Resin particles and use thereof

Abstract

The present invention addresses the problem of providing polyhydroxyalkanoate resin pellets in which undesirable odor is suppressed. As a solution, the following (i)-(iii) are provided: i) a polyhydroxyalkanoate resin pellet in which the total residual amount of unsaturated fatty acids is 10 ppm by mass or less; (ii) polyhydroxyalkanoate resin particles in which the total residual amount of crotonic acid is 10 ppm by mass or less; and (iii) polyhydroxyalkanoate resin particles in which the total residual amount of pentenoic acid is 60 mass ppm or less.

Description

Technical Field

[0001] The present invention relates to resin particles and uses thereof, and more particularly to resin particles, external preparations containing the resin particles, coating materials containing the resin particles, resin compositions containing the resin particles, and anti-blocking agents containing the resin particles. Background Art

[0002] Resin particles can arbitrarily adjust the specific surface area / particle shape / particle structure, so they are modified and their physical properties are improved by compounding them into various materials / articles. The main uses of resin particles include cosmetic compounding agents such as foundation, antiperspirant, and exfoliant; various preparations such as matting agents, rheology modifiers, anti-blocking agents, smoothness imparting agents, light diffusers, and medical diagnostic test agents for coating materials (paints); and additives in molded products such as automotive materials and building materials. Examples of resin particles include urethane, acrylic, silicone, and polyethylene.

[0003] On the other hand, in recent years, attention to environmental issues has been increasing. In order to reduce environmental burdens such as microplastics, all fields using resins are seeking to use materials derived from non-petroleum raw materials and biodegradable materials. For example, this is also required in fields using resin particles such as cosmetics and coating materials (paints).

[0004] In this context, various biodegradable resin particles are known.

[0005] Patent Document 1 describes cellulose acetate particles having an average particle size of 80 nm to 100 μm, a sphericity of 0.7 to 1.0, a surface smoothness of 80% to 100%, and a total degree of acetyl substitution of cellulose acetate of 0.7 to 2.9. Patent Document 1 also describes that the cellulose acetate particles have excellent biodegradability and texture and can be used by being mixed in a cosmetic composition.

[0006] Patent Document 2 describes a kind of aliphatic polyester resin particles, wherein the volume average particle size is 2 to 30 μm, the proportion of particles with a particle size of less than 1 μm is 15% by volume or less, and the proportion of particles with a particle size of more than 30 μm is 6% by volume or less. It also describes that: cosmetics containing the aliphatic polyester resin particles are environmentally friendly, and have excellent spreadability, skin adhesion, touch (no foreign body feeling and astringency, softness, sliding property, smoothness) and transparency when applied.

[0007] Patent Document 3 describes polyhydroxyalkanoate particles obtained by pulverizing aggregates of primary particles. The polyhydroxyalkanoate particles can be used as a matting agent or delustering agent for a coating composition, and can be used to produce a coating that reduces the proportion of petrochemical substances and is better than or comparable to conventional coatings containing matting agents based on petrochemical raw materials.

[0008] Patent Document 4 describes a biodegradable resin particle comprising polyhydroxyalkanoate, wherein the particle contains 10 to 10,000 ppm of calcium, has a volume average particle size of 2 to 50 μm, and has a BET specific surface area of ​​0.8 to 10 m 2 / g, and the linseed oil absorption is 50 to 300 ml / 100 g. The biodegradable resin particles have a small particle size, and when applied to the skin, they have excellent adhesion to the skin and light ductility on the skin, and can be mixed with external preparations such as cosmetics and quasi-medical products and used appropriately.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent No. 6609726

[0012] Patent Document 2: International Publication No. 2017 / 195642

[0013] Patent Document 3: Japanese Patent No. 5671631

[0014] Patent Document 4: International Publication No. 2020 / 262509 Summary of the invention

[0015] Problem that the invention aims to solve

[0016] Cellulose acetate particles have a strong astringent feel and have problems with touch when blended into cosmetics. They also have problems with odor caused by components generated by hydrolysis and are not satisfactory in terms of biodegradability in water.

[0017] The aliphatic polyester resin particles of Patent Document 2 and the biodegradable resin particles containing polyhydroxyalkanoate of Patent Documents 3 and 4 have not been studied in terms of heat resistance and odor of the resin particles, and biodegradability of the resin particles in water. Furthermore, the polyhydroxyalkanoate particles of Patent Document 3 are obtained by pulverization using a jet mill, so the particle shape is unstable, and when mixed with cosmetics, the texture during application is not satisfactory.

[0018] The first problem to be solved by the present invention is to provide polyhydroxyalkanoate resin particles with suppressed odor.

[0019] The second problem to be solved by the present invention is to provide polyhydroxyalkanoate resin particles having suppressed odor, excellent biodegradability in water, and little astringency.

[0020] The third problem to be solved by the present invention is to provide polyhydroxyalkanoate resin particles which have suppressed odor, excellent biodegradability in water, little astringency, and excellent dispersibility in external preparations.

[0021] A fourth problem to be solved by the present invention is to provide one or more of an external preparation containing the polyhydroxyalkanoate resin particles, a coating material containing the polyhydroxyalkanoate resin particles, a resin composition containing the polyhydroxyalkanoate resin particles, and an anti-blocking agent containing the polyhydroxyalkanoate resin particles.

[0022] Solutions for solving problems

[0023] The present inventors have conducted intensive studies to solve the above-mentioned problems and, as a result, have found that the above-mentioned problems can be solved by specific polyhydroxyalkanoate resin particles, thereby completing the present invention.

[0024] The invention for solving the first problem in the present invention is the invention described in the following Items 1 to 4.

[0025] The invention for solving the second problem in the present invention is the invention described in the following Item 5.

[0026] The invention for solving the third problem in the present invention is the invention described in the following Item 6.

[0027] The invention for solving the fourth problem in the present invention is the invention described in the following Items 7 to 10.

[0028] [Item 1] A polyhydroxyalkanoate resin particle, wherein the total amount of residual unsaturated fatty acids is 10 ppm by mass or less.

[0029] [Item 2] A polyhydroxyalkanoate resin particle, wherein the total residual amount of crotonic acid is 10 mass ppm or less.

[0030] [Item 3] A polyhydroxyalkanoate resin particle, wherein the total residual amount of pentenoic acid is 60 ppm by mass or less.

[0031] [Item 4] The polyhydroxyalkanoate resin particles according to any one of Items 1 to 3, wherein the polyhydroxyalkanoate resin comprises a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin.

[0032] [Item 5] The polyhydroxyalkanoate resin particles according to any one of Items 1 to 4, wherein the volume average particle size is 1 μm or more and 40 μm or less.

[0033] [Item 6] The polyhydroxyalkanoate resin particles according to any one of Items 1 to 5, wherein the water content is 0.2% by mass or more and 0.8% by mass or less.

[0034] [Item 7] An external preparation comprising the polyhydroxyalkanoate resin particles according to any one of Items 1 to 6.

[0035] [Item 8] A coating material comprising the polyhydroxyalkanoate resin particles according to any one of Items 1 to 6.

[0036] [Item 9] A resin composition comprising the polyhydroxyalkanoate resin particles according to any one of Items 1 to 6.

[0037] [Item 10] An anti-blocking agent comprising the polyhydroxyalkanoate resin particles according to any one of Items 1 to 6.

[0038] Effects of the Invention

[0039] The present invention can provide polyhydroxyalkanoate resin particles having a total residual amount of unsaturated fatty acids within a specific range, polyhydroxyalkanoate resin particles having a total residual amount of crotonic acid within a specific range, and polyhydroxyalkanoate resin particles having a total residual amount of pentenoic acid within a specific range, and can provide polyhydroxyalkanoate resin particles with suppressed odor.

[0040] The present invention can provide polyhydroxyalkanoate resin particles having a total residual amount of unsaturated fatty acids and a volume average particle size within specific ranges, and can provide polyhydroxyalkanoate resin particles having suppressed odor, excellent biodegradability in water, and less astringent feeling.

[0041] The present invention can provide polyhydroxyalkanoate resin particles having a total residual amount of unsaturated fatty acids, a volume average particle size and a moisture content within specific ranges, and can provide polyhydroxyalkanoate resin particles having suppressed odor, excellent biodegradability in water, less astringency, and excellent dispersibility in external preparations.

[0042] The present invention can provide an external preparation containing specific polyhydroxyalkanoate resin particles, a coating material containing specific polyhydroxyalkanoate resin particles, a resin composition containing specific polyhydroxyalkanoate resin particles, and an anti-blocking agent containing specific polyhydroxyalkanoate resin particles. DETAILED DESCRIPTION

[0043] Hereinafter, the resin particles of the present invention, the external preparation containing the resin particles, the coating material containing the resin particles, the resin composition containing the resin particles, and the anti-blocking agent containing the resin particles will be described in detail.

[0044] In addition, in this specification, the numerical range can be set as a range consisting of arbitrary combinations of the upper limit value and the lower limit value described.

[0045] [Polyhydroxyalkanoate resin particles]

[0046] In the present invention, the polyhydroxyalkanoate resin particles refer to resin particles that are substantially composed of a polyhydroxyalkanoate resin, and the resin particles may contain other components.

[0047] The resin particles may contain one type of polyhydroxyalkanoate resin alone, or may contain two or more types of polyhydroxyalkanoate resins.

[0048] Examples of other components include various components used when producing the resin pellets and various components added to improve the properties of the resin pellets.

[0049] <Polyhydroxyalkanoate resin>

[0050] The polyhydroxyalkanoate resin constituting the polyhydroxyalkanoate resin particles of the present invention is a biodegradable resin containing repeating units derived from an aliphatic hydroxycarboxylic acid, and may be a homopolymer or a copolymer.

