Cosmetic

Abstract

Provided is a cosmetic containing particles that decompose in the environment after use and do not remain in the form of particles (solid matter), and that exhibit high flexibility, slipperiness, and light diffusibility when added to a cosmetic.　This cosmetic comprises at least one of the following types of particles (i) and (ii). (i) Spherical elastomer particles that have a volume average particle size of 1.0-100 μm and that are crosslinked particles of a copolymer having a polyester structure and a polyether structure. (ii) Composite elastomer particles that have polyorganosilsesquioxane or silica on the surface of the spherical elastomer particles.

Description

cosmetics

[0001] The present invention relates to a cosmetic preparation containing elastomer spherical particles having a copolymer having a polyester and polyether structure as a constituent unit and / or elastomer composite particles having polyorganosilsesquioxane or silica on the surface of the elastomer spherical particles.

[0002] Makeup cosmetics such as foundation are intended to conceal morphological problems such as wrinkles, pores, and rough skin texture, as well as color problems such as skin blemishes and freckles, and to make the skin appear smooth and beautiful, and in recent years, emphasis has been placed on a natural, unartificial finish (bare skin feel). A natural finish of a cosmetic product is evaluated when it is free of unnatural gloss (luster), has excellent uniformity of makeup film application, and has high transparency.

[0003]

[0003] Conventionally, many new materials and technologies have been proposed to obtain a natural finish while maintaining the effects of the above-mentioned makeup cosmetics. In particular, cosmetics containing various types of diffuse reflection type powders are known as a method for concealing morphological defects.

[0004] Patent Document 1 proposes a multi-layer cosmetic composition for concealing wrinkles that combines a first-layer makeup base containing an adhesive substance with a second-layer makeup finishing agent containing a light-diffusing and light-reflecting powder. This multi-layer cosmetic composition for concealing wrinkles uses, for example, a light-diffusively reflecting composite powder in which talc particles are coated with an acrylic polymer.

[0005] However, this cosmetic has the drawback that if the cosmetic film is left on the skin for a long period of time, the sebum mixes with the adhesive substance, causing the powder and adhesive substance to fall outside the appropriate mixing range, thereby reducing the cosmetic's effectiveness.

[0006] Patent Document 2 discloses a flaky fine powder obtained by coating the surface of a flaky material such as natural mica with spherical silica fine particles. This flaky fine powder uses spherical fine particles that have a large surface diffuse scattering effect for light, and so when this flaky fine powder is used as a cosmetic ingredient, it is said to have the following technical effects: "It is possible to suppress the excessive gloss of the substrate mica and to exert a so-called soft focus effect that makes fine wrinkles less noticeable. It is also possible to obtain cosmetics that have further improved smoothness and feel during use."

[0007] However, because the flaky fine powder has such excellent slipperiness, cosmetics containing it tend to smudge during application, making it difficult to apply the cosmetic evenly, and thus failing to achieve a natural finish. Furthermore, the silica fine particles used as a coating agent reduce the contact area of ​​the composite powder with the skin, thereby reducing its adhesion to the skin and making the composite powder more likely to peel off from the skin due to physical impacts such as rubbing against clothing, thereby reducing the durability of the cosmetic effect. Furthermore, reducing the proportion of silica fine particles in the flaky fine powder to improve the adhesion of the composite powder to the skin is disadvantageous in that it is no longer effective against morphological problems.

[0008] Other similar techniques aimed at avoiding morphological problems or achieving a natural finish include a cosmetic containing a pigment with a core-shell structure in which a flaky extender pigment is used as a core, which is coated with colored pigment-containing titanium dioxide, and this is further coated with a light-diffusing powder (Patent Document 3); a technique in which a composite powder in which the surface of a clay mineral is coated with an inorganic metal hydroxide such as aluminum hydroxide is blended into a cosmetic (Patent Documents 4 and 5); a cosmetic containing a powder having a refractive index of 1.6 to 1.7 such as barium sulfate, which has a layer coated on the surface with a high refractive index metal oxide, and further coated thereon with one or more layers selected from yellow iron oxide, black iron oxide, and red iron oxide (Patent Document 6); and a cosmetic containing a silica / zinc oxide composite obtained by combining silica sol with zinc oxide or the like (Patent Document 7).

