Polymer particles and their uses

Abstract

To provide a polymer particle that is eco-friendly, offers a smooth, moist feel, and provides excellent coatability.SOLUTION: Polymer particles comprise biodegradable polymers (A), wherein the volume-based cumulative 50% particle size (D50) by is 1-100 μm; the value determined by dividing the volume-based cumulative 90% particle size (D90) by the particle size (D50) is 1.0 and 3.5; and the repose angle is 33-65 degrees. The biodegradable polymers (A) preferably should comprise at least one selected from cellulose, cellulose resin and polyester resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to polymer particles and uses thereof. [Background technology]

[0002] Particles are widely used in cosmetics, paints, optical applications, resins, building materials, etc. Functions required for particles include light diffusion, concealment, coatability, and touch imparting, and properties required for particles include refractive index, dispersibility, slipperiness, flexibility, etc. For example, in cosmetics and paints, particles with a soft touch are preferred in terms of touch imparting, etc. In recent years, with increasing interest in the environment, particles with low environmental impact are in demand, and biodegradable particles in particular have attracted attention. Patent Document 1 describes a method for producing polylactic acid-based resin microparticles made of polylactic acid derived from non-petroleum raw materials as particles that reduce environmental impact, and the polylactic acid-based resin microparticles. Patent Document 2 describes porous resin microparticles made of biodegradable polyester thermoplastic resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 105140 [Patent Document 2] International Publication No. 2017 / 056908 Summary of the Invention [Problem to be solved by the invention]

[0004] However, these biodegradable particles are not satisfactory in terms of feel. Therefore, an object of the present invention is to provide polymer particles which are environmentally friendly, have a smooth and moist touch, and have excellent coatability. [Means for solving the problem]

[0005] As a result of intensive research to achieve the above-mentioned object, the inventors of the present application discovered that polymer particles containing a biodegradable polymer and exhibiting specific properties can be obtained which are environmentally friendly, have a smooth and moist feel, and have excellent coatability, and thus arrived at the present invention. That is, the polymer particles of the present invention are polymer particles containing a biodegradable polymer (A), and have a volume-based cumulative 50% particle diameter (D50) of 1 to 100 μm, a value obtained by dividing the volume-based cumulative 90% particle diameter (D90) by the particle diameter (D50) of 1.0 to 3.5, and an angle of repose of 33 to 65 degrees.

[0006] The polymer particles of the present invention preferably satisfy at least one of the following 1) to 5). 1) The biodegradable polymer (A) contains at least one selected from cellulose, a cellulose-based resin, and a polyester-based resin. 2) The polyester resin includes at least one selected from an aliphatic polyester resin and an aliphatic-aromatic polyester resin. 3) The enthalpy of fusion is 0 to 140 J / g. 4) The oleic acid absorption is 30 to 150 mL / 100 g. 5) The polymer particles further contain at least one selected from a surfactant and a water-soluble polymer, and the total weight ratio of the surfactant and the water-soluble polymer to the polymer particles is 0.001 to 10% by weight.

[0007] The cosmetic preparation of the present invention contains the above-mentioned polymer particles. The coating composition of the present invention contains the above-described polymer particles. Effect of the Invention

[0008] The particles of the present invention are environmentally friendly, have a smooth and moist feel, and are excellent in coatability. Since the cosmetic preparation of the present invention contains the above-mentioned particles, it is environmentally friendly, has a smooth and moist feel, and is excellent in applicability. Since the coating composition of the present invention contains the above-mentioned particles, it is environmentally friendly, has a smooth and moist touch, and has excellent coatability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] [Polymer particles] The polymer particles of the present invention contain a biodegradable polymer (A), have a volume-based cumulative 50% particle diameter (D50) of 1 to 100 μm, a value obtained by dividing the volume-based cumulative 90% particle diameter (D90) by the particle diameter (D50) of 1.0 to 3.5, and have an angle of repose of 33 to 65 degrees, and are environmentally friendly, have a smooth and moist feel, and have excellent coatability. The polymer particles of the present invention will be described below.

[0010] The polymer particles of the present invention have a volume-based cumulative 50% particle size (D50) of 1 to 100 μm. If the particle size (D50) is less than 1 μm, the smooth feel is inferior, and if it exceeds 100 μm, the rough feel is felt and the moist feel is inferior. The lower limit of the particle size (D50) is preferably 1.5 μm, more preferably 2.0 μm, and even more preferably 2.5 μm, and the upper limit of the particle size (D50) is preferably 50 μm, more preferably 40 μm, even more preferably 30 μm, and particularly preferably 20 μm. Furthermore, for example, 1 to 50 μm is preferable, 1.5 to 30 μm is more preferable, and 2 to 20 μm is particularly preferable.

[0011] The polymer particles of the present invention satisfy the condition that the value (D90 / D50) obtained by dividing the cumulative 90% particle diameter (D90) based on volume by the above-mentioned particle diameter (D50) is 1.0 to 3.5. If the value exceeds 3.5, the polymer particles are likely to cause unevenness when applied, and the smooth feel is inferior, the texture is rough, and the moist feel is inferior. The lower limit of the value is more preferably 1.1, even more preferably 1.3, and particularly preferably 1.5, and the upper limit of the value is preferably 3.0, more preferably 2.8, even more preferably 2.5, and particularly preferably 2.2. Furthermore, for example, 1.1 to 3.0 is more preferable, 1.3 to 2.8 is even more preferable, and 1.3 to 2.5 is particularly preferable.