[0051] Examples of the aliphatic hydroxycarboxylic acid include 3-hydroxypropionate, 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, 3-hydroxydodecanoate, 3-hydroxytetradecanoate, 3-hydroxyhexadecanoate, 3-hydroxyoctadecanoate, lactic acid, 4-hydroxybutyrate, 4-hydroxyvalerate, 5-hydroxyvalerate, and 6-hydroxyhexanoate.

[0052] The polyhydroxyalkanoate resin is preferably a poly(3-hydroxyalkanoate) polymer or copolymer containing a repeating unit represented by the general formula (1).

[0053] -[-CH(R)-CH 2 CO-O-]-(1)

[0054] (Wherein, R in formula (1) is -C n H 2n+1 The alkyl group represented by n is an integer of 1 to 15.

[0055] In the present invention, as a polyhydroxyalkanoate resin, 3-hydroxybutyrate units are preferably used as the main component (for example, 50 mol% or more, preferably 80 mol% or more). For example, it is preferred to use one or more selected from the group consisting of a copolymer of a 3-hydroxybutyrate unit and a 3-hydroxyvalerate unit, i.e., a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin, a copolymer of a 3-hydroxybutyrate unit and a 3-hydroxyhexanoate unit, i.e., a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) resin, and a copolymer of a 3-hydroxybutyrate unit and a 3-hydroxyoctanoate unit, i.e., a poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) resin as the main component, and the main component is more preferably a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin.

[0056] As a polyhydroxyalkanoate resin, by using a resin having a 3-hydroxybutyrate unit as the main component (for example, 50 mol% or more, preferably 80 mol% or more), such as a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin, a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) resin, a poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) resin, preferably a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin as the main component, the resin has excellent biodegradability, especially biodegradability in water, and can cope with the microplastic problem that has become a problem in recent years. By having a specific color value, it is easier to integrate the color tone and is less conspicuous than ordinary white particles, especially when it is made into a smoothness-imparting agent for foundation of cosmetics or an admixture for antiperspirants.

[0057] <Total residual amount of unsaturated fatty acids, crotonic acid or valerenoic acid>

[0058] In the polyhydroxyalkanoate resin particles according to one embodiment of the present invention, the total residual amount of unsaturated fatty acids is 10 mass ppm or less, preferably 8 mass ppm or less, more preferably 6 mass ppm or less, and further preferably 5 mass ppm or less, based on the entire polyhydroxyalkanoate resin particles.

[0059] In the polyhydroxyalkanoate resin particles according to one embodiment of the present invention, the total residual amount of crotonic acid is 10 mass ppm or less, preferably 8 mass ppm or less, more preferably 6 mass ppm or less, and further preferably 5 mass ppm or less, based on the entire polyhydroxyalkanoate resin particles.

[0060] In the polyhydroxyalkanoate resin particles according to one embodiment of the present invention, the total residual amount of pentenoic acid is 60 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 5 mass ppm or less, relative to the entire polyhydroxyalkanoate resin particles.

[0061] Polyhydroxyalkanoate resin is partially decomposed by heat, etc., to generate unsaturated fatty acids. For example, by decomposition, crotonic acid, etc. are generated by 3-hydroxybutyrate units in polyhydroxyalkanoate resin, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, etc. are generated by 3-hydroxyvalerate units, 2-hexenoic acid, etc. are generated by 3-hydroxycaproate units, and unsaturated fatty acids such as 2-octenoic acid are generated by 3-hydroxyoctanoate units, and are included in polyhydroxyalkanoate resin particles. These unsaturated fatty acids can give off a unique peculiar smell, and therefore, when polyhydroxyalkanoate resin particles are compounded into external preparations, etc., it is possible to cause a problem of peculiar smell to external preparations, etc.

[0062] The total residual amount of unsaturated fatty acids is measured by the method described in Examples below.

[0063] <Volume Average Particle Size>

[0064] The volume average particle size of the polyhydroxyalkanoate resin particles of the present invention is not particularly limited. For example, it is 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 6 μm or more, for example, 40 μm or less, preferably 33 μm or less, more preferably 30 μm or less, and particularly preferably 25 μm or less. When the volume average particle size is less than 1 μm, astringency is likely to occur in an external preparation containing polyhydroxyalkanoate resin particles. In addition, the feel when applying an external preparation containing polyhydroxyalkanoate resin particles (the feel when applied to the skin) may deteriorate. When the volume average particle size exceeds 40 μm, the feel when applying an external preparation containing polyhydroxyalkanoate resin particles (the feel when applied to the skin) may deteriorate.

[0065] The volume average particle size is measured by the method described in Examples below.

[0066] <Moisture content>

[0067] The water content of the polyhydroxyalkanoate resin particles of the present invention is not particularly limited. For example, it is 0.2% by mass or more, preferably 0.3% by mass or more, for example, 0.8% by mass or less, preferably 0.7% by mass or less. When the water content is less than 0.2% by mass or exceeds 0.8% by mass, when the polyhydroxyalkanoate resin particles are added to the external preparation, they may not be uniformly dispersed in the external preparation.

[0068] Here, the moisture content of the polyhydroxyalkanoate resin particles means the water content in the polyhydroxyalkanoate resin particles when the polyhydroxyalkanoate resin particles are taken as 100% by mass.

[0069] The water content can be measured by, for example, the method described in Examples below.

[0070] <Average circularity>

[0071] The average circularity of the polyhydroxyalkanoate resin particles of the present invention is not particularly limited. For example, it is 0.75 or more, preferably 0.78 or more, more preferably 0.8 or more, for example, 1.0 or less, preferably 0.99 or less. By setting the average circularity to 0.8 or more, it is possible to achieve an excellent touch when applying an external preparation containing polyhydroxyalkanoate resin particles.

[0072] The average circularity is measured by the method described in Examples below.

[0073] <Color Tone>

[0074] The color tone of the polyhydroxyalkanoate resin particles of the present invention is not particularly limited.

[0075] L * a * b * L in the color system * The value is, for example, 70 or more, preferably 75 or more, and more preferably 80 or more.

[0076] L * a * b * a in the color system * The value is, for example, -3.0 or more, preferably -2.5 or more, more preferably -2.0 or more, and is, for example, +2.0 or less, preferably +1.5 or less, more preferably +1.0 or less.

[0077] L * a * b * b in the color system * The value is, for example, +1.0 or more, preferably +1.5 or more, more preferably +2.0 or more, and is, for example, +7.0 or less, preferably +6.5 or less, more preferably +6.0 or less.

[0078] The preferred one is: * a * b * In the color system, L * Value is 70 or above, a * -3.0 or more and +2.0 or less, b * The value is +1.0 or more and +7.0 or less, and more preferably: * a * b * In the color system, L * Value is 80 or above, a *The value is -2.0 or more and +1.0 or less, b * The value is greater than +2.0 and less than +6.0.

[0079] L * a * b * Color system (L * a * b * The color space was standardized by the International Commission on Illumination (CIE) in 1976 and is the color system adopted in JIS Z 8781-4 in Japan. * a * b * The colorimetric system is a colorimetric system commonly used to represent the color of an object.

[0080] In L * a * b * In the color system, L * The value is an indicator of the brightness of the color. * Values ​​closer to 100 make the color lighter (white), and values ​​closer to 0 make the color darker (black).

[0081] In L * a * b * In the color system, a * The value is an indicator of the intensity relative to the hue of red and green. * Values ​​closer to the + direction represent a red hue, and values ​​closer to the - direction represent a green hue.

[0082] In L * a * b * In the color system, b * The value is an index that indicates the intensity relative to the hue of yellow and blue. * Values ​​closer to the + direction indicate a yellow hue, and values ​​closer to the - direction indicate a blue hue.

[0083] L * a * b * L in the color system * value, a * Value and b * When polyhydroxyalkanoate resin particles having specific color values ​​and having values ​​in the above-mentioned specific ranges are used as a blending agent for external preparations (cosmetics) such as a smoothness-imparting agent for foundation and a blending agent for antiperspirants, it is easier to integrate color tones than conventional white particles. In addition, polyhydroxyalkanoate resin particles are less conspicuous and can achieve natural makeup, so they are preferred.

[0084] <Other ingredients>

[0085] The polyhydroxyalkanoate resin particles of the present invention may contain a fluidity regulator, an ultraviolet absorber, a light stabilizer, a pigment (e.g., an extender pigment, a coloring pigment, a metal pigment, a mica powder pigment, etc.), a dye, a moisturizer, a surfactant, a resin other than the polyhydroxyalkanoate resin, a fragrance, a clay mineral, a preservative / bactericide, an anti-inflammatory agent, an antioxidant, an ultraviolet absorber, a pH regulator (e.g., triethanolamine), a special compounding additive, a pharmaceutical active ingredient, etc., as required.

[0086] <Purpose>

[0087] The polyhydroxyalkanoate resin particles of the present invention can be used in various preparations including various cosmetics such as foundations, antiperspirants, and exfoliants, compounding agents for coating materials, compounding agents for resin compositions, anti-blocking agents, matting agents for coating materials (paints), rheology modifiers, smoothness imparting agents, light diffusing agents, fine ceramic sintering molding aids, fillers for adhesives, medical diagnostic test agents, and additives in molded products such as automotive materials and building materials.

[0088] <Method for producing polyhydroxyalkanoate resin particles>

[0089] The method for producing the polyhydroxyalkanoate resin particles of the present invention is not particularly limited. For example, the following methods may be mentioned:

[0090] (I) A production method (production method I), comprising the steps of mixing and kneading a molten polyhydroxyalkanoate resin with an aqueous emulsifier solution to obtain a slurry of the polyhydroxyalkanoate resin, washing and dehydrating the slurry, drying a filter cake of the obtained polyhydroxyalkanoate resin particles, and then crushing the slurry;

[0091] (II) A manufacturing method (manufacturing method II), comprising the steps of emulsifying / dispersing a polyhydroxyalkanoate resin by heating in the presence of an organic solvent including an alcohol solvent, water and a dispersion stabilizer, cooling to obtain a dispersion of the polyhydroxyalkanoate resin, separating polyhydroxyalkanoate resin particles from the dispersion, and drying.