[0009] However, although these composite powders exhibit a certain degree of soft focus effect due to their light diffusion effect, they are composed of inorganic metal oxides or inorganic metal hydroxides, and therefore, in terms of the feel of the cosmetic when used, the hardness of the composite powder itself means that they are not fully satisfactory in terms of softness, moistness, smoothness, etc.

[0010] On the other hand, for the purpose of improving the feel of cosmetic powders when used, i.e., imparting a feel of use such as a dry and smooth feeling, spreadability, adhesiveness, etc., Patent Document 8 proposes particles in which the surface of scaly inorganic particles is coated with polyurethane, a styrene-butadiene copolymer, a silicone elastomer, or a polyolefin elastomer, and it is said that this gives a soft and moist feel to the touch.

[0011] Another document proposes particles having a silicone elastomer attached to or coated on their surface, and a method for producing the same. For example, Patent Document 9 proposes a method of grinding and mixing a silicone elastomer having a reactive functional group with silica, but because the silica particles that serve as base particles are ground, it is not possible to obtain particles that maintain their original shape and particle size. That is, it is not possible to obtain particles with a specific shape, such as granular, plate-like, or rod-like, and it is also difficult to control the particle size. Patent Document 10 proposes a method of mixing base particles with a curable silicone that will serve as a silicone elastomer and then curing the silicone, but the resulting particles contain multiple base particles. Patent Document 11 also proposes a method of emulsifying and dispersing a mixture of silica particles that serve as base particles and a curable silicone that will serve as a silicone elastomer in water, and then curing the silicone. Patent Document 12 proposes a method of emulsifying and dispersing a mixture of an aqueous dispersion of silica particles and a curable silicone that will serve as a silicone elastomer in water, and then curing the silicone. However, both methods result in particles that contain multiple base particles or particles that do not contain any base particles.

[0012] Therefore, Patent Document 13 proposes adding an acidic or alkaline substance and a compound selected from alkoxysilanes, silanol group-containing silanes, and partial condensates thereof to a mixed aqueous dispersion in which powder and silicone elastomer are dispersed, and then causing a hydrolysis and condensation reaction of this compound to produce composite particles in which silicone elastomer is attached to the surface of core powder using silicone resin as a binder.Cosmetics containing this composite particle have the smooth, soft, and moist feel that is characteristic of silicone elastomers, and have good spreadability, softness, adhesion, and blendability, and can impart a skin topography correcting effect.

[0013] Furthermore, silicone rubber spherical particles are used in a wide range of cosmetics and cosmetic materials, including makeup cosmetics such as foundations and makeup bases, skin care cosmetics such as creams and emulsions, and sunscreen cosmetics, for the purposes of imparting a soft feel, smoothness, and other sensations upon use to cosmetics, scattering light to create a natural finish, and making pores and wrinkles less visible.

[0014] For example, proposed cosmetics include those containing polymethylsilsesquioxane particles and powders (Patent Document 14), makeup cosmetics containing spherical silicone rubber particles and powders (Patent Document 15), and cosmetics containing silicone composite particles and powders in which silicone rubber spherical particles are coated with a polyorganosilsesquioxane resin (Patent Document 16). As described above, these silicone rubber spherical particles and composite particles in which silicone rubber spherical particles are coated with a polyorganosilsesquioxane resin can impart a soft feel, smoothness, and other usability sensations to cosmetics.