[0012] The polymer particles of the present invention are not particularly limited, but the value (D10 / D50) obtained by dividing the cumulative 10% particle size (D10) based on volume by the above particle size (D50) is preferably 0.1 to 1.0. When the value is 0.1 or more, the smooth feel tends to be improved. The upper limit of the value is more preferably 0.9, even more preferably 0.8, and particularly preferably 0.7, and the lower limit of the value is more preferably 0.2, even more preferably 0.25, and particularly preferably 0.3. Furthermore, for example, 0.1 to 0.9 is more preferable, 0.2 to 0.8 is even more preferable, and 0.3 to 0.7 is particularly preferable. The particle size (D50), particle size (D90), and particle size (D10) of the polymer particles are those according to the method described in the Examples.

[0013] The repose angle of the polymer particles of the present invention is 33 to 65 degrees. When the repose angle of the polymer particles is within the above range, the powder is easily accumulated and a powder layer is easily formed, so that a smooth and moist touch can be obtained when applied. The lower limit of the repose angle is preferably 35 degrees, more preferably 38 degrees, even more preferably 40 degrees, and particularly preferably 42 degrees, and the upper limit of the repose angle is preferably 63 degrees, more preferably 60 degrees, even more preferably 58 degrees, and particularly preferably 55 degrees. Furthermore, for example, 35 to 63 degrees is more preferable, 38 to 63 degrees is even more preferable, and 40 to 60 degrees is particularly preferable. The repose angle of the polymer particles is determined by the method described in the Examples.

[0014] The polymer particles of the present invention are not particularly limited, but it is preferable that the value obtained by dividing the collapse angle by the above-mentioned repose angle (collapse angle / repose angle) is 0.5 to 1.0, since a more moist touch can be obtained. The lower limit of the numerical value is more preferably 0.55, even more preferably 0.60, and particularly preferably 0.65, and the upper limit of the numerical value is more preferably 0.98, even more preferably 0.95, and particularly preferably 0.92. Furthermore, for example, 0.55 to 0.98 is more preferable, 0.60 to 0.98 is even more preferable, and 0.65 to 0.98 is particularly preferable. The collapse angle of the polymer particles is measured by the method described in the Examples.

[0015] The sphericity of the polymer particles of the present invention is not particularly limited, but is preferably 0.7 to 1.0. When the sphericity is 0.7 or more, the smooth feel tends to be improved. The sphericity is more preferably 0.8 to 1.0, further preferably 0.85 to 1.0, and particularly preferably 0.9 to 1.0. The sphericity of the polymer particles can be calculated, for example, by image analysis, by dividing the minor axis of a particle photographed by a scanning electron microscope or the like by the major axis. In this case, when the ratio of the minor axis to the major axis is 1, the sphericity is 1.

[0016] The oleic acid oil absorption of the polymer particles of the present invention is not particularly limited, but is preferably 30 to 150 mL / 100 g in terms of excellent smoothness. The lower limit of the oil absorption is preferably (1) 35 mL / 100 g, (2) 40 mL / 100 g, (3) 45 mL / 100 g, and (4) 50 mL / 100 g in this order (the larger the value in parentheses, the more preferable). On the other hand, the upper limit of the oil absorption is preferably (1) 130 mL / 100 g, (2) 120 mL / 100 g, (3) 110 mL / 100 g, (4) 100 mL / 100 g, (5) 95 mL / 100 g, (6) 90 mL / 100 g, and (7) 85 mL / 100 g in this order (the larger the value in parentheses, the more preferable). The oil absorption of the polymer particles is measured by the method described in the Examples. For example, the oil absorption amount of the polymer particles is more preferably 40 to 120 mL / 100 g, and further preferably 45 to 100 mL / 100 g. The oil absorption amount of the polymer particles is measured by the method described in the Examples.

[0017] The water absorption of the polymer particles of the present invention is not particularly limited, but is preferably 20 to 150 mL / 100 g in terms of excellent smoothness. The lower limit of the water absorption is preferably (1) 25 mL / 100 g, (2) 30 mL / 100 g, (3) 35 mL / 100 g, and (4) 40 mL / 100 g in this order (the larger the value in parentheses, the more preferable). On the other hand, the upper limit of the water absorption is preferably (1) 140 mL / 100 g, (2) 130 mL / 100 g, (3) 120 mL / 100 g, (4) 110 mL / 100 g, (5) 100 mL / 100 g, (6) 90 mL / 100 g, and (7) 85 mL / 100 g in this order (the larger the value in parentheses, the more preferable). For example, the water absorption amount of the polymer particles is more preferably 30 to 120 mL / 100 g, and further preferably 40 to 100 mL / 100 g. The water absorption amount of the polymer particles is measured by the method described in the Examples.

[0018] The true specific gravity of the polymer particles of the present invention is not particularly limited, but is preferably 0.8 to 1.8 g / cm. 3 The lower limit of the true specific gravity is preferably (1) 0.85 g / cm because of its excellent smooth feel. 3 , (2) 0.90 g / cm 3 , (3) 0.93 g / cm 3 , (4) 0.95 g / cm 3 , (5) 0.98 g / cm 3 , (6) 1.0 g / cm 3 (The larger the value in parentheses, the more preferable it is.) On the other hand, the preferable upper limit of the true specific gravity is (1) 1.7 g / cm 3 , (2) 1.6 g / cm 3 , (3) 1.55 g / cm 3 , (4) 1.5 g / cm 3 , (5) 1.45 g / cm 3 , (6) 1.4 g / cm 3 (The larger the value in parentheses, the more preferable it is.) Furthermore, for example, 0.90 to 1.55 g / cm 3 More preferably, 1.0 to 1.4 g / cm 3 is more preferred.