[0092] <Manufacturing method I>

[0093] As the production method I for producing the polyhydroxyalkanoate resin particles of the present invention, there can be exemplified, for example, a production method including the steps (I-1) to (I-4) shown below.

[0094] (I-1) a step of mixing / kneading a polyhydroxyalkanoate resin raw material powder or polyhydroxyalkanoate resin raw material pellets with an emulsifier aqueous solution by using a disperser, thereby mixing / kneading a molten polyhydroxyalkanoate resin with an emulsifier aqueous solution to obtain a polyhydroxyalkanoate resin slurry (kneading / slurrying step);

[0095] (I-2) a step of washing / dehydrating the polyhydroxyalkanoate resin slurry (washing / dehydration step);

[0096] (I-3) A step of drying the cake of the polyhydroxyalkanoate resin particles obtained in the above (I-2), disintegrating the cake, and classifying the cake as necessary to obtain polyhydroxyalkanoate resin particles (granulation step).

[0097] In the polyhydroxyalkanoate resin particles obtained by the steps (I-1) to (I-3), at least one of the total residual amount of unsaturated fatty acids such as crotonic acid, hexenoic acid, and pentenoic acid as decomposition products, the total residual amount of crotonic acid, and the total residual amount of pentenoic acid is reduced. Thus, the odor of the polyhydroxyalkanoate resin particles can be suppressed.

[0098] (Mixing / slurrying process)

[0099] {Emulsifier aqueous solution}

[0100] The aqueous emulsifier solution used in the kneading / slurrying step is not particularly limited as long as it contains at least an emulsifier and water as components and can emulsify the polyhydroxyalkanoate resin in a molten state to form a slurry.

[0101] The emulsifier constituting the emulsifier aqueous solution is not particularly limited. Examples thereof include anionic surfactants including fatty acid salts having 4 to 18 carbon atoms such as sodium lauryl sulfate and sodium oleate; cationic surfactants such as lauryl trimethylammonium chloride; zwitterionic surfactants such as N-laurylglycine; and nonionic surfactants such as nonylphenyl polyethylene oxide, glycerol fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, lecithin, and alkylene oxide adducts thereof. In addition, examples include natural polymers such as starch, casein, gelatin, alginic acid, alginates, locust bean gum, guar gum, gum arabic, xanthan gum, agar, carrageenan, crystalline cellulose, and pectin; semi-synthetic polymers such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, propylene glycol alginate, and cationic modified starch; polyvinyl alcohol resins, polyacrylamide, polyvinyl pyrrolidone, polyacrylic acid, polyethyleneimine, anionic or cationic modified products thereof, hydrophobic modified products thereof, poly(meth)acrylic acid, polyvinyl pyrrolidone, polyvinylamine, polymaleic acid (anhydride), polystyrene sulfonic acid, copolymers of (meth)acrylic acid or maleic anhydride and vinyl monomers (e.g., (meth)acrylates, aromatic vinyl monomers (styrene, etc.), olefin monomers, etc.), modified polyesters (modified products based on succinic anhydride, maleic anhydride, polyethylene oxide, etc.), polyoxyethylene polymers, and the like. One or more of the group consisting of water-soluble polymers.

[0102] In the present invention, considering the situation where the emulsifier remains, etc., a biodegradable emulsifier is preferred, and for example, at least one selected from the group consisting of polyvinyl alcohol resins (polyvinyl alcohol, partially saponified polyvinyl alcohol, partially saponified polyvinyl alcohol containing functional groups (such as sulfonic acid groups, carboxyl groups, amino groups, etc.), partially saponified polyvinyl alcohol containing terminal hydrophobic groups, etc.), starch, modified polyester (modified products based on succinic anhydride, maleic anhydride, polyethylene oxide, etc.), and polyoxyethylene polymers. Polyvinyl alcohol resins are particularly preferred.

[0103] {Disperser}

[0104] As a disperser, as long as the polyhydroxyalkanoate resin raw material powder or polyhydroxyalkanoate resin raw material pellet can be made into a molten state, the shear force required for granulating the polyhydroxyalkanoate resin in the molten state can be applied, there is no particular limitation. For example, a dispersant selected from the group consisting of various extruders, homogenizers, homogenizers, colloid mills, kneading extruders (KNEADER-RUDER), high-performance dispersers, high-viscosity liquid stirrers, etc. can be listed. Preferably, a screw extruder, more preferably a twin-screw co-extruder, a single screw extruder.

[0105] There is no particular limitation on the method of mixing / kneading the polyhydroxyalkanoate resin raw material powder or polyhydroxyalkanoate resin raw material pellets with the emulsifier aqueous solution using a dispersing means. For example, the following methods may be mentioned:

[0106] (i) A method of adding an aqueous emulsifier solution to a molten polyhydroxyalkanoate resin under stirring;

[0107] (ii) A method in which a polyhydroxyalkanoate resin raw material powder or polyhydroxyalkanoate resin raw material pellets and an aqueous emulsifier solution are added together and mixed / kneaded.

[0108] When an extruder is used, the above-mentioned method (i) is preferred.

[0109] In the above method (i), when a screw extruder such as a twin-screw co-rotating extruder is used, it is preferred that: a polyhydroxyalkanoate resin raw material powder or polyhydroxyalkanoate resin raw material pellets are continuously supplied from the hopper portion of the extruder, and an emulsifier aqueous solution is continuously pressed into the supply port provided at any position of the extruder except the resin melting time, and mixed and kneaded. Supply ports for the emulsifier aqueous solution can be provided at multiple locations as needed. Thus, the polyhydroxyalkanoate resin can be melted, mixed and kneaded with the emulsifier aqueous solution, and the polyhydroxyalkanoate resin slurry can be continuously manufactured.

[0110] (Washing / dehydration process)

[0111] The washing / dehydration process includes adding water to the polyhydroxyalkanoate resin slurry obtained by the aforementioned mixing / slurrying process and then performing a dehydration process, which can be performed more than once. Through the washing / dehydration process, the polyhydroxyalkanoate resin in the polyhydroxyalkanoate resin slurry is washed, and a filter cake of polyhydroxyalkanoate resin particles can be obtained by performing a dehydration process. For example, a centrifugal dehydrator or a pressurized dehydrator can be used for the dehydration process. In the washing / dehydration process, the amount of water added, the number of washing / dehydration processes, the dehydration conditions, etc. are not particularly limited and can be appropriately set.

[0112] (Pelletization process)

[0113] The granulation step includes drying the cake of the polyhydroxyalkanoate resin particles obtained in the washing / dehydration step, and then crushing and, if necessary, classifying the cake, thereby obtaining polyhydroxyalkanoate resin particles.

[0114] The drying conditions and the disintegration conditions are not particularly limited and can be appropriately set.

[0115] The broken polyhydroxyalkanoate resin particles can be classified as needed. As the classification method, wind classification, airflow classification, screen classification, etc. can be listed. In order to prevent the polyhydroxyalkanoate resin particles from absorbing moisture in the air, the classification is preferably carried out in an air atmosphere with a relative humidity of 30% or less, preferably 20% or less.

[0116] In order to prevent the polyhydroxyalkanoate resin particles from absorbing moisture in the air, it is preferred that they be sealed with a packaging material that is not easily permeable to moisture and stored as a packaged article.

[0117] <Manufacturing method II>

[0118] As the production method II for producing the polyhydroxyalkanoate resin particles of the present invention, for example, there can be exemplified a production method including the steps (II-1) to (II-4) shown below.

[0119] (II-1) a step of emulsifying / dispersing a polyhydroxyalkanoate resin by heating and stirring in the presence of an organic solvent including at least one alcohol solvent, water, and a dispersion stabilizer, for example, at a temperature of 110° C. to 180° C. to obtain a dispersion of the polyhydroxyalkanoate resin (emulsification / dispersion step)

[0120] (II-2) Thereafter, a step of cooling to obtain a dispersion of polyhydroxyalkanoate resin particles having a surface coated with a dispersion stabilizer (cooling / granulation step)

[0121] (II-3) A step of removing the coated dispersion stabilizer as necessary to obtain a polyhydroxyalkanoate resin particle dispersion from which the dispersion stabilizer on the surface has been removed (dispersion stabilizer removal step)

[0122] (II-4) A step of filtering / washing / dehydrating / drying the polyhydroxyalkanoate resin particle dispersion obtained by the above (II-2) or (II-3), and classifying as needed to obtain polyhydroxyalkanoate resin particles (granulation step)

[0123] In the polyhydroxyalkanoate resin particles obtained by the steps (II-1) to (II-4), at least one of the total residual amount of unsaturated fatty acids such as crotonic acid, hexenoic acid, and pentenoic acid as decomposition products, the total residual amount of crotonic acid, and the total residual amount of pentenoic acid is reduced, and further, the content of organic solvents is reduced. Thus, the odor of the polyhydroxyalkanoate resin particles can be suppressed.

[0124] (Emulsification / dispersion process)

[0125] {Organic solvents including alcoholic solvents}

[0126] In the method II for producing polyhydroxyalkanoate resin particles of the present invention, the alcohol solvent contained in the organic solvent used in the emulsification / dispersion step is not particularly limited. For example, one or more selected from the group consisting of methanol, ethanol, propanol, hexanol, ethylene glycol, diethylene glycol, 3-alkoxy-3-methyl-1-butanol and 3-alkoxy-3-methyl-1-butyl acetate (wherein the number of carbon atoms of the alkoxy group is 1 to 5) can be cited.