[0015] JP 6-128122 Publication International Publication No. 92 / 03119 Pamphlet JP 8-188723 JP 9-20609 JP 2002-146238 JP 2003-40737 Patent 3702072 Patent 3963635 JP 8-3451 Publications JP-A-3-294357, JP-A-2-232263, JP-A-3-281536, JP-A-2011-1332, JP-A-63-297313, JP-A-8-12524, JP-A-9-20631

[0016] However, the silicone rubber spherical particles, polymethylsilsesquioxane particles, and silicone composite particles formed by coating silicone rubber spherical particles with a polyorganosilsesquioxane resin, which are incorporated into various cosmetics and the like, are likely to remain in the environment without being decomposed when released or leached into natural environments such as soil, land water, seawater, or the ocean, because the particle structure does not contain a skeleton or unit that has or imparts degradability.

[0017] In addition, plastics that have flowed into the ocean and microplastics that have been broken down and refined to millimeter to micrometer sizes have the ability to adsorb harmful substances and pathogens present in the environment, and there are concerns that marine organisms could accidentally ingest these and have a negative impact on the ecosystem, so moves are beginning to be made to regulate these microplastics.On the other hand, spherical particles that do not fall under the category of microplastics and are incorporated into various cosmetics, etc., include silica and biodegradable cellulose powder, but in terms of flexibility, slipperiness, and light diffusion, they are inferior to silicone rubber spherical particles, polymethylsilsesquioxane particles, and silicone composite particles made of silicone rubber spherical particles coated with polyorganosilsesquioxane resin.

[0018] In light of this background, there is a demand for elastomeric spherical particles that decompose in the environment after use, do not remain as particles (solid matter), and can exhibit high flexibility, slipperiness, and light diffusing properties when incorporated into cosmetics.

[0019] The present invention has been made in view of the above circumstances, and aims to provide a cosmetic containing elastomer spherical particles and / or elastomer composite particles whose constituent units are (co)polymers that are highly degradable in natural environments including soil, land water, and marine / seawater due to external stimuli such as light, heat, acids and bases, or the action of microorganisms and fungi.

[0020] As a result of intensive research conducted by the present inventors to achieve the above-mentioned object, they discovered that a cosmetic containing elastomer spherical particles and / or elastomer composite particles, which are crosslinked particles of a copolymer having a specific polyester structure and a polyether structure, can solve the above-mentioned problems, and thus completed the present invention.

[0021] Accordingly, the present invention provides the following cosmetic preparations. [1]. A cosmetic preparation containing at least one type of particle selected from the following (i) and (ii): (i) elastomeric spherical particles having a volume average particle size of 1.0 to 100 μm, which are crosslinked particles of a copolymer having a polyester structure and a polyether structure; (ii) elastomeric composite particles having polyorganosilsesquioxane or silica on the surface of the elastomeric spherical particles (i). [2]. The cosmetic preparation according to [1], wherein the copolymer is a polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule. [3]. The cosmetic preparation according to [2], wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (1) or (2): (In general formula (1), R 1 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 2 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (3a), (3b), or (3c), where k is a number that satisfies 1≦k≦10, l is a number that satisfies 1≦l≦1,000, m is a number that satisfies 1≦m≦1,000, and n is a number that satisfies 1≦n≦100. 3 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 4 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (4a) or (4b), each p independently represents a number that satisfies 1≦p≦10, each l independently represents a number that satisfies 1≦l≦1,000, each m independently represents a number that satisfies 1≦m≦1,000, and each q independently represents a number that satisfies 1≦q≦100. (In general formulas (3a), (3b), (3c), (4a) and (4b), R 5 each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms; R 6each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.) [4]. The cosmetic according to [2], wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (5): (In general formula (5), R 1 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 2 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (3a), (3b), or (3c), l is a number that satisfies 1≦l≦1,000, m is a number that satisfies 1≦m≦1,000, and each r is independently a number that satisfies 1≦r≦100. (In general formulas (3a), (3b) and (3c), R 5 each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms; R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.) [5]. The cosmetic according to any one of [1] to [4], wherein the elastomer spherical particles have a rubber hardness of 10 to 80 measured by a Type A durometer as defined in JIS K 6253. [6]. The cosmetic according to any one of [1] to [5], wherein the cosmetic is a skin care cosmetic. [7]. The cosmetic according to any one of [1] to [5], wherein the cosmetic is a makeup cosmetic. [8]. The cosmetic according to any one of [1] to [5], wherein the cosmetic is a sun care cosmetic.