[0019] The melting enthalpy of the polymer particles of the present invention is not particularly limited, but is preferably 0 to 140 J / g. When the melting enthalpy is within the above range, the polymer has crystalline and amorphous parts, so that it has a moderate hardness and improves the smooth and moist touch when applied. The lower limit of the melting enthalpy is preferably 10 J / g, more preferably 20 J / g, even more preferably 30 J / g, and particularly preferably 35 J / g, and the upper limit of the melting enthalpy is preferably 130 J / g, more preferably 125 J / g, even more preferably 120 J / g, and particularly preferably 115 J / g. Furthermore, for example, 20 to 130 J / g is more preferable, 30 to 120 J / g is even more preferable, and 30 to 115 J / g is particularly preferable. The melting enthalpy of the polymer particles is measured by the method described in the Examples.

[0020] The polymer particles of the present invention contain a biodegradable polymer (A) (hereinafter, sometimes referred to as polymer (A)). A biodegradable polymer is a polymer that is decomposed by microorganisms present in nature and ultimately becomes carbon dioxide gas, water, etc. The polymer (A) has a solubility in water of 0 g / mL to 0.01 g / mL at 25° C. The solubility is more preferably 0 g / mL to 0.005 g / mL, and even more preferably 0 g / mL to 0.001 g / mL.

[0021] The polymer (A) is not particularly limited as long as it is a polymer having a solubility in water at 25° C. of 0 g / mL to 0.01 g / mL. Examples of the polymer (A) include naturally occurring waxes such as carnauba wax, candelilla wax, rice wax, and beeswax; polysaccharides such as cellulose, cellulose acetate, ethyl cellulose, cellulose ether derivatives, cellulose acetate propionate, cellulose acetate butyrate, cellulose derivatives, chitin, chitosan, and starch; polylactic acid, polypropionyl alcohol, and the like. , polycaprolactone, polycaprolactone butylene succinate, polybutylene adipate caprolactone, polybutylene succinate hydroxycaproate, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate carbonate, polybutylene succinate terephthalate, polybutylene succinate adipate terephthalate, polybutylene succinate lactate, polyethylene terephthalate copolymer, polybutylene Examples of the polyester resin include polyester-based resins such as ethylene adipate terephthalate, polytetramethylene adipate terephthalate, polybutylene adipate, polyethylene succinate, polyethylene adipate, polyethylene adipate terephthalate, polyethylene terephthalate succinate, polytetramethylene succinate, polypropylene succinate, polyhydroxyalkanoate, polyhydroxybutyrate, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), polyhydroxybutyrate valerate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyacyl), polyhydroxyacyl, polyglycolic acid, and lactic acid-glycolic acid copolymers, and one or more of these may be used in combination.

[0022] From the viewpoint of reducing the burden on the environment, the polymer (A) preferably contains at least one selected from naturally occurring waxes, polysaccharides, and polyester-based resins, more preferably contains at least one selected from cellulose-based resins such as cellulose acetate, ethyl cellulose, cellulose ether derivatives, cellulose acetate cellulose propionate, cellulose acetate cellulose butyrate, and cellulose derivatives, cellulose, and polyester-based resins, and further preferably contains a polyester-based resin.

[0023] The polyester resin is not particularly limited, but it is preferable to include at least one selected from aliphatic polyester resins and aliphatic-aromatic polyester resins, since this makes it easier to obtain polymer particles having the angle of repose of the present invention, provides a more moist feel, and is more biodegradable. As the aliphatic polyester resin, an aliphatic polyester resin containing an aliphatic polyhydric alcohol and an aliphatic polycarboxylic acid as constituent components, or an aliphatic polyester resin containing an aliphatic oxycarboxylic acid component as a constituent component is preferable.

[0024] Examples of aliphatic polyhydric alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, and pentaerythritol, and may be composed of one or more kinds.

[0025] Examples of the aliphatic polycarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, azelaic acid, octyl succinic acid, fumaric acid, maleic acid, itaconic acid, decamethylene dicarboxylic acid, and anhydrides thereof, and the like. The aliphatic polycarboxylic acid may be composed of one or more kinds. Examples of the aliphatic oxycarboxylic acid include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxydimethylbutyric acid, hydroxymethylbutyric acid, and lower alkyl esters or derivatives such as esters thereof, and the aliphatic oxycarboxylic acid may be composed of one or more kinds.

[0026] The aliphatic-aromatic polyester resin is not particularly limited as long as the constituent components of the polyester resin include at least one selected from an aliphatic polyhydric alcohol, an aliphatic polycarboxylic acid, and an aliphatic oxycarboxylic acid, and further include an aromatic polycarboxylic acid or a derivative thereof. Examples of the aromatic polycarboxylic acid include o-phthalic acid, terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, trimellitic acid, and pyromellitic acid, and the like may be composed of one or more kinds. From the viewpoint of biodegradability, the proportion of the constituent component derived from aromatic polyvalent carboxylic acid in the constituent components of the aliphatic-aromatic polyester resin is preferably 40 unit mol % or less.

[0027] Examples of aliphatic polyester resins and aliphatic-aromatic polyester resins include polylactic acid, polycaprolactone butylene succinate, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate carbonate, polybutylene succinate terephthalate, polybutylene adipate terephthalate, polytetramethylene adipate terephthalate, polybutylene adipate, polybutylene succinate adipate terephthalate, polybutylene succinate lactate, polyethylene succinate, polyethylene adipate poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), polyhydroxybutyrate valerate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyacyl), polyhydroxyacyl, and the like.

[0028] The weight ratio of the polymer (A) in the polymer particles of the present invention is not particularly limited, but is preferably 10 to 100% by weight. When the weight ratio is 10% by weight or more, biodegradability tends to improve, and it is preferable in that the burden on the environment is further reduced. The lower limit of the weight ratio is preferably (1) 30% by weight, (2) 40% by weight, (3) 50% by weight, (4) 60% by weight, (5) 70% by weight, (6) 80% by weight, and (7) 90% by weight (the larger the value in parentheses, the more preferable). On the other hand, the upper limit of the content is preferably (1) 99.999% by weight, (2) 99.99% by weight, (3) 99.9% by weight, (4) 99% by weight, and (5) 98% by weight (the larger the value in parentheses, the more preferable). Furthermore, for example, 30 to 100% by weight is more preferable, and 50 to 100% by weight is even more preferable.