[0127] In the present invention, 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate (hereinafter also referred to as a specific solvent) are preferably contained. From the viewpoint of oil absorption characteristics and particle formation, the proportion of the specific solvent in the organic solvent is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. Examples of solvents other than the specific solvent that may be contained in the organic solvent include lower alcohols such as methanol and ethanol; and acetate-based solvents such as ethyl acetate and butyl acetate.

[0128] As a specific solvent, a solvent marketed by Kuraray under the trade name of SOLFIT can also be used. In addition, 3-alkoxy-3-methyl-1-butanol can be manufactured by a known method (for example, a method described in International Publication No. 2013 / 146370). The number of carbon atoms of the alkoxy group in the specific solvent is independently 1 to 5. When the number of carbon atoms of the alkoxy group is greater than 5, the solubility sometimes deteriorates. As specific examples of alkoxy groups, methoxy, ethoxy, propoxy, butoxy, and pentoxy groups can be listed. Propoxy, butoxy, and pentoxy groups include not only straight-chain ones, but also isomers that can be obtained. Alkoxy groups are preferably methoxy, ethoxy, and propoxy groups.

[0129] 3-Alkoxy-3-methyl-1-butanol and 3-alkoxy-3-methyl-1-butyl acetate (wherein the number of carbon atoms of the alkoxy group is 1 to 5) are highly safe alcohol solvents. By using these solvents, spherical polyhydroxyalkanoate resin particles with controlled volume average particle size, narrow particle size distribution and excellent color tone can be produced.

[0130] In addition, 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate are biodegradable and have low skin irritation, so it is possible to suppress adverse effects caused by residues when used in applications such as cosmetics. In particular, they are useful as solvents when wet-forming polyhydroxyalkanoate resins into particles.

[0131] Moreover, 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate dissolve or plasticize the polyhydroxyalkanoate resin at a high temperature of, for example, 110° C. or higher, but do not dissolve the polyhydroxyalkanoate resin at room temperature (25° C.), so the alcohol solvent can be easily reused, which is industrially advantageous. Furthermore, by using 3-alkoxy-3-methyl-1-butanol and 3-alkoxy-3-methyl-1-butyl acetate (wherein the number of carbon atoms of the alkoxy group is 1 to 5) as an alcohol solvent, the oil absorption property of the polyhydroxyalkanoate resin particles can be improved.

[0132] {Dispersion stabilizer}

[0133] In the method for producing polyhydroxyalkanoate resin particles of the present invention, the dispersion stabilizer used in the emulsification / dispersion process is not particularly limited. As long as the polyhydroxyalkanoate resin is emulsified / dispersed by heating / stirring in the presence of at least one alcohol solvent and water, for example, heating / stirring at 110°C or more and 180°C or less, it functions as a dispersion stabilizer. For example, the surface can be treated with a silane coupling agent, a non-animal surface treatment agent, etc. Among these, as a dispersion stabilizer, preferably a sparingly water-soluble inorganic compound particle.

[0134] The poorly water-soluble inorganic compound is a substance having a solubility in water of less than 2.0 g / L, preferably less than 1.0 g / L, more preferably less than 100 mg / L, and further preferably less than 50 mg / L. For example, one or more of the group consisting of calcium carbonate, barium carbonate, magnesium carbonate, silicon dioxide, aluminum oxide, titanium oxide, calcium sulfate, barium sulfate, magnesium sulfate, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate, and calcium metasilicate can be listed. Among these, carbonates are preferred from the viewpoint of being easily removed after use, and calcium carbonate is particularly preferred.

[0135] As a surface treatment agent for treating the surface of the poorly water-soluble inorganic compound, there is no particular limitation as long as it can impart hydrophobicity. Examples include oils selected from hydrocarbon oils, ester oils, lanolin, etc.; silicones such as dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc.; fluorine compounds such as esters containing perfluoroalkyl groups, perfluoroalkyl silanes, perfluoropolyethers, and polymers having perfluoroalkyl groups; silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane; titanium coupling agents such as isopropyl triisostearoyl titanate and isopropyl tri(dioctylpyrophosphate acyloxy) titanate; metal soaps; fatty acids; amino acids such as acylglutamic acid, lecithins such as hydrogenated egg yolk lecithin, etc., and one or more of the group consisting of the like.

[0136] In particular, calcium carbonate surface-treated with a silane coupling agent or a non-animal surface treatment agent is preferred because it has high compatibility with the polyhydroxyalkanoate resin, is excellent in dispersion stability, and can easily control the particle size of the polyhydroxyalkanoate resin particles.

[0137] The particle size of the sparingly water-soluble inorganic compound particles is not particularly limited, but preferably the primary particle size is small in order to increase the specific surface area. The average primary particle size of the sparingly water-soluble inorganic compound particles is, for example, 10 nm or more, for example, 1000 nm or less, preferably 500 nm or less, and more preferably 200 nm or less.

[0138] From the viewpoint of sufficient stirring and mixing and the viewpoint of productivity, the amount of the organic solvent used in the emulsification / dispersion step is, for example, 5 parts by mass or more, for example, 1200 parts by mass or less, preferably 800 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of the polyhydroxyalkanoate resin particles.

[0139] From the viewpoint of fully stirring and mixing and the viewpoint of productivity, the amount of the dispersion stabilizer used in the emulsification / dispersion process is, for example, 5% by mass or more, for example, 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less relative to the polyhydroxyalkanoate resin particles. In addition, various surfactants can also be used in combination on the basis of the dispersion stabilizer as a sparingly water-soluble inorganic compound. As the amount of surfactant added, for example, 0.01 to 0.5 parts by mass can be used relative to 100 parts by mass of water.

[0140] When the polyhydroxyalkanoate resin particles are heated and stirred, stirring can be performed by a liquid phase stirring method using a stirring blade, a mixing method using a homogenizer, a mixing method using ultrasonic irradiation, etc. The stirring speed and time are not particularly limited as long as the polyhydroxyalkanoate resin is uniformly dispersed in the solvent.

[0141] (Cooling / Pelletizing Process)

[0142] The cooling method of the polyhydroxyalkanoate resin dispersion is not particularly limited. In the present invention, it is preferred to slowly cool from the heating temperature to the cooling temperature, for example, the cooling rate is set to be 0.5°C / min or more and 5.0°C / min or less. In addition, cooling is preferably performed while stirring. The stirring rate can be set to the same range as the stirring rate during heating and stirring. The cooling temperature is not particularly limited, for example, it is 5°C or more and 45°C or less.

[0143] Thereby, a dispersion of polyhydroxyalkanoate-based resin particles whose surfaces are coated with a dispersion stabilizer (a sparingly water-soluble inorganic compound or the like) can be obtained.

[0144] (Dispersion stabilizer removal process / particle formation process)

[0145] The polyhydroxyalkanoate resin particle dispersion having the surface coated with the dispersion stabilizer (poorly water-soluble inorganic compound) obtained by cooling is separated from the solvent by filtration, washing, dehydration and drying, and classified as necessary to obtain the polyhydroxyalkanoate resin particles of the present invention.

[0146] In the case of obtaining polyhydroxyalkanoate resin particles whose surface is not covered with a dispersion stabilizer (poorly water-soluble inorganic compound), it is sufficient to add a step of removing the dispersion stabilizer (poorly water-soluble inorganic compound) using an acid that decomposes / dissolves the dispersion stabilizer (poorly water-soluble inorganic compound) before filtering. When the dispersion stabilizer is decomposed / dissolved, from the viewpoint of inhibiting the hydrolysis of the polyhydroxyalkanoate resin and preventing the reduction of the extension on the skin when added to the external preparation, it is preferred to add an acid in a range that does not become a strong acid, for example, 1.05 to 1.50 times the necessary molar number, more preferably 1.05 to 1.20 times the necessary molar number of the acid, stir at 40°C or below, and filter and wash within 24 hours, more preferably within 12 hours.

[0147] Thereafter, the polyhydroxyalkanoate resin particles of the present invention can be obtained by drying the mixture by a reduced pressure drying method or a spray drying method.

[0148] The dried polyhydroxyalkanoate resin particles can be classified as needed. As classification methods, wind classification, airflow classification, screen classification, etc. can be listed. In order to prevent the polyhydroxyalkanoate resin particles from absorbing moisture in the air, the classification is preferably carried out in an air atmosphere with a relative humidity of 30% or less, preferably 20% or less.

[0149] In order to prevent the polyhydroxyalkanoate resin particles from absorbing moisture in the air, it is preferred that they be sealed with a packaging material that is not easily permeable to moisture and stored as a packaged article.

[0150] [Topicals]

[0151] The external preparation of the present invention comprises the polyhydroxyalkanoate resin particles of the present invention. The type of external preparation is not particularly limited. For example, cosmetics such as scented powder, face powder (loose powder, pressed powder, etc.), foundation (powder foundation, liquid foundation, emulsified foundation, etc.), lipstick, lip balm, blush, eyebrow cosmetics, nail polish, etc. can be listed; cosmetics for cleaning such as soap, shower gel, facial cleanser, exfoliating facial cleanser, toothpaste, etc.; emulsion preparations such as pre-shave milk and body milk; external preparations for the body such as talcum powder and baby powder; skin care cosmetics such as lotion, vanishing cream, emulsion (cosmetic emulsion), etc.; sunscreen cosmetics, tanning products, antiperspirants (liquid antiperspirants, solid antiperspirants, cream antiperspirants, etc.), facial masks, shampoo cosmetics, hair dyes, haircuts, aromatic cosmetics, bath preparations, shaving creams, etc.

[0152] In particular, from the viewpoint of utilizing the low odor and water biodegradability characteristics of the polyhydroxyalkanoate resin particles, cosmetics are preferred, and color cosmetics, cleansing cosmetics, skin care cosmetics, and the like are more preferred.

[0153] When the external preparation of the present invention is a cosmetic, the content of the polyhydroxyalkanoate resin particles can be appropriately adjusted according to the type of cosmetic, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and from the viewpoint of making production cost, stability, and touch good, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less.