[0022] Cosmetics containing the elastomeric spherical particles and / or elastomer composite particles of the present invention can provide cosmetics that have good spreadability, softness, adhesion, and blendability, and have excellent skin contouring effects. Furthermore, elastomeric composite particles obtained by adhering polyorganosilsesquioxane or silica to the surface of elastomeric spherical particles are excellent in spreadability, ease of use, adhesion, dispersibility, contouring effects, water resistance, and sebum resistance. Cosmetics using such composite particles of the present invention can be easily spread, soft, and spread evenly, and have excellent dispersibility, sebum resistance, and cosmetic wear. Furthermore, regardless of the type of cosmetic they are incorporated into, they can provide cosmetics that have excellent stability that does not change with temperature or over time. Furthermore, the elastomeric spherical particles and / or elastomer composite particles have a polyester structure with a degradable unit skeleton within the particles, and the crosslinked structure of the particles is cleaved in the presence of moisture, making them degradable. In particular, particles having a poly-ε-caprolactone structure, which is a microorganism-recognition skeleton, as the polyester structure in the particles are expected to be environmentally degradable and biodegradable. Therefore, cosmetics containing the elastomer spherical particles and / or elastomer composite particles of the present invention are expected to be used as materials that reduce environmental impact.

[0023] 1 is an electron microscope photograph of elastomer spherical particles obtained in Preparation Example 1. 2 is an electron microscope photograph of elastomer spherical particles obtained in Preparation Example 3. 3 is an electron microscope photograph (magnification x 1,000) of elastomer composite particles (silica-coated elastomer spherical particles) obtained in Preparation / Production Example 3. 4 is an electron microscope photograph (magnification x 7,500) of elastomer composite particles (silica-coated elastomer spherical particles) obtained in Preparation / Production Example 3.

[0024] The cosmetic of the present invention is characterized by containing: (i) elastomer spherical particles having a volume average particle size of 1.0 to 100 μm, which are crosslinked particles of a copolymer having a polyester structure and a polyether structure; and / or (ii) elastomer composite particles having polyorganosilsesquioxane or silica on the surface of the elastomer spherical particles.

[0025] The present invention will be described in detail below in the following order: I. Elastomeric spherical particles and a method for producing elastomer spherical particles, II. Elastomeric composite particles and a method for producing elastomer composite particles, III. Elastomeric spherical particles and a method for producing cosmetics using elastomer composite particles, and IV. Elastomeric spherical particles and cosmetics containing elastomer composite particles.

[0026] I. Elastomeric Spherical Particles and Method for Producing Elastomeric Spherical Particles The elastomer spherical particles blended in the cosmetic of the present invention refer to polymers (crosslinked particles) of copolymers having a polyester structure and a polyether structure.

[0027] The shape of the elastomeric spherical particles is preferably spherical. In the present invention, "spherical" does not refer only to a true sphere, but also includes deformed ellipsoids with an average aspect ratio (length of longest axis / length of shortest axis) typically ranging from 1 to 4, preferably from 1 to 2, more preferably from 1.0 to 1.6, and even more preferably from 1.0 to 1.4. As described in the production method described below, when a copolymer having a polyester structure and a polyether structure is emulsified, suspended, and dispersed using a surfactant or suspending agent and crosslinked, the resulting particles have a spherical shape. The shape of the elastomeric spherical particles can be confirmed, for example, by observation using an optical microscope or electron microscope. The aspect ratio is calculated by measuring the lengths of the longest and shortest axes of 50 randomly selected particles from a micrograph and averaging the results.