[0029] When the polymer (A) contains at least one selected from cellulose, cellulose-based resins, and polyester-based resins, the total weight percentage of the cellulose, cellulose-based resins, and polyester-based resins in the polymer (A) is not particularly limited, but is preferably 10 to 100% by weight. If the total weight percentage is 10% by weight or more, it is preferable in that biodegradability tends to be improved. The total weight percentage is more preferably 30 to 100% by weight, even more preferably 50 to 100% by weight, and most preferably 70 to 100% by weight.

[0030] The polymer particles of the present invention may contain a polymer other than the polymer (A) (hereinafter, sometimes referred to as "other polymer"). Examples of other polymers include thermoplastic resins such as polyvinyl resins, polyacrylic resins, polystyrene resins, polyolefin resins, polyether resins, polyamide resins, and thermoplastic polyurethane resins; and thermosetting resins such as silicone resins, phenolic resins, and unsaturated polyester resins. These may be used alone or in combination of two or more.

[0031] The polymer particles of the present invention may contain, in addition to the polymer (A), at least one selected from a surfactant, an organic substance other than the above polymer components, and an inorganic substance. The surfactant is not particularly limited, but examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and silicone-based surfactants. Specific examples thereof include anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkyl ether carboxylate salts, alkyl ether sulfate salts, alkyl phosphate salts, polyoxyalkylene alkyl ether acetate salts, alkylbenzene sulfonate salts, polyoxyalkylene alkyl ether sulfate salts, higher fatty acid amide sulfonate salts, higher fatty acid alkali metal salts, alkyl phosphate salts, polyoxyalkylene alkyl ether phosphate salts, long-chain sulfosuccinate salts, and N-acylamino acid salts; cationic surfactants such as quaternary ammonium salts and alkylamine salts; polyoxyalkylene oxide-added alkyl ethers, and polyoxyalkylene styrenates. Examples of the surfactant include nonionic surfactants such as phenyl ether, ester compounds of polyhydric alcohols and monovalent fatty acids, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, glycerin fatty acid esters, PEG-hydrogenated castor oil, polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil, higher fatty acid PEG glyceryls, higher fatty acid sorbitans, polyoxyalkylene sorbitol fatty acid esters, polyglycerin fatty acid esters, alkyl glycerin ethers, polyoxyalkylene cholesteryl ethers, alkyl polyglucosides, sucrose fatty acid esters, and polysorbates; amphoteric surfactants such as amino acid-based, betaine-type, hydrogenated lecithin, and lecithin; and silicone-based surfactants such as modified dimethicone. These surfactants may be used alone or in combination of two or more.

[0032] The organic matter is not particularly limited, but examples thereof include water-soluble polymers, waxes, oils, fatty acids, fatty acid metal salts, amino acid compounds, and the like, and one or more of these may be used in combination. The water-soluble polymer is not particularly limited as long as it has a solubility in water at 25°C of more than 0.01 g / mL, and examples thereof include sodium polyacrylate, polyvinylpyrrolidone, polyvinyl alcohol, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, dextrin, sodium alginate, potassium alginate, mannan, xylan, xyloglucan, gum arabic, tamarind gum, pectin, pullulan, casein, xanthan gum, carrageenan, tragacanth gum, gelatin, hydroxyethyl cellulose, hydroxypropyl methylcellulose, methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose, and the like.

[0033] Examples of the wax include higher alcohols, synthetic waxes, and paraffins. Examples of oils include almond oil, olive oil, rice bran oil, squalane, silicone oil, mineral oil, alkanes, and alkyl benzoates. Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, and cerotic acid.

[0034] Examples of fatty acid metal salts include calcium laurate, zinc laurate, potassium laurate, zinc myristate, sodium myristate, zinc palmitate, sodium stearate, magnesium stearate, zinc stearate, calcium stearate, aluminum stearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, calcium behenate, zinc behenate, magnesium behenate, calcium montanate, zinc montanate, magnesium montanate, and aluminum montanate.

[0035] Examples of amino acid compounds include N-lauroyl-L-arginine, N-lauroyl-L-lysine, N-hexanoyl-L-lysine, N-oleyl-L-lysine, N-palmitoyl-L-lysine, N-stearinoyl-L-lysine, N-hexanoyl-L-lysine, N-myristenoyl-L-lysine, N-capryloyl-L-lysine, and N-decanoyl-L-lysine.

[0036] Examples of inorganic substances include, but are not limited to, wollastonite, sericite, kaolin, mica, clay, talc, bentonite, smectite, alumina silicate, pyrophyllite, montmorillonite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, boron nitride, silicon carbide, magnesium silicate, calcium silicate, magnesium aluminometasilicate, magnesium aluminometasilicate, hydroxyapatite, titanium oxide, silica, alumina, mica, titanium dioxide, zinc oxide, magnesium oxide, zinc oxide, hydrosaltite, and boron nitride.

[0037] The polymer particles of the present invention are not particularly limited, but further contain at least one selected from a surfactant and a water-soluble polymer, and when the total weight ratio of the surfactant and the water-soluble polymer in the polymer particles is 0.001 to 10% by weight, it is preferable in that it is easy to obtain polymer particles having the specific performance of the present invention and improves the moist touch. The lower limit of the total amount is preferably (1) 0.002% by weight, (2) 0.005% by weight, (3) 0.01% by weight, (4) 0.02% by weight, (5) 0.05% by weight, and (6) 0.1% by weight (the larger the value in parentheses, the more preferable). On the other hand, the upper limit of the weight ratio is preferably (1) 8% by weight, (2) 6% by weight, (3) 5% by weight, (4) 4% by weight, and (5) 3% by weight (the larger the value in parentheses, the more preferable). Furthermore, for example, 0.001 to 8% by weight is more preferable, and 0.001 to 6% by weight is even more preferable.