[0154] In the external preparation of the present invention, in the scope of not damaging the effect of the present invention, commonly used host or additive can be mixed as required. As this host or additive, for example, one or more of the group consisting of water, lower alcohol (alcohol with carbon number less than 5), grease and wax, hydrocarbon, higher fatty acid, higher alcohol, sterol, fatty acid ester, metal soap, wetting agent, surfactant, macromolecular compound, color material raw material, spices, clay minerals, antiseptic / bactericide, anti-inflammatory agent, antioxidant, ultraviolet light absorber, organic-inorganic composite particles, pH adjusting agent (trolamine etc.), special compounding additive, pharmaceutical active ingredient etc. can be listed.

[0155] Examples of the fats and oils and waxes include, for example, avocado oil, almond oil, olive oil, cocoa butter, beef tallow, sesame oil, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, peach kernel oil, castor oil, grape oil, macadamia oil, mink oil, egg yolk oil, wood wax, coconut oil, rosehip oil, hydrogenated oil, silicone oil, deep-sea fish oil, carnauba wax, candelilla wax, spermaceti, jojoba oil, montan wax, beeswax, lanolin, and the like.

[0156] Examples of the hydrocarbon include at least one selected from the group consisting of liquid paraffin, vaseline, paraffin, ceresin, microcrystalline wax, squalane, and the like.

[0157] Specific examples of higher fatty acids include one or more selected from fatty acids having 11 or more carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, hydroxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acids.

[0158] Specific examples of higher alcohols include at least one selected from the group consisting of alcohols having 6 or more carbon atoms, such as lauryl alcohol, cetyl alcohol, cetearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol, and decyltetradecyl alcohol.

[0159] Specific examples of sterol include one or more selected from the group consisting of cholesterol, dihydrocholesterol, and phytosterol.

[0160] Examples of the fatty acid ester include linoleic acid esters such as ethyl linoleate; lanolin fatty acid esters such as isopropyl lanolin fatty acid; lauric acid esters such as hexyl laurate; myristic acid esters such as isopropyl myristate, myristyl myristate, cetyl myristate, and octyldodecyl myristic acid; oleic acid esters such as decyl oleate and octyldodecyl oleate; dimethyloctanoate such as hexyldecyl dimethyloctanoate; isooctanoate such as cetyl isooctanoate (cetyl 2-ethylhexanoate); isononanoic acid; One or more of the group consisting of isononanoic acid esters such as ethylhexyl isononanoate, isononyl isononanoate, and isotridecyl isononanoate; palmitate esters such as isopropyl palmitate, ethylhexyl palmitate, and decyl palmitate; trimyristin, tri(caprylic acid / capric acid)glyceryl, propylene glycol dioleate, triisostearic acid glyceryl, triisooctanoin, cetyl lactate, myristyl lactate, diisostearate malate, cholesteryl isostearate, and 12-hydroxystearate cholesteryl fatty acid esters.

[0161] As oils such as fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, and fatty acid ester oils, non-volatile oils are preferred, and non-volatile oils having a viscosity of 550 mPa·s or less at 20°C are more preferred, non-volatile oils having a viscosity of 1 to 550 mPa·s are further preferred, and non-volatile oils having a viscosity of 5 to 550 mPa·s are particularly preferred. Such non-volatile oils are combined with the polyhydroxyalkanoate resin particles of the present invention to have good compatibility with oils, and the particles can be evenly coated, and effects such as a harmonious bright makeup after coating, excellent adhesion to the skin, light spreading on the skin, and excellent stability over time can be obtained. As the non-volatile oil having a viscosity of 550 mPa·s or less at 20°C, there can be cited one or more selected from the group consisting of liquid paraffin, squalane, olive oil, castor oil, jojoba oil, mink oil, macadamia oil, hexyl laurate, isopropyl myristate, octyldodecyl myristate, cetyl isooctanoate (cetyl 2-ethylhexanoate), ethylhexyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, ethylhexyl palmitate, decyl palmitate, tri(caprylic acid / capric acid)glyceryl, triisostearic acid glyceryl, triisooctanoic acid glyceryl, etc. From the viewpoint of showing the above-mentioned effect, the content of the above-mentioned non-volatile oil in the cosmetic of the present invention is preferably 1 to 20% by mass. The non-volatile oil in this specification refers to an oil that remains on the skin for at least several hours at room temperature (23°C) and atmospheric pressure and has a vapor pressure of less than 0.13 Pa (0.01 mmHg).

[0162] Examples of the metal soap include at least one selected from the group consisting of zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and zinc undecylenate.

[0163] Examples of the moisturizer include at least one selected from the group consisting of glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerol, xylitol, and maltitol.

[0164] Examples of the surfactant include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates, and phosphate salts; cationic surfactants such as amine salts and quaternary ammonium salts; amphoteric surfactants such as betaine type, amino acid type, imidazoline type, and lecithin; and nonionic surfactants such as fatty acid monoglycerides, polyethylene glycol, propylene glycol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerol fatty acid esters, and ethylene oxide condensates. At least one surfactant may be selected from the group consisting of the following.

[0165] Examples of the polymer compound include natural polymer compounds such as gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, Irish moss, quince seeds, gelatin, shellac, rosin, and casein; semi-synthetic polymer compounds such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, and crystalline cellulose; and one or more of the group consisting of synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon particles, poly(meth)acrylate particles (e.g., polymethyl methacrylate particles), polystyrene particles, silicone particles, urethane particles, polyethylene particles, and resin particles such as silica particles.

[0166] Examples of color material raw materials include inorganic pigments such as iron oxide (red iron oxide, yellow iron oxide, black iron oxide, etc.), ultramarine, iron blue pigment, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silicon dioxide, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, and ceramic powder; and one or more selected from the group consisting of tar pigments such as azo, nitro, nitroso, xanthene, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene.

[0167] Powdered raw materials such as resin particles and color material raw materials may also be used as those that have been pre-surface treated. As a surface treatment method, known surface treatment techniques may be used, and examples include treatments selected from the group consisting of oil treatments based on hydrocarbon oils, ester oils, lanolin, etc.; silicone treatments based on dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc.; fluorine compound treatments based on esters containing perfluoroalkyl groups, perfluoroalkyl silanes, perfluoropolyethers, and polymers having perfluoroalkyl groups; silane coupling agent treatments based on 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc.; titanium coupling agent treatments based on isopropyl triisostearoyl titanate, isopropyl tri(dioctylpyrophosphate acyloxy) titanate, etc.; metal soap treatments; amino acid treatments based on acylglutamic acid, etc.; lecithin treatments based on hydrogenated egg yolk lecithin, etc.; collagen treatments; polyethylene treatments; moisture retention treatments; inorganic compound treatments; mechanochemical treatments, etc.

[0168] Examples of the fragrance include one or more selected from the group consisting of anisaldehyde, benzyl acetate, geraniol, and the like.

[0169] Examples of clay minerals include components having multiple functions such as physical pigments and adsorbents, for example, one or more selected from the group consisting of talc, mica, sericite, titanium sericite (sericite covered with titanium oxide), muscovite, and VEEGUM (registered trademark) manufactured by VANDERBILT.

[0170] Examples of the antiseptic / bactericide include one or more selected from the group consisting of methyl paraben, ethyl paraben, propyl paraben, benzalkonium, benzylethonium, and the like.

[0171] Examples of the antioxidant include at least one selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, propyl gallate, and tocopherol.

[0172] As the ultraviolet absorber, for example, one or more selected from the group consisting of inorganic absorbers such as microparticle titanium oxide, microparticle zinc oxide, microparticle cerium oxide, microparticle iron oxide, and microparticle zirconium oxide; and organic absorbers such as benzoic acid-based, p-aminobenzoic acid-based, o-aminobenzoic acid-based, salicylic acid-based, cinnamic acid-based, benzophenone-based, and dibenzoylmethane-based.

[0173] Examples of the special compounding additives include hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, and prednisone; vitamins such as vitamin A, vitamin B, vitamin C, and vitamin E; skin astringent material preparations such as citric acid, tartaric acid, lactic acid, aluminum chloride, aluminum / potassium sulfate, aluminum closa, zinc p-phenolsulfonate, and zinc sulfate; hair promoters such as cantharides tincture, pepper tincture, root ginger tincture, Japanese swertia extract, garlic extract, cyperus rotundus, carpronium chloride, pentadecanoic acid glyceride, vitamin E, estrogen, and photosensitizers; and one or more whitening agents such as magnesium ascorbyl phosphate and kojic acid.

[0174] [Coating material]

[0175] The coating material of the present invention comprises the polyhydroxyalkanoate resin particles of the present invention. In the coating material of the present invention, in addition to the polyhydroxyalkanoate resin particles of the present invention, a binder resin, an ultraviolet curable resin, a solvent, etc. may be included as needed. As the binder resin, for example, a resin soluble in an organic solvent or water or an emulsion type resin dispersible in water may be used.

[0176] In the present invention, the binder resin is not particularly limited. For example, it can be selected from polyhydroxyalkanoate resins (e.g., polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, poly(succinic acid / ethylene terephthalate), poly(succinic acid / butylene terephthalate), poly(adipate / terephthalate), poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly Biodegradable resins such as poly(3-hydroxyoctanoate), poly(3-hydroxybutyrate / 3-hydroxyhexanoate), poly(3-hydroxybutyrate-3-hydroxyvalerate), poly(ε-caprolactone), poly(β-propiolactone), polyamide 4, starch resins, cellulose resins, and glucosamine resins; and one or more of the group consisting of acrylic resins, alkyd resins, polyamide resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0177] In the present invention, the UV curable resin includes polyfunctional (meth)acrylate resins such as polyol polyfunctional (meth)acrylates, and polyfunctional urethane acrylate resins synthesized from diisocyanates, polyols, and (meth)acrylates having a hydroxyl group, etc. Among them, polyfunctional (meth)acrylate resins are preferred, and polyol polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule are more preferred. Specific examples of the polyol multifunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule include at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.