[0028] In the present invention, the volume average particle size of the elastomeric spherical particles is in the range of 1.0 to 100 μm, preferably 1.0 to 50 μm, and more preferably 2.0 to 20 μm. If the volume average particle size is greater than 100 μm, the fluidity of the particles decreases and the tendency to aggregate increases, making it impossible to impart sufficient smoothness and light diffusion properties to the particles. Furthermore, if the volume average particle size is less than 1.0 μm, the particles may have a reduced silky feel and a rough texture, resulting in reduced light diffusion properties. The volume average particle size of the elastomeric spherical particles is a value measured as follows. Prior to measuring the volume average particle size, the particle sizes of 50 particles are randomly selected from a micrograph of the elastomeric spherical particles, and the average particle size is determined to be equal to or less than 1 μm. A dispersion liquid is prepared by redispersing the elastomer spherical particles in water using various surfactants, and if the result of the above determination is 1 μm or more, the volume average particle size is indicated as a value measured by an electrical resistance method, and if the result of the determination is less than 1 μm, the volume average particle size is indicated as a value measured by a laser diffraction / scattering method.

[0029] It is preferable that the rubber (elastomer) that is a component of the elastomer spherical particles is free of tackiness or stickiness. The rubber hardness of the rubber (elastomer) that is a component of the elastomer spherical particles, as measured using a Type A durometer as specified in JIS K6253, is preferably in the range of 10 to 80, more preferably 20 to 70. Furthermore, as measured using an Asker Rubber Hardness Tester Type C as specified in the Society of Rubber Industry Standards (SRIS), the rubber hardness of the rubber (elastomer) that is a component of the elastomer spherical particles is preferably in the range of 10 to 90, more preferably 20 to 90, and even more preferably 40 to 90. If the rubber hardness value in each measurement is less than 10, the particles will tend to aggregate more easily and disperse less well. Furthermore, if the rubber hardness measured using a Type A durometer is greater than 80, the soft feel will be reduced, which is undesirable.

[0030] The elastomer spherical particles are further preferably particles made of a polyester-polyether copolymer polymer having at least two radically polymerizable unsaturated groups in one molecule, i.e., crosslinked particles of a polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule.

[0031] The polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule is preferably a copolymer represented by the following general formula (1) or (2). (In general formula (1), R 1 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 2 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (3a), (3b), or (3c), where k is a number that satisfies 1≦k≦10, l is a number that satisfies 1≦l≦1,000, m is a number that satisfies 1≦m≦1,000, and n is a number that satisfies 1≦n≦100. 3 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 4 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (4a) or (4b), each p independently represents a number that satisfies 1≦p≦10, each l independently represents a number that satisfies 1≦l≦1,000, each m independently represents a number that satisfies 1≦m≦1,000, and each q independently represents a number that satisfies 1≦q≦100. (In general formulas (3a), (3b), (3c), (4a) and (4b), R 5 each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms; R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0032] R 1 Examples of alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene groups, and preferably methylene, ethylene, trimethylene, and tetramethylene groups.

[0033] R 3Examples of alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene groups, and preferably methylene, ethylene, trimethylene, and tetramethylene groups.

[0034] R 2 represents a radically polymerizable functional group-containing organic group represented by general formula (3a), (3b), or (3c), and R 4 represents a radical polymerizable functional group-containing organic group represented by general formula (4a) or (4b). In general formulas (3b), (3c), (4a), and (4b), R 5 Examples of R include alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene, and are preferably methylene, ethylene, trimethylene, or tetramethylene. 6 Examples of the radical polymerizable functional group-containing organic groups represented by general formulas (3a), (3b), (3c), (4a), and (4b) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, or another alkyl group having 1 to 3 carbon atoms, and preferably a hydrogen atom or a methyl group. Specific examples of the radical polymerizable functional group-containing organic groups represented by general formulas (3a), (3b), (3c), (4a), and (4b) include residues derived from polymerizable monomers, and specific examples of the polymerizable monomers include hydroxyl group-containing (meth)acrylic acid esters, isocyanate group-containing (meth)acrylic acid esters, and (meth)acrylic acid chlorides.