[0038] The polymer particles of the present invention are not particularly limited, but preferably have a biodegradability of 1% or more after 10 days as measured in accordance with JIS K6950: 2000. The lower limit of the biodegradability is preferably (1) 3%, (2) 5%, (3) 10%, (4) 15%, (5) 20%, (6) 25%, and (7) 30% in that order (the larger the number in parentheses, the more preferable it is).

[0039] The polymer particles of the present invention can be produced, for example, by a method including the following steps 1 to 3 (hereinafter sometimes referred to as a particle production method). Step 1: Mixing a biodegradable polymer (A), a surfactant, a water-soluble polymer, and water to obtain a preliminary mixed liquid. Step 2: Heat and stir the preliminary mixture obtained in step 1 to obtain a heated dispersion. Step 3: Cooling the heated dispersion obtained in step 2

[0040] The method for producing polymer particles of the present invention is preferable in that particles having a smooth and moist touch can be suitably produced when no organic solvent is used. It is presumed that by producing polymer particles in water without using an organic solvent, surfactants and water-soluble polymers are likely to be present at the interface between the particles and water during particle formation, which contributes to the surface properties of the particles. It is also presumed that by not using an organic solvent, the polarity of the particle surface is appropriately maintained during particle formation, and the particles have a specific particle size distribution and angle of repose, resulting in particles with a moist touch. It is also believed that the lipophilic group of the surfactant affects the polymer structure, making it easier to have a specific angle of repose and a specific enthalpy of fusion, resulting in polymer particles with excellent smooth and moist touch. It is also preferable not to use an organic solvent, as this is environmentally friendly.

[0041] The surfactant is not particularly limited, but the surfactants described above can be used. The surfactant to be used is preferably at least one selected from an anionic surfactant and a nonionic surfactant, and more preferably a nonionic surfactant, because this makes it possible to make the shape of the polymer particles more uniform, makes it easier to obtain polymer particles having a specific particle size distribution and angle of repose, and improves the moist feel of the polymer particles. The anionic surfactant is not particularly limited, but it is preferable to use at least one selected from sulfate ester salts and sulfonate salts, and it is more preferable to use a sulfonate salt. The nonionic surfactant is not particularly limited, but it is preferable to use an ester compound of a polyhydric alcohol and a monovalent fatty acid, and it is more preferable to use at least one selected from glycerin fatty acid esters and higher fatty acid sorbitans.

[0042] The surfactant is not particularly limited, but it is preferable to use a nonionic surfactant with an HLB value of 1 to 13, since this tends to have a specific melting enthalpy. The HLB value is more preferably 1 to 11, further preferably 1 to 10, and particularly preferably 1.5 to 10. The HLB value can be calculated, for example, from the following Griffin method formula (1). HLB = 20 × (molecular weight of hydrophilic group / total molecular weight) (1) Furthermore, it is preferable to use an ester type or ester salt type surfactant, since it is easy to obtain polymer particles having a specific particle size distribution and angle of repose, and the surfactant has an excellent moist feel to the touch.

[0043] The surfactant may be finally contained in the polymer particles. When the surfactant is contained in the particles, it is preferable because it is easier to obtain polymer particles having a specific angle of repose. It is considered that the presence of the surfactant near the surface of the polymer particles affects the surface state more and makes it easier to obtain a specific angle of repose. The weight ratio of the surfactant in the polymer particles is not particularly limited, but is preferably 0.001 to 10% by weight, and the upper limit of the weight ratio is more preferably 7% by weight, and even more preferably 5% by weight. On the other hand, the lower limit of the weight ratio is more preferably 0.005% by weight, and even more preferably 0.01% by weight. Furthermore, for example, it is more preferably 0.001 to 7% by weight, and even more preferably 0.001 to 5% by weight.

[0044] The water-soluble polymer may be any of those mentioned above. In terms of facilitating the production of polymer particles having a specific particle size and particle size distribution, a water-soluble polymer having a viscosity of 2 to 200,000 mPa s in a 4% aqueous solution at 20°C is preferred. The water-soluble polymer is preferably at least one selected from polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and carboxymethyl cellulose, and more preferably polyvinyl alcohol, in that polymer particles having a specific particle size and particle size distribution can be easily obtained and the smooth feel can be further improved.

[0045] The water-soluble polymer may be finally contained in the polymer particles. The presence of the water-soluble polymer in the polymer particles is thought to facilitate the production of polymer particles having a specific angle of repose, leading to a smoother feel. The weight ratio of the water-soluble polymer in the polymer particles is not particularly limited, but is preferably 0.001 to 10% by weight, and the upper limit of the weight ratio is more preferably 8% by weight, and even more preferably 5% by weight. On the other hand, the lower limit of the weight ratio is more preferably 0.002% by weight, and even more preferably 0.005% by weight. Furthermore, for example, it is more preferably 0.001 to 8% by weight, and even more preferably 0.001 to 5% by weight.

[0046] (Process 1) Step 1 is a step of mixing the polymer (A), a surfactant, a water-soluble polymer, and water to obtain a preliminary mixed liquid. When the polymer particles contain components other than the polymer (A), the surfactant, and the water-soluble polymer, it is preferable to add and mix the other components in this step.