[0178] When using an ultraviolet curable resin, it is preferred to use a photopolymerization initiator in combination. The photopolymerization initiator is not particularly limited. For example, one or more of the group consisting of acetophenone, benzoin, benzophenone, phosphine oxide, ketal, α-hydroxyalkyl phenone, α-aminoalkyl phenone, anthraquinone, thioxanthone, azo compounds, peroxides (described in Japanese Patent Laid-Open No. 2001-139663, etc.), 2,3-dialkyl diketone compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium, onium salts, borate salts, active halogen compounds, α-acyl oxime esters, etc. can be cited.

[0179] These binder resins or ultraviolet curable resins can be appropriately selected according to the adhesion of the coating material to the coating substrate, the use environment, and the like.

[0180] In the present invention, the content of each component also varies depending on the film thickness of the formed coating, the average particle size of the resin particle group and the coating method. When the total content of the binder resin (solid content when using an emulsion type water-based resin) and the resin particle group of the present invention is set to 100% by mass, the addition amount of the resin particle group of the present invention is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and further preferably 5 to 40% by mass.

[0181] In the present invention, the solvent is not particularly limited, and it is preferred to use a solvent that can dissolve or disperse the binder resin or the ultraviolet curable resin. For example, if it is an oil-based coating material (oil-based paint), hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether, etc., can be listed. If it is a water-based coating material (water-based paint), water, alcohols, etc. can be used. These solvents can be used alone or in combination of two or more. The solvent content in the coating material is usually about 20 to 60% by mass relative to the total amount of the coating material.

[0182] In order to adjust the viscosity of the coating material, one or more of these solvents may be used as a diluent as necessary.

[0183] In the present invention, the coating material may contain known coating surface conditioners, fluidity conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, dyes, etc. as necessary.

[0184] In the present invention, the method of forming a coating film using a coating material is not particularly limited, and any known method can be used. Examples include spray coating, roller coating, brush coating, inkjet, rod coating, and dipping. In addition, for coating on a substrate such as a thin film in a thin layer form, reverse roll coating, gravure coating, die coating, and comma coating can be listed.

[0185] Alternatively, a cross-linked coating film can be formed by applying the coating to an arbitrary coating surface such as a substrate to form a coating film, and then, if necessary, curing the coating film after drying the coating film.

[0186] The coating material is used to be applied to various substrates to form a coating film. The substrate is not particularly limited, and examples thereof include metal, wood, glass, ceramic, plastic, etc. In the present invention, the coating material can also be applied to transparent substrates such as polyethylene terephthalate (PET), polycarbonate (PC), acrylic resin, etc.

[0187] [Resin composition]

[0188] The resin composition of the present invention contains the polyhydroxyalkanoate resin particles of the present invention. The resin composition of the present invention contains a base resin in addition to the polyhydroxyalkanoate resin particles of the present invention.

[0189] In the present invention, the base resin is not particularly limited. Examples thereof include polyhydroxyalkanoate resins (e.g., polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, poly(succinic acid / ethylene terephthalate), poly(succinic acid / butylene terephthalate), poly(adipate / terephthalate), poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3-hydroxyoctanoate), poly(3-hydroxybutyrate / 3-hydroxyhexanoate), poly(3-hydroxybutyrate / 3-hydroxyvalerate), etc.), poly(ε-caprolactone), poly(β-propiolactone), polyamide 4, starch resins, cellulose resins, glucosamine resins, etc. Biodegradable resin; thermoplastic resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 66, polyamide 12, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), AS resin (acrylonitrile-styrene copolymer resin), polyethylene, polypropylene, polyacetal, polyamide-imide, polyethersulfone, polyimide, polyphenylene ether, polyphenylene sulfide, polystyrene, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, polyvinyl chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer (ETFE resin), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA resin), polyether ketone; and one or more of the group consisting of thermosetting resins such as epoxy resins and urethane resins.

[0190] In the present invention, the content of the polyhydroxyalkanoate resin particles of the present invention in the resin composition also varies depending on the thickness of the formed article, the average particle size of the polyhydroxyalkanoate resin particles and the molding method. When the total content of the base resin and the polyhydroxyalkanoate resin particles of the present invention is set to 100% by mass, the content of the polyhydroxyalkanoate resin particles of the present invention is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and further preferably 1 to 30% by mass.

[0191] In the present invention, the resin composition may contain known additives as required. Examples of the additives include reinforcing fibers such as glass fibers and carbon fibers; flame retardants, flow modifiers, ultraviolet absorbers, heat stabilizers, light stabilizers, lubricants, body pigments, coloring pigments, metallic pigments, dyes, and the like.

[0192] In the present invention, the method for producing the resin composition is not particularly limited, and the resin composition can be produced by mixing the resin particle group with the base resin using a conventionally known method such as a mechanical pulverization and mixing method. In the mechanical pulverization and mixing method, the resin particle group and the base resin are mixed and stirred using a device such as a Henschel mixer, a V-type mixer, a TURBULA agitator, a HYBRIDIZER, a rock mixer, etc., thereby producing the resin composition.

[0193] In the present invention, the method for forming a molded product using a resin composition is not particularly limited, and known methods can be used. For example, the resin particle group of the present invention is mixed with a base resin using a mixer, and a melt mixer such as an extruder is used to mix the pellets formed by the resin composition, and the pellets are molded by extrusion, injection, blow molding, etc., thereby obtaining a molded product of any shape suitable for automotive materials, building materials, packaging materials, etc.

[0194] [Anti-blocking agent]

[0195] The anti-blocking agent of the present invention comprises the polyhydroxyalkanoate resin particles of the present invention. The anti-blocking agent may contain, in addition to the polyhydroxyalkanoate resin particles of the present invention, a known antioxidant, a fluidity regulator, a light stabilizer, a coloring pigment, etc. as required.

[0196] The content of the polyhydroxyalkanoate resin particles of the present invention in the anti-blocking agent of the present invention is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

[0197] The anti-blocking agent of the present invention is used to prevent the surfaces of the resin films in contact from adhering to each other and not peeling off (blocking) when the resin film is rolled up, and to provide irregularities on the surface of the resin film.

[0198] In the present invention, the resin film that can use the anti-blocking agent is not particularly limited. For example, polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, poly(succinic acid / ethylene terephthalate), poly(succinic acid / butylene terephthalate), poly(adipate / butylene terephthalate), poly(ε-caprolactone), poly(β-propiolactone), polyamide 4, poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3-hydroxyoctanoate), poly(3-hydroxybutyrate / 3-hydroxyhexanoate), poly(3-hydroxypentanoate), poly(3-hydroxyheptanoate), poly(3-hydroxyoctanoate), poly(3-hydroxybutyrate / 3-hydroxyhexanoate), poly(3-hydroxybutyrate / 3-hydroxypentanoate), poly(3-hydroxypentanoate / 3-hydroxypent ... A film of one or more resins selected from the group consisting of biodegradable resins such as esters), starch resins, cellulose resins, and glucosamine resins; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyolefin resins such as polyethylene resin and polypropylene resin; (meth)acrylic resins; polystyrene resins; polyether sulfone resins; polyurethane resins; polycarbonate resins; polysulfone resins; polyether resins; polymethylpentene resins; polyether ketone resins; (meth)acrylonitrile resins; norbornene resins; amorphous polyolefin resins; polyamide resins; polyimide resins; and cellulose triacetate resins.

[0199] The content of the resin particles of the present invention in the resin film also varies depending on the thickness of the film to be formed, the average particle size of the resin particles, and the molding method. The content of the resin particles of the present invention in the resin film is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, further preferably 0.01 to 3% by mass, and particularly preferably 0.01 to 1% by mass.

[0200] Example

[0201] Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "%" means "mass %".

[0202] [Measurement method, etc.]

[0203] <Unsaturated fatty acid residue>

[0204] The quantitative analysis of the residual unsaturated fatty acid content was performed as follows.

[0205] (1) Pre-extraction treatment method

[0206] About 1 g of polyhydroxyalkanoate resin particles were accurately weighed and placed in a centrifugal tube, 5 mL of methanol was added and mixed, ultrasonic extraction was performed for 15 minutes, and the mixture was fully mixed again. Centrifugal separation was performed at 3,500 rpm for 30 minutes, and the supernatant was filtered using a non-aqueous 0.2 μm chromatographic disk 13N (manufactured by JL SCIENCE) to prepare a test solution, which was then measured by UHPLC.

[0207] (2) Measurement method

[0208] The conditions for the UHPLC determination of the above test solution are as follows. The standard peak area value obtained by chromatography using a standard solution is used to quantify the unsaturated fatty acids. In the quantification, a standard curve prepared by Shimadzu chromatograph workstation LabSolutions is used. The concentration of each unsaturated fatty acid in the test solution is determined based on the standard curve, and the content of each unsaturated fatty acid (unsaturated fatty acid residue) is calculated based on the obtained results.