[0035] Examples of hydroxyl group-containing (meth)acrylic acid esters include hydroxyalkyl esters of (meth)acrylic acid having 2 to 8 carbon atoms, such as hydroxyethyl (meth)acrylic acid ester and hydroxypropyl (meth)acrylic acid ester, and carboxy(meth)acrylates, such as carboxyethyl (meth)acrylate, (meth)acryloyloxyethyl succinate, and (meth)acryloyloxyethyl phthalate. Examples of isocyanate group-containing (meth)acrylic acid esters include isocyanate ethyl (meth)acrylic acid ester, isocyanate propyl (meth)acrylic acid ester, isocyanate butyl (meth)acrylic acid ester, and isocyanate hexyl (meth)acrylic acid ester. Examples of (meth)acrylic acid chlorides include acryloyl chloride, methacryloyl chloride, acryloyl bromide, and methacryloyl bromide.

[0036] The polyester structure (unit) of the polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule is preferably an aliphatic polyester, which is considered to have or have high degradability. Examples of aliphatic polyesters include poly-ε-caprolactone, poly-β-propiolactone, γ-butyrolactone, polylactic acid, polyhydroxybutyrate, polyglycolic acid, polyethylene adipate, polyhydroxybutyric acid, polyethylene succinate, and polybutylene succinate. In particular, from the viewpoints of degradability and ease of handling, those having a poly-ε-caprolactone structure are preferred.

[0037] In general formula (1), k's each independently represent a number within the range of 1≦k≦10, and preferably a number within the range of 1≦k≦6. In general formula (2), p's each independently represent a number within the range of 1≦p≦10, and preferably a number within the range of 1≦p≦6.

[0038] In general formula (1), n ​​is independently a number satisfying 1≦n≦100, preferably a number satisfying 1≦n≦50, and more preferably a number satisfying 2≦n≦20. In general formula (2), q is independently a number satisfying 1≦q≦100, preferably a number satisfying 1≦q≦50, and more preferably a number satisfying 2≦q≦20. When the values ​​of n and q are greater than the upper limit values, the crystallinity increases due to the intramolecular / intermolecular interactions of the polymer caused by the ester structure (unit). If the fluidity of the copolymer is too low, this may affect the handleability in the preparation step of the emulsion (suspension) composition described below.

[0039] In general formulas (1) and (2), l is a number within the range of 1≦l≦1,000, preferably 2≦l≦100. In general formulas (1) and (2), m is a number within the range of 1≦m≦1,000, preferably 10≦m≦500. If the value of l is greater than the upper limit, the crystallinity increases due to the intramolecular / intermolecular interactions of the polymer caused by the ethylene oxide structure (unit), which may reduce the fluidity of the copolymer. In this case, as described above, this may undesirably affect the handleability in the preparation process of the emulsion (suspension) composition described below.

[0040] The polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule is preferably a copolymer represented by the following general formula (5) or (6), from the viewpoints of ease of handling of raw materials and production. (In general formula (5), R 1 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 2 each independently represents a radically polymerizable functional group-containing organic group represented by general formula (3a), (3b) or (3c), l is a number of 1≦l≦1,000, m is a number of 1≦m≦1,000, and r is a number of 1≦r≦100. (In general formula (6), R 3 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 4each independently represents a radically polymerizable functional group-containing organic group represented by general formula (4a) or (4b), l is a number that satisfies 1≦l≦1,000, m is a number that satisfies 1≦m≦1,000, and each s is independently a number that satisfies 1≦s≦100.

[0041] [Method of Producing Polyester-Polyether Copolymer] Before describing the method of producing the elastomeric spherical particles, a method of producing the polyester-polyether copolymer constituting the elastomeric spherical particles will be described. Examples of methods for producing polyester-polyether copolymers include starting materials such as various polyethers containing active hydrogen, such as polyethers having hydroxyl groups, carboxy-modified polyethers, and amino-modified polyethers, and ring-opening polymerization of cyclic ε-caprolactone, γ-butyrolactone, or the like to obtain poly-ε-caprolactone-modified polyethers or poly-γ-butyrolactone-modified polyethers. Subsequently, polymerizable monomers having radically polymerizable unsaturated groups are introduced via ester bonds, ether bonds, urethane bonds, amide bonds, or the like. From the viewpoint of reactivity during production, it is preferable that the terminal structures of the various polyethers have reactive functional groups bonded to primary carbon atoms.