[0047] In step 1, the mixing ratio of the polymer (A) is not particularly limited, but is preferably 1 to 200 parts by weight per 100 parts by weight of water. When the ratio is within the above range, it is preferable that polymer particles having a more uniform shape and a specific particle size and particle size distribution are easily obtained. The lower limit of the mixing ratio is more preferably 3 parts by weight, even more preferably 5 parts by weight, and most preferably 10 parts by weight. On the other hand, the upper limit of the mixing ratio is more preferably 180 parts by weight, even more preferably 160 parts by weight, and most preferably 150 parts by weight. Furthermore, for example, 5 to 200 parts by weight is more preferable, and 10 to 180 parts by weight is even more preferable.

[0048] In step 1, the mixing ratio of the surfactant is not particularly limited, but is preferably 0.001 to 10 parts by weight relative to 100 parts by weight of the polymer (A). When the ratio is within the above range, polymer particles having a specific particle size distribution and angle of repose are easily obtained, and the moist touch of the obtained polymer particles tends to be improved, which is preferable. The lower limit of the mixing ratio is preferably 0.01 parts by weight, more preferably 0.05 parts by weight, and particularly preferably 0.1 parts by weight. The upper limit of the mixing ratio is more preferably 7 parts by weight, even more preferably 5 parts by weight, and particularly preferably 3 parts by weight. Furthermore, for example, 0.001 to 7 parts by weight is more preferable, and 0.01 to 7 parts by weight is even more preferable.

[0049] In step 1, the mixing ratio of the water-soluble polymer to water is not particularly limited, but is preferably 0.1 to 100 parts by weight per 100 parts by weight of water. When the ratio is within the above range, polymer particles having a specific particle size and particle size distribution are easily obtained, and the dispersibility of the obtained polymer particles tends to be improved. The lower limit of the ratio is more preferably 0.5 parts by weight, even more preferably 1 part by weight, and particularly preferably 2 parts by weight. On the other hand, the upper limit of the ratio is more preferably 80 parts by weight, even more preferably 70 parts by weight, and particularly preferably 60 parts by weight. Also, for example, 0.5 to 100 parts by weight is more preferable, and 1 to 100 parts by weight is even more preferable.

[0050] When the polymer particles of the present invention are produced by mixing a surfactant and a water-soluble polymer, the viscosity of the liquid during production is improved by the water-soluble polymer, and the efficiency of particle uniformization is improved by the surfactant, which is considered to contribute to uniform particle size distribution and surface properties of the particles, and it is preferable that polymer particles having a specific particle size, particle size distribution, and angle of repose are easily obtained.Furthermore, in terms of further improving the smooth and moist touch, it is even more preferable that the weight ratios of the surfactant and the water-soluble polymer are within the above-mentioned ranges.

[0051] (Process 2) Step 2 is a step of heating and stirring the preliminary mixture obtained in step 1 to obtain a heated dispersion. The pressure during heating and stirring in step 2 is not particularly limited, but is preferably 0.1 to 10 MPa. When the pressure is within the above range, polymer particles having a specific particle size distribution tend to be obtained, which is preferable. The pressure is preferably equal to or higher than the saturated vapor pressure of water at the heating temperature. The heating temperature is not particularly limited, but is preferably 80 to 300°C. When the temperature is within the above range, polymer particles having a specific particle size, particle size distribution, and specific angle of repose are easily obtained, and the shape of the obtained polymer particles tends to be more uniform, which is preferable. The temperature is preferably a temperature equal to or higher than the softening point or melting point of the polymer (A), more preferably a temperature 5°C or higher than the softening point or melting point of the polymer (A), even more preferably a temperature 10°C or higher, and particularly preferably a temperature 15°C or higher. By heating to a temperature equal to or higher than the softening point or melting point, the lipophilic group of the surfactant acts on the polymer (A) and easily affects the resin structure, and the surfactant and the water-soluble polymer are uniformly present at the interface between the polymer (A) and water, which is preferable because particles having a specific particle size, particle size distribution, and specific angle of repose are easily obtained. In step 2, it is preferable to heat the polymer (A) to a temperature equal to or higher than the softening point or melting point thereof and stir the polymer (A) under a pressure of 0.1 MPa or more, since this makes it easier to obtain polymer particles having a specific particle size and particle size distribution.

[0052] The stirring method is not particularly limited, and it is sufficient that the mixture is stirred to a degree that allows it to be mixed. The heating time is not particularly limited, but is preferably 1 to 30 hours. When the time is 1 hour or more, resin particles are more uniformly dispersed and have a specific particle diameter and particle size distribution, which is preferable. When the time is 30 hours or less, production efficiency tends to improve. The lower limit of the time is more preferably 2 hours, even more preferably 3 hours, and most preferably 5 hours. The upper limit of the heating time is more preferably 25 hours, even more preferably 20 hours, and most preferably 15 hours. Furthermore, for example, 3 to 20 hours is more preferable, and 3 to 15 hours is even more preferable.

[0053] (Step 3) Step 3 is a step of cooling the heated dispersion obtained in step 2. By cooling the heated dispersion in step 2, a dispersion of polymer particles can be obtained. The cooling method is not particularly limited, but it is preferable to cool the heated dispersion obtained in step 2 to 5 to 50° C. The cooling rate is not particularly limited, but it may be rapid cooling or natural cooling by air cooling or the like. In step 3, stirring may be continued at the stirring speed in step 2, or stirring may be stopped. The dispersion after cooling is an aqueous dispersion containing polymer particles.

[0054] The polymer particles of the present invention may be used in the form of a dispersion, a wet powder, or a dry powder. The wet powder can be obtained by dehydrating the dispersion in step 3 using, for example, a centrifuge, a pressure press, a vacuum dehydrator, or the like. The obtained dispersion may be subjected to a dehydration treatment after a measure for reducing the liquid viscosity is taken. Examples of a method for reducing the liquid viscosity include a method for diluting the dispersion by adding water, a method for salting out a water-soluble component, and a method for decomposing a water-soluble component with an oxidizing agent or an enzyme.

