toyobo Co., Ltd.
Flexural modulus (JIS K7171) 108 MPa,
Melting point (DSC) 200 ° C.,
Compression set (JIS K6262, 70 ° C) 55%

[Measurement method of melting point of resin]
After the DSC (thermal scanning calorimeter; heat flux type) Seiko Electronics Co., Ltd. 1200R type measuring device was used to raise the temperature at a rate of temperature increase of 20 ° C./min and hold at 260 ° C. for 1 minute. The temperature was lowered at 20 ° C./min, held at −50 ° C. for 1 minute, then measured at 20 ° C./min to 260 ° C., and the peak top temperature of the observed endothermic peak at the second temperature rise was determined by the melting point of the resin component. It was.

[Method for measuring bulk modulus of particles]
The resin particles are compression-molded at a pressure of 60 MPa to form a tablet (thickness 3 mm × 25 mmφ). The tablet is subjected to a compression test with a universal tensile tester at a compression speed of 1 mm / min. The volume elastic modulus (MPa) is defined by the gradient of the load and deformation amount (compression amount) in the elastic deformation region.

混練物を取り出し後、冷却し、１０倍（重量）の純水に浸漬することにより、マトリックス成分を溶解した。生成した粒子分散水溶液を、孔径０．４５μｍの酢酸セルロース製メンブレンフィルターにてろ過し、メンブレンフィルターにより回収された粒子を、再度１０倍量の純水に分散させ、３０分程度攪拌下で洗浄後、再びろ過した。このような洗浄操作は二回繰り返した。２回洗浄した試料を４５℃のオーブン中で一昼夜乾燥させ、微粒子を得た。
得られた樹脂粒子の走査型電子顕微鏡（高倍率ＦＥ−ＳＥＭ）写真をデジタル画像化し、２００〜３００個の粒子について粒子径を測定し、数（個数）平均粒子径（Ｄｎ）、体積平均粒子径（Ｄｗ）、粒子径分布（Ｄｗ／Ｄｎ）及び、ＣＶ値（粒子径の標準偏差／数平均粒子径×１００）を計算式により算出した。
結果を表２に示す。さらに、熱可塑性エラストマー樹脂粒子の体積弾性率は、樹脂粒子を圧力６０ＭＰａで圧縮成形してタブレット（厚み３ｍｍ×２５ｍｍφ）を成型し、このタブレットを圧縮速度１ｍｍ／分で圧縮してせん断変形させ、荷重と圧縮量との関係に基づいて弾性変形領域での体積弾性率を算出した。なお、圧縮試験の測定データのサンプリングレート（データの取り込み速度）は１μｍで測定した。結果を表２に示す。

Examples 1-7
Using a lab plast mill, a matrix component and a thermoplastic elastomer composed at the ratio shown in Table 1 are mixed at the ratio shown in Table 1, and kneaded at the temperature, time, and rotation speed shown in Table 1. Got.

The kneaded product was taken out, cooled, and immersed in 10 times (by weight) pure water to dissolve the matrix component. The generated aqueous dispersion of particles is filtered through a cellulose acetate membrane filter having a pore size of 0.45 μm, and the particles recovered by the membrane filter are dispersed again in 10 times the amount of pure water and washed with stirring for about 30 minutes. And filtered again. Such a washing operation was repeated twice. The sample washed twice was dried overnight in a 45 ° C. oven to obtain fine particles.
A scanning electron microscope (high-magnification FE-SEM) photograph of the obtained resin particles is converted into a digital image, the particle diameter is measured for 200 to 300 particles, and the number (number) average particle diameter (Dn) and volume average particle are measured. The diameter (Dw), the particle diameter distribution (Dw / Dn), and the CV value (standard deviation of particle diameter / number average particle diameter × 100) were calculated by a calculation formula.
The results are shown in Table 2. Furthermore, the volume modulus of elasticity of the thermoplastic elastomer resin particles is such that the resin particles are compression-molded at a pressure of 60 MPa to form a tablet (thickness 3 mm × 25 mmφ), and this tablet is compressed at a compression speed of 1 mm / min to be subjected to shear deformation. Based on the relationship between the load and the compression amount, the bulk modulus in the elastic deformation region was calculated. Note that the measurement rate of the measurement data of the compression test was measured at 1 μm. The results are shown in Table 2.

表２から明らかな通り、本発明の樹脂粒子はＤw／Ｄnが小さく、ＣＶ値も小さい。それでありながら、粒子の体積弾性率も小さい。また実施例１２と実施例１３との対比から明らかな通り環状構造を有する多糖類を水溶性助剤として用いた場合には粒子の粒径の分布が小さくなりＤw／Ｄnが小さく、ＣＶ値も小さくなる。 Examples 8-13
It was carried out in the same manner as in Example 1 except that a continuous kneader (KRC S-1 Kneader manufactured by Kurimoto Steel Works) was used as a kneading method instead of a lab plast mill. The mixing ratio of each component and the operating conditions of the continuous kneader (kneader barrel temperature, paddle rotation speed, raw material feed speed) are shown in Table 3, and the evaluation results of the obtained resin particles are shown in Table 1, respectively.

As is apparent from Table 2, the resin particles of the present invention have a small Dw / Dn and a small CV value. Nevertheless, the bulk modulus of the particles is also small. As is clear from the comparison between Example 12 and Example 13, when a polysaccharide having a cyclic structure is used as a water-soluble auxiliary agent, the particle size distribution of the particles becomes small, Dw / Dn is small, and the CV value is also low. Get smaller.

Claims (5)

The resin particle which consists of a thermoplastic elastomer which satisfy | fills all the conditions shown below, Comprising: The resin particle whose volume elastic modulus of the resin particle measured by the following volume elastic modulus measuring method is 20 Mpa or less.
B) The flexural modulus obtained by a method according to JIS K7171 is 500 MPa or less.
B) The compression set measured at 70 ° C. obtained by a method according to JIS K6262 is 30% or more.
C) Melting point (Tm) measured by DSC method is 150 ° C. or higher.
[Method for measuring bulk modulus of particles]
The resin particles are compression-molded at a pressure of 60 MPa to form a tablet (thickness 3 mm × 25 mmφ). The tablet is subjected to a compression test with a universal tensile tester at a compression speed of 1 mm / min. The volume elastic modulus (MPa) is defined by the gradient of the load and deformation amount (compression amount) in the elastic deformation region. The resin particles according to claim 1, wherein the number average particle diameter Dn is 0.1 to 20 µm, and the ratio Dw / Dn of the volume average particle diameter Dw to the number average particle diameter Dn is 2.0 or less. The resin particle according to claim 1, wherein the resin particle is composed of a crystalline polyester elastomer or a crystalline polyamide elastomer. A melt-kneaded water-soluble auxiliary agent composed of at least the water-soluble polysaccharide (A1) and a crystalline thermoplastic elastomer are melt-kneaded to produce a dispersion in which the crystalline thermoplastic elastomer is dispersed. A method for producing a crystalline thermoplastic elastomer having a bulk modulus of 20 MPa or less by eluting the dispersion with an aqueous solvent. The method according to claim 4, wherein the water-soluble polysaccharide (A1) is composed of at least one selected from oligosaccharides and polysaccharides having at least one cyclic structure.