[0042] In the above-described production method, reaction conditions include, but are not limited to, the following: To 1.0 equivalent of an active hydrogen-containing polyether, such as a polyether or a carboxy-modified polyether, 3.0 to 4.0 equivalents (functional group equivalent ratio) of cyclic-ε-caprolactone are added, for example, and the reaction is carried out at 120°C for 4 to 6 hours in the presence of a conventional ring-opening polymerization catalyst, to obtain a poly-ε-caprolactone-modified polyether. Next, to 1.0 mole of hydroxyl groups in the obtained poly-ε-caprolactone-modified polyether, 1.0 to 1.25 moles (functional group equivalent ratio) of a (meth)acrylic acid chloride such as acrylic acid chloride or an isocyanate group-containing (meth)acrylic acid ester such as isocyanate ethyl (meth)acrylate is added, for example, and a reaction catalyst is added as necessary, followed by reaction at 40 to 100°C for 4 hours or longer. After the reaction, the crude product is quenched with alcohol or the like, and then by-products are removed by filtration, washing with water, and / or adsorption treatment. Finally, the solvent is distilled off to obtain an acrylic-modified poly-ε-caprolactone polyether (polyester-polyether copolymer).

[0043] When a polyether having a hydroxyl group is used as a starting material, examples of polyester-polyether copolymers include those represented by formulas (7a) and (7b) (only one side structure is shown due to the symmetrical structure).

[0044] In formulas (7a) and (7b), R 5 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R 6 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. l, m, and r are 1≦l≦1,000, 1≦m≦1,000, and 1≦r≦30, and preferably 2≦l≦100, 10≦m≦500, and 2≦r≦10.

[0045] When a carboxy-modified polyether is used as a starting material, examples of polyester-polyether copolymers include those shown in formulas (8a) and (8b) (only one end is shown due to the symmetrical structure).

[0046] In formulas (8a) and (8b), R5 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R 6 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Furthermore, l, m, s, and t are 1≦l≦1,000, 1≦m≦1,000, 1≦s≦30, and 0≦t≦10, and preferably 2≦l≦100, 10≦m≦500, 2≦s≦10, and 1≦t≦10.

[0047] The catalyst used in the ring-opening polymerization of cyclic-ε-caprolactone may be any known catalyst, and is not limited thereto. Specific examples include organotitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, and tetra-n-butoxytitanium; organotin compounds such as di-n-butyltin laurate, diisobutyltin oxide, and dibutyltin diacetate; acetates of magnesium, calcium, zinc, and the like; antimony oxide; stannous halides; and perchloric acid.

[0048] The amount of the ring-opening polymerization catalyst added may be in the range of 1 to 10,000 ppm, preferably 10 to 1,000 ppm, based on the ε-caprolactone monomer (cyclic ε-caprolactone).

[0049] As a method for introducing a polymerizable monomer having a radically polymerizable unsaturated group into the poly-ε-caprolactone-modified polyether, various catalysts may be used depending on the reaction substrate (reactive functional group) of the polymerizable monomer and the skeleton to be formed, and a conventionally known catalyst may be used.