[0209] Unsaturated fatty acid content (mg / kg) = measured value (μg / mL) × methanol extraction volume (mL) ÷ sample mass (g)

[0210] (3) UHPLC assay conditions

[0211] Unsaturated fatty acids

[0212] <uhplc>

[0213] Apparatus: "NexeraX2" manufactured by Shimadzu Corporation Ultra-high performance liquid chromatography Column: Kinetex 1.7μmC18 100A (2.1mmI.D.×50mmL)

[0214] Column temperature: 40°C

[0215] Pump temperature: room temperature (23°C)

[0216] Mobile phase: (A: 0.05% trifluoroacetic acid (TFA) / B: acetonitrile)

[0217] Mobile phase conditions: (0→0.5min=B conc. 90%, 0.5→0.51min=B conc. 90%→80%, 0.51→2min=B conc. 80%, 2→2.5min=B conc. 80%→20%, 2.5→3min=B conc. 20%, 3→3.5min=B conc. 20%→90%, 3.5→5min=B conc. 90%

[0218] Flow rate: 0.6mL / min

[0219] Measurement time: 5min

[0220] Injection volume: 1μL

[0221] Detector: PDA = 210nm (crotonic acid, 2-pentenoic acid), 200nm (4-pentenoic acid)

[0222] ·Standard solution preparation method

[0223] Using the automatic dilution function of the autosampler of the "NexeraX2" ultra-high performance liquid chromatograph manufactured by Shimadzu Corporation, the 1,000 mg / L standard solution was diluted 10 times with methanol to make a 100 mg / L standard solution, and the 50 mg / L standard solution was diluted 20 times with methanol. Furthermore, the 100 mg / L standard solution was diluted 5 times to make a 20 mg / L standard solution. The 50 mg / L standard solution was diluted 5 times to make a 10 mg / L standard solution. The 20 mg / L standard solution was diluted 5 times to make a 4 mg / L standard solution. The 10 mg / L standard solution was diluted 10 times to make a 1 mg / L standard solution. The 1 mg / L standard solution was diluted 5 times to make a 0.2 mg / L standard solution.

[0224] 4-pentenoic acid was also measured by the following method.

[0225] 4-Pentenoic acid

[0226] (1) Pre-extraction treatment method

[0227] About 1 g of polyhydroxyalkanoate resin particles were weighed, immersed in 10 mL of acetone, and subjected to ultrasonic extraction for 30 minutes. 1 mL of the extract (supernatant) was taken into a vial for measurement, 0.5 mL of bis(trimethylsilyl)trifluoroacetamide (BSTFA) was added and gently shaken, and the mixture was allowed to stand for more than 1 hour to be derivatized (trimethylsilylated), and then measured using a gas chromatography-mass spectrometer (GC-MS).

[0228] (2) Measurement method

[0229] The conditions for the GC-MS determination of the above-mentioned test solution are as follows. The standard peak area value obtained by chromatography using the standard solution is taken to perform quantification of unsaturated fatty acids. In quantification, a standard curve prepared by the standard solution is used. The concentration of each unsaturated fatty acid in the test solution is obtained according to the standard curve, and the content (unsaturated fatty acid residue) of each unsaturated fatty acid is calculated according to the obtained results.

[0230] 4-Pentenoic acid amount (μg / g) = 4-Pentenoic acid concentration of test solution (μg / mL) × extraction amount (mL) ÷ sample mass (g)

[0231] (3) GC-MS measurement conditions

[0232] Apparatus: Agilent Technologies 7890A GC / 5975C MSD system

[0233] Column: Agilent J&W DB-5ms, 30m×0.25mm i.d., membrane thickness 0.25μm

[0234] Inlet temperature: 250℃

[0235] Carrier gas: Helium 1ml / min

[0236] Split ratio: 10:1

[0237] Oven temperature: 50℃(1min)-10℃ / min-300℃(5min)

[0238] Injection volume: 1μL

[0239] Ionization method: Electron impact ionization method (EI method: 70eV)

[0240] Measurement mode: Selected ion monitoring (SIM) mode

[0241] Monitor ion: Quantitative ion m / z157 (4-pentenoic acid TMS)

[0242] ·Standard solution preparation method

[0243] 0.1 g of 4-pentenoic acid was placed in a 10 mL volumetric flask and fixed to volume with acetone to prepare a 1000 μg / mL standard stock solution. This was diluted with acetone to prepare 500, 100, 50, 10, 5, 1, and 0.5 μg / mL standard solutions. Derivatization was performed in the same manner as the sample extract.

[0244] <Volume Average Particle Size>

[0245] The volume average particle size of the polyhydroxyalkanoate resin particles was measured using a particle size distribution analyzer ("Multisizer 4e" manufactured by Beckman Coulter). The measurement was performed by appropriately selecting an aperture calibrated according to the user manual according to the particle size to be measured.

[0246] As the measurement sample, the following sample was used: a sample obtained by dispersing 0.1 g of polyhydroxyalkanoate resin particles in 10 ml of a 0.1% by mass nonionic surfactant aqueous solution using a touch stirrer ("TOUCHMIXER MT-31" manufactured by Yamato Scientific) and an ultrasonic cleaner ("ULTRASONIC CLEANER VS-150" manufactured by VELVO-CLEAR) to prepare a dispersion.

[0247] In the measurement, the beaker was stirred slowly in advance to such an extent that no bubbles were mixed in, and 100,000 polyhydroxyalkanoate resin particles were measured to determine the particle size of each polyhydroxyalkanoate resin particle.

[0248] The volume average particle size of the polyhydroxyalkanoate resin particles is the arithmetic mean of 100,000 particles in a volume-based particle size distribution.

[0249] <Moisture content>

[0250] The moisture content of polyhydroxyalkanoate resin particles was measured by Karl Fischer method as follows. That is, 0.4 g of the polyhydroxyalkanoate resin particle sample was placed in a "CA-200" Karl Fischer moisture measuring device and a "VA-236S" moisture vaporization device manufactured by MITSUBISHI CHEMICAL ANALYTECH, and the measurement was performed. The anolyte and cathode liquid used in the measurement were AQUAMICRON AX and AQUAMICRON CXU manufactured by Mitsubishi Chemical Corporation, respectively. The measurement temperature was set to 150°C. The carrier gas used was N 2 . The flow rate of the carrier gas is set to 250 mL / min. The number of sample tests is set to 3. The moisture content of the air itself at the sample collection site is measured twice, and the average value is set as the blank value. The blank value is subtracted from each measurement result and divided by the sample mass to calculate the moisture content of the sample. The moisture content of the sample is calculated using the following formula.

[0251] Moisture content = [measured moisture content (μg) - blank moisture content (μg)] ÷ 1000000 ÷ sample mass (g) × 100

[0252] The three measurement results obtained by the above-mentioned measurement method were averaged to obtain the water content of the sample.

[0253] <Average circularity>

[0254] The average circularity of the polyhydroxyalkanoate resin particles was measured using a flow particle image analyzer (“FPIA (registered trademark)-3000S” manufactured by Sysmex Corporation).

[0255] The measurement was performed as follows.

[0256] 0.05 g of sodium alkylbenzene sulfonate as a dispersant was added to 20 ml of ion exchange water to obtain a surfactant aqueous solution. 0.02 g of polyhydroxyalkanoate resin particles were added to the obtained surfactant aqueous solution, and an ultrasonic cleaner (VELVO-CLEAR, "VS-150") was used as a disperser to disperse the polyhydroxyalkanoate resin particles in the surfactant aqueous solution for 2 minutes to obtain a dispersion liquid for measurement.

[0257] As the sheath liquid used in the aforementioned flow-type particle image analyzer, a particle sheath (manufactured by Sysmex, "PSE-900A") was used, and the aforementioned dispersion for measurement was introduced into the aforementioned flow-type particle image analyzer equipped with a standard objective lens (10 times), and measurement was performed under the following measurement conditions.

[0258] Measurement mode: LPF measurement mode

[0259] Particle size measurement range: 0.5~200μm

[0260] Particle roundness measurement range: 0.2~1.0

[0261] Number of particles measured: 100,000

[0262] In the measurement, before the measurement starts, the automatic focus adjustment of the flow-type particle image analyzer is performed using a suspension of standard polymer particles (manufactured by THERMO FISHERSCIENTIFIC, "5200A" (a suspension obtained by diluting standard polystyrene particles with ion-exchanged water)). It should be noted that the average circularity refers to the average value of the value obtained by dividing the perimeter calculated from the diameter of a true circle having the same area as the projected area of ​​the polyhydroxyalkanoate resin particles in the image obtained by photographing the dispersion for measurement by the perimeter of the polyhydroxyalkanoate resin particles in the photographed image.

[0263] <Color Tone>

[0264] The color tone of the polyhydroxyalkanoate resin particles was determined by using L * a * b * The color system is obtained by colorimetric measurement.

[0265] The polyhydroxyalkanoate resin particles were filled into a measuring container (powder tank) (manufactured by Konica Minolta Sensing Co., Ltd., "CR-A50"), and the particles were smoothed along the container mouth. The L of the filled polyhydroxyalkanoate resin particles was measured using a colorimeter (manufactured by Konica Minolta Sensing Co., Ltd., "CR-300"). * value, a * Value and b * value.

[0266] [Manufacturing of resin pellets]

[0267] <Production Example 1>

[0268] A poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin raw material powder ("ENMAT Y1000" manufactured by Cheonan Bio Co., Ltd.) was continuously supplied at 15 kg / h to a 26 mm twin-screw extruder ("TEM-26" manufactured by Toshiba Machine Co., Ltd.), extruded from a strand die of Φ5×5 holes installed at the front end of the extruder, and the strand was cooled and pelletized using a pelletizer to obtain poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin raw material pellets. The resin temperature at the die outlet was 188°C.

[0269] [Manufacturing of calcium carbonate dispersion]

[0270] <Production Example 2>

[0271] In a 2L quartz glass pot mill, 3500g of 5mm zirconia beads, 100g of calcium carbonate ("Bai Yanhua PZ" manufactured by SHIRAISHI CALCIUM; primary particle size: 80nm), 450g of ion exchange water, and 450g of 3-methoxy-3-methyl-1-butanol ("Solfit Fine Grade" manufactured by Kuraray Co., Ltd.) were added, and the mixture was treated at a peripheral speed of 100rpm for 24 hours in a ball mill rotating frame to obtain a calcium carbonate dispersion.