[0055] The dry powder can be obtained by drying the wet powder using a tray dryer, an indirect heating dryer, a fluidized bed dryer, a vacuum dryer, a vibration dryer, an airflow dryer, etc. Alternatively, the dispersion obtained in step 3 can be dried using a spray dryer, a fluidized bed dryer, etc. to obtain a dry powder. The dried powder may be classified by air classification, screen classification, or the like.

[0056] [Applications of polymer particles] The polymer particles of the present invention can be used in cosmetics, paints, optical applications, resins, building materials, etc. In particular, the polymer particles of the present invention are excellent in smooth and moist touch, and therefore can be suitably used in cosmetics and coating compositions.

[0057] When used in cosmetics, it can be used in combination with known cosmetic ingredients. Examples of cosmetic ingredients include oils, surfactants, alcohols, water, moisturizers, gelling agents, thickeners, powders other than the polymer particles of the present invention, UV absorbers, preservatives, antibacterial agents, antioxidants, functional ingredients, etc. Examples of the form of the cosmetic containing the polymer particles of the present invention include powder, solid, cream, gel, liquid, mousse, spray, etc. The weight ratio of the polymer particles to the entire cosmetic is not particularly limited, but is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight.

[0058] When used in a coating composition, it can be used in combination with known coating components. The weight proportion of the polymer particles in the entire coating composition is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and further preferably 1 to 10% by weight. EXAMPLES

[0059] Examples of the particles of the present invention will be specifically described below. Note that the present invention is not limited to these examples. In addition, the particles of the examples and comparative examples were measured for physical properties and further evaluated in the following manner. It should be noted that Example 4 is a reference example.

[0060] (Measurement of particle size (D10), particle size (D50), particle size (D90) of polymer particles) Measurements were performed using a laser diffraction scattering type particle size distribution measuring device (Microtrac particle size distribution meter (model 9320-HRA), manufactured by Nikkiso Co., Ltd.) by irradiating ultrasonic waves for 120 seconds using the wet measurement method. The volume-based cumulative particle diameter means the diameter of particles relative to a predetermined ratio of the cumulative distribution obtained by integrating all particles in order from the smallest volume.

[0061] In principle, laser diffraction scattering particle size analyzers measure the distribution of cumulative particle sizes based on volume, and the measurement values ​​of the cumulative 10% particle size (D10), cumulative 50% particle size based on volume (D50), and cumulative 90% particle size based on volume (D90) can be confirmed using the measuring device's software.

[0062] (Measurement of angle of repose and angle of collapse of polymer particles) The measurement was performed using a multi-function powder property measuring instrument (MULTITESTER MT-1001, manufactured by Seishin Enterprise Co., Ltd.) at room temperature of 25° C. and humidity of 40%.

[0063] (Measurement of Melting Enthalpy of Polymer Particles) A differential scanning calorimeter (Jada DSC LAB SYSTEC, manufactured by ParkinElmer) was used as the measuring device, and the temperature was raised from 30° C. to 250° C. at a rate of 10° C. / min under a nitrogen atmosphere to calculate the fusion enthalpy. Specifically, the sum of the enthalpies of all the obtained endothermic peaks was regarded as the fusion enthalpy of the polymer particles.

[0064] (Measurement of Sphericity of Polymer Particles) Particles were observed at 1000x magnification using a scanning electron microscope, and the short and long diameters of 30 randomly selected particles were measured. The short diameter was divided by the long diameter for each particle to calculate the value, and the average of the calculated values ​​for the 30 particles was taken as the sphericity. For example, when the ratio of the short diameter to the long diameter is 1, the sphericity is 1.

[0065] (Measurement of water absorption and oil absorption of polymer particles) Based on the JIS-K5101 oil absorption measurement method, the water absorption was measured using ion-exchanged water and the oil absorption was measured using oleic acid.

[0066] (Evaluation of polymer particles) 1 g of particles was weighed out and placed in the center of a 10 cm x 10 cm piece of black artificial leather (product name: Suppurare, manufactured by Ideatech Japan), and spread using a finger in a circular motion. The smoothness, moist feeling, and applicability of the polymer particles were evaluated according to the following criteria. <Smoothness> ◎: Feels smooth. 〇: Feels somewhat smooth. ×: Feels rough and not very smooth. <Moisturizing feeling> ◎: Feels moist to the touch. 〇: Feels slightly moist to the touch. △: Feels slightly dry. ×: Feels dry. <Applicability> ◎: Can be applied evenly. ◯: Can be applied fairly evenly. ×: The powder tends to aggregate, resulting in non-uniform application.

[0067] Example 1 300 parts by weight of water, 100 parts by weight of polybutylene succinate, 1 part by weight of sorbitan monolaurate (HLB value: 8.6), and 20 parts by weight of polyvinyl alcohol were mixed and charged into a 1 L pressure vessel, which was then sealed. The temperature inside the vessel was raised to 140°C, and the mixture was stirred at 400 rpm per minute under a pressure of 0.5 MPa for 3 hours, and then cooled to 50°C to obtain an aqueous dispersion of particles. An oxidizing agent was added to the aqueous dispersion, which was then dehydrated by filtration, dried at 50°C, and classified to obtain particles 1. The weight percentage of the surfactant in particles 1 was 0.5% by weight, and the weight percentage of polyvinyl alcohol was 0.3% by weight. The physical properties of the obtained particles 1 are shown in Table 1.

[0068] Example 2 300 parts by weight of water, 80 parts by weight of polyhydroxyalkanoate, 20 parts by weight of polybutylene succinate, 3 parts by weight of sorbitan monolaurate (HLB value: 8.6), and 20 parts by weight of polyvinyl alcohol were mixed and charged into a 1 L pressure vessel and sealed. The temperature inside the vessel was raised to 160°C, and the mixture was stirred at 400 rpm per minute under a pressure of 1.0 MPa for 10 hours, and then cooled to 50°C to obtain an aqueous dispersion of particles. An oxidizing agent was added to the aqueous dispersion, and the mixture was washed with a large amount of water, dehydrated by filtration, dried at 50°C, and classified to obtain particles 2. The weight percentage of the surfactant in particles 2 was 0.8% by weight, and the weight percentage of polyvinyl alcohol was 0% by weight. The physical properties of the obtained particles 2 are shown in Table 1.

[0069] Example 3 200 parts by weight of water, 50 parts by weight of polybutylene succinate, 50 parts by weight of polybutylene succinate adipate, 0.1 parts by weight of sorbitan monolaurate (HLB value: 8.6), 0.5 parts by weight of diethylhexyl sodium sulfosuccinate, and 30 parts by weight of polyvinyl alcohol were mixed and charged into a 1 L pressure vessel and sealed. The temperature inside the vessel was raised to 140°C, and the mixture was stirred at 200 rpm per minute under a pressure of 1.0 MPa for 5 hours, and then cooled to 50°C to obtain an aqueous dispersion of particles. The aqueous dispersion was washed with a large amount of water, dehydrated by filtration, dried at 50°C, and classified to obtain particles 3. The weight percentage of the surfactant in particles 3 was 0% by weight, and the weight percentage of polyvinyl alcohol was 0.01% by weight. The physical properties of the obtained particles 3 are shown in Table 1.

[0070] Example 4 300 parts by weight of water, 100 parts by weight of polybutylene adipate terephthalate, 2 parts by weight of sorbitan sesquioleate (HLB value: 3.7), and 30 parts by weight of polyvinyl alcohol were mixed and charged into a 1 L pressure-resistant container and sealed. The temperature inside the container was raised to 140°C, and the mixture was stirred at 400 rpm per minute under a pressure of 1.0 MPa for 5 hours, and then cooled to 50°C to obtain an aqueous dispersion of particles. The aqueous dispersion was washed with a large amount of water, dehydrated by filtration, dried at 50°C, and classified to obtain particles 4. The weight percentage of the surfactant in particles 4 was 0% by weight, and the weight percentage of polyvinyl alcohol was 0%. The physical properties of the obtained particles 4 are shown in Table 1.

[0071] Comparative Example 1 20 parts by weight of water, 10 parts by weight of polybutylene succinate, 30 parts by weight of 3-methoxy-3-methyl-1-butanol, 35 parts by weight of a 10% aqueous solution of calcium phosphate tribasic, and 0.04 parts by weight of sodium lauryl sulfate were mixed and charged into a 1L pressure-resistant container and sealed. The temperature inside the container was raised to 120°C, and the mixture was stirred at 400 rpm per minute at a pressure of 0.5 MPa for 1 hour, and then cooled to 30°C to obtain a particle dispersion. 14 parts by weight of 20% hydrochloric acid was added to the dispersion, and after stirring for 20 minutes, the mixture was dehydrated by filtration, washed with a large amount of water, dried at 50°C, and classified to obtain particles. The evaluation results of the obtained particles are shown in Table 1.

[0072] [Table 1]

[0073] The polymer particles of Examples 1 to 4 had a smooth and moist feel to the touch, and it was also confirmed that they had excellent coatability. On the other hand, the particles of Comparative Example 1 were inferior in smoothness, were a powder that felt dry, and had poor applicability. The particles of the present invention contain a biodegradable polymer and exhibit specific physical properties, and thus have an excellent smooth and moist feel to the touch. [Industrial Applicability]

[0074] The polymer particles of the present invention have a smooth and moist feel and are therefore useful as an additive for cosmetics and coating agents. The polymer particles of the present invention have a smooth and moist feel and are biodegradable, and therefore can be used as an environmentally friendly material as an additive in various products such as cosmetics, paints, coating compositions, films, molded articles, etc.

Claims

1. A polymer particle comprising a biodegradable polymer (A) and at least one selected from a surfactant and a water-soluble polymer, and not containing 3-alkoxy-3-methyl-1-butanol, 3-alkoxy-3-methyl-1-butyl acetate, an ester-based organic solvent, a chlorine-based organic solvent, an aromatic hydrocarbon, a ketone-based solvent, or a lower alcohol, The biodegradable polymer (A) is a polyester resin, The weight ratio of the biodegradable polymer (A) in the polymer particles is 50% by weight or more, A volume-based cumulative 50% particle size (D50) is 1 to 100 μm; a value obtained by dividing the volume-based cumulative 90% particle size (D90) by the particle size (D50) is 1.0 to 3.5; The angle of repose is 33 to 65 degrees. The water absorption is 20 to 130 mL / 100 g. Polymer particles are used as an additive in cosmetics.

2. 2. The polymer particles according to claim 1, wherein the polyester resin comprises at least one selected from an aliphatic polyester resin and an aliphatic-aromatic polyester resin.

3. 3. The polymer particles according to claim 1, having a melting enthalpy of 0 to 140 J / g.

4. 3. The polymer particles according to claim 1, wherein the oleic acid oil absorption is from 30 to 150 mL / 100 g.

5. The weight ratio of the biodegradable polymer (A) in the polymer particles is 90 to 99.999% by weight, and the total weight ratio of the surfactant and the water-soluble polymer in the polymer particles is 0.001 to 10% by weight.

6. A cosmetic comprising the polymer particles according to claim 1 or 2.

Images