[0272] [Example / Comparative Example]

[0273] <Example 1>

[0274] The poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin raw material pellets obtained in Production Example 1 were continuously supplied at 7.5 kg / h to a 57 mm twin-screw extruder (L / D=31.6 manufactured by Osaka Seiki Co., Ltd.), and a 15% aqueous solution of partially saponified polyvinyl alcohol ("GOHSENOL GL-05" manufactured by Mitsubishi Chemical Corporation) was continuously injected at 10.7 kg / h from an injection port provided at the barrel portion of the third stage from the input portion. A slurry in which poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin pellets were dispersed in the partially saponified polyvinyl alcohol aqueous solution was continuously obtained from a Φ7 rod-shaped die mounted at the front end of the extruder. Regarding the barrel temperature of the extruder, among the total 9 sections, the raw material pellet input section is 100°C, the resin melting zone 2 is 200°C, the emulsification zone 2 including the polyvinyl alcohol aqueous solution injection section is 220°C, the rear emulsification zone 2 is 200°C, the cooling zone 3 is 120°C, and the front end mold is 170°C.

[0275] The obtained slurry was washed with 60°C water using a small centrifugal dehydrator and then dehydrated. The filter cake of the obtained poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles was dried in an oven at 80°C for 24 hours, broken up with a stirrer, and further classified using a 25 μm sieve to remove coarse particles to obtain poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles.

[0276] It was confirmed that no residual crotonic acid, residual 2-pentenoic acid, or residual 4-pentenoic acid was detected in the obtained poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles, and the total residual amount of unsaturated fatty acids was less than 10 mass ppm. In addition, the volume average particle size was 11.2 μm, the water content was 0.28 mass %, the average circularity was 0.91, and the L * The value is 93.0, a * The value is -0.7, b * The value is +4.3.

[0277] <Example 2>

[0278] Into a 2L autoclave equipped with a stirring blade and a thermometer, 104 g of a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin raw material powder ("ENMAT Y1000" manufactured by Cheonan Bio Co., Ltd.), 432.2 g of 3-methoxy-3-methyl-1-butanol as a solvent, 432.2 g of ion-exchanged water, 31.2 g of triacetin (manufactured by Daihachi Chemical Industry Co., Ltd.), and 156 g of a calcium carbonate dispersion obtained in Production Example 2 as a dispersion stabilizer were added, and heated to an internal temperature of 150° C. while stirring at a rotation speed of 600 rpm. After reaching 150° C., emulsification was performed for 90 minutes. Thereafter, the mixture was cooled to 30° C. over 1 hour while maintaining a stirring rotation speed of 600 rpm to obtain a suspension.

[0279] To the obtained suspension was added 76 ml of 20% hydrochloric acid (1.14 times the necessary molar number), and the mixture was stirred for 10 minutes to decompose calcium carbonate. Then, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were separated using a centrifuge (manufactured by TANABE WILLTEC).

[0280] The separated poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were washed with ion-exchanged water in an amount 20 times the amount of the added resin.

[0281] The washed poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were dried at 60° C. and a vacuum degree of 0.05 MPa for 20 hours.

[0282] The dried poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were classified in an air atmosphere with a relative humidity of 20% using a classifier ("Hi-BOLTER NR300" manufactured by TOYO HITEC) equipped with a wire mesh with a mesh size of 45 μm. The classification was performed by allowing the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles to flow along an air flow with a relative humidity of 20%, and by causing the air flow to hit the wire mesh to remove particles having a particle size that does not pass through the mesh of the wire mesh.

[0283] It was confirmed that no residual crotonic acid, residual 2-pentenoic acid, or residual 4-pentenoic acid was detected in the obtained poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles, and the total residual amount of unsaturated fatty acids was less than 10 mass ppm. In addition, the volume average particle size was 18.9 μm, the water content was 0.38 mass %, the average circularity was 0.87, and the L * The value is 96.3, a * The value is -0.8, b * The value is +2.0.

[0284] <Example 3>

[0285] The poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin raw material pellets obtained in Production Example 1 were continuously supplied at 7.5 kg / h to a 57 mm twin-screw extruder (manufactured by Osaka Seiki Co., Ltd., L / D=31.6), and a 7% aqueous solution of partially saponified polyvinyl alcohol ("GOHSENOL GH-20R" manufactured by Mitsubishi Chemical Corporation) was continuously injected at 10.7 kg / h from an injection port provided at the barrel portion at the third stage from the input portion. A slurry in which poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin pellets were dispersed in the partially saponified polyvinyl alcohol aqueous solution was continuously obtained from a Φ30 rod-type die installed at the front end of the extruder. Regarding the barrel temperature of the extruder, among the total 9 sections, the raw material pellet input section is 100°C, the resin melting zone 2 is 220°C, the emulsification zone 2 including the polyvinyl alcohol aqueous solution injection section is 220°C, the rear emulsification zone 2 is 200°C, the cooling zone 3 is 160°C, and the front end mold is 160°C.

[0286] The poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were separated from the obtained slurry using a centrifuge (manufactured by TANABE WILLTEC CO., LTD.).

[0287] The separated poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were washed with 60° C. ion-exchanged water in an amount 20 times the amount of the resin.

[0288] The washed poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles were dried at 80° C. and a vacuum degree of 0.05 MPa for 20 hours.

[0289] The dried poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin pellets were crushed with a cutter and then classified in an air atmosphere with a relative humidity of 20% using a classifier ("Hi-BOLTER NR300" manufactured by TOYO HITEC) equipped with a wire mesh with a mesh size of 45 μm. The classification was performed by allowing the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin pellets to flow along an air flow with a relative humidity of 20%, and by causing the air flow to hit the wire mesh to remove particles having a particle size that does not pass through the mesh of the wire mesh.

[0290] It was confirmed that no residual crotonic acid, residual 2-pentenoic acid, or residual 4-pentenoic acid was detected in the obtained poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles, and the total residual amount of unsaturated fatty acids was less than 10 mass ppm. In addition, the volume average particle size was 6.8 μm, the water content was 0.43 mass%, the average circularity was 0.92, and the L * The value is 92.7, a * The value is -0.4, b * The value is +3.4.

[0291] <Example 4>

[0292] In Example 2, the resin particles were obtained in the same manner as in Example 2 except that the amount of triacetin was changed to 20.8 g. It was confirmed that in the obtained poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles, no residual crotonic acid, residual 2-pentenoic acid, or residual 4-pentenoic acid was detected, and the total residual amount of unsaturated fatty acids was 10 mass ppm or less. In addition, the volume average particle size was 32.2 μm, the water content was 0.31 mass %, the average circularity was 0.89, and the L * The value is 94.9, a * The value is -0.7, b * The value is +2.9.

[0293] [Preparation of external preparations]

[0294] A mixture was prepared by mixing 15 parts by mass of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles of Example 2, 21 parts by mass of sericite, 51 parts by mass of muscovite, 0.6 parts by mass of red iron oxide, 1 part by mass of yellow iron oxide, and 0.1 parts by mass of black iron oxide using a Henschel mixer.

[0295] On the other hand, 1 part by mass of sorbitan sesquioleate and 0.2 parts by mass of a preservative were mixed and dissolved in 10 parts by mass of cetyl 2-ethylhexanoate to prepare a dissolved product.

[0296] After the mixture and the dissolved substance were uniformly mixed, 0.1 parts by mass of fragrance was added and uniformly mixed, and then pulverized and sieved to prepare a foundation material. The foundation material was compression-molded in a metal dish to prepare a powder foundation.

[0297] It was confirmed that the powder foundation (external preparation) containing the poly (3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles of Example 2 had no odor and did not produce astringency, had an excellent feel when applied (the feel when applied to the skin), and had excellent adhesion to the skin and light spreading on the skin.

[0298] [Preparation of coating material]

[0299] Using a stirring degassing device, 2 parts by mass of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin particles of Example 1 and 20 parts by mass of a commercially available acrylic water-based glossy paint (manufactured by Kanpe Hapio, trade name: SUPERHIT) were mixed for 3 minutes and degassed for 1 minute to obtain a coating material. The obtained coating was applied to an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device provided with a plate with a gap of 50 μm, and then dried to obtain a coating film. The obtained coating film was measured using a gloss meter (manufactured by HORIBA, "GLOSS CHECKER IG-330"). The gloss (60°) of the coating film was 1.

[0300] The present invention can be implemented in various other forms without exceeding its spirit or main features. Therefore, the above-mentioned embodiments are merely illustrative in all aspects and are not to be interpreted as restrictive. The scope of the present invention is indicated by the claims and is not limited to the text of the specification. Furthermore, all modifications and changes within the scope of the equivalents of the claims fall within the scope of the present invention.< / uhplc>

Claims

1. A polyhydroxyalkanoate resin particle, wherein: The total residual amount of unsaturated fatty acids is 10 mass ppm or less.

2. A polyhydroxyalkanoate resin particle, wherein: The total residual amount of crotonic acid was 10 mass ppm or less.

3. A polyhydroxyalkanoate resin particle, wherein: The total residual amount of pentenoic acid was 60 mass ppm or less.

4. The polyhydroxyalkanoate resin particles according to any one of claims 1 to 3, wherein The polyhydroxyalkanoate-based resin includes a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) resin. The polyhydroxyalkanoate resin particles according to any one of claims 1 to 3, which have a volume average particle size of 1 μm or more and 40 μm or less. The polyhydroxyalkanoate resin particles according to any one of claims 1 to 3, wherein the water content is 0.2% by mass or more and 0.8% by mass or less. 7 . An external preparation comprising the resin particles according to claim 1 . 8 . A coating material comprising the polyhydroxyalkanoate resin particles according to claim 1 . 9 . A resin composition comprising the polyhydroxyalkanoate resin particles according to claim 1 . 10 . An anti-blocking agent comprising the polyhydroxyalkanoate resin particles according to claim 1 .