[0050] When the reaction between a polymerizable monomer and a poly-ε-caprolactone-modified polyether is an esterification reaction, examples of the (esterification) catalyst used in the esterification reaction include alcoholates, carboxylates, or chelate compounds of titanium, zirconium, tin, aluminum, and zinc, as well as Lewis acid catalysts such as boron trifluoride and boron trifluoride etherate; acid catalysts such as hydrochloric acid, sulfuric acid, hydrogen bromide, acetic acid, trifluoroacetic acid, methanesulfonic acid, and p-toluenesulfonic acid; and amine catalysts such as pentamethyldiethylenetriamine (PMDETA), trimethyltriazacyclononane (TACN), triethylamine (TEA), 4-(N,N-dimethylamino)pyridine (DMAP), 1,4-diazabicyclo(2,2,2)octane (DABCO), and tetramethylethylenediamine (TMEDA). Among these, amine catalysts are preferred from the viewpoints of stability of the product obtained by the esterification reaction and economy.

[0051] When an amine catalyst is used, a dehydration condensation agent may be added to improve the reaction efficiency. Examples of the dehydration condensation agent that can be used include, but are not limited to, 1,1'-carbonyldiimidazole (CDI), N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC.HCl), and 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU).

[0052] When the reaction between a polymerizable monomer and a poly-ε-caprolactone-modified polyether is a urethanization reaction, examples of the catalyst used in the urethanization reaction include amines such as triethylamine, triethylenediamine, pentamethylenediethylenetriamine, N,N-dimethylethanolamine, 1,4-diazabicyclo(2,2,2)octane (DABCO), pyridine, and N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA); organic tin compounds such as di-n-butyltin laurate, diisobutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate (DBTL), and dioctyltin dineodecanoate; tetramethoxytitanium, tetraethoxysilane, and the like. organic titanium compounds such as titanium dioxide, tetra-n-propoxy titanium, tetrabutoxy titanium, tetrakis(octyloxy) titanium, titanium acetylacetonate, titanium tetraacetylacetonate, dodecylbenzenesulfonic acid titanium compound, phosphate ester titanium complex, titanium triethanolaminate, titanium diisopropoxybis(ethylacetoacetate); organic zirconium compounds such as n-propyl zirconate, n-butyl zirconate, zirconium tetraacetylacetonate, zirconium dibutoxybis(ethylacetoacetate), zirconium octylate compound; and organic iron compounds such as tris(2,4-pentanedionato)iron(III).

[0053] The amount of catalyst added when introducing these polymerizable monomers having radically polymerizable unsaturated groups may be in the range of 1 to 10,000 ppm, preferably 10 to 1,000 ppm, based on the polymerizable monomer.

[0054] During the reaction, a polymerization inhibitor or antioxidant can be used to inhibit the polymerization reaction of the (meth)acrylate group during the reaction. Examples of the polymerization inhibitor or antioxidant include, but are not limited to, hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,4-dimethyl-6-t-butylphenol, p-benzoquinone, dibutylhydroxytoluene, 2,5-dihydroxy-p-benzoquinone, and mequinol.

[0055] A method for producing a polyester-polyether copolymer includes, when a carboxy-modified polyether is used as a starting material, an esterification reaction with a poly-ε-caprolactone-modified (meth)acrylate represented by the following formula (9): Commercially available poly-ε-caprolactone-modified (meth)acrylates include PLACCEL FA2D, PLACCEL FA10L, PLACCEL FN2D, and PLACCEL FM4 (manufactured by Daicel Corporation). In general formula (9), R 7 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and v satisfies 1≦v≦50, preferably 1≦v≦30.

[0056] Examples of methods for producing the polyester-polyether copolymer include, but are not limited to, the following. To 1.0 mole of carboxy groups in the carboxy-modified polyether, 1.0 to 1.25 moles (functional group equivalent ratio) of poly-ε-caprolactone-modified (meth)acrylate (formula (9)) and 0.1 to 5.0 moles of an esterification catalyst are added and mixed, and the mixture is stirred at 15 to 150°C for 10 to 30 minutes. Optionally, 1.0 to 1.25 moles of a dehydration condensation agent are added thereto, and the mixture is reacted at 15 to 150°C for 4 to 20 hours. After the reaction, the crude product is filtered, washed with water, and / or subjected to an adsorption treatment to remove by-products, and finally the solvent is distilled off to obtain an acrylic-modified polyester(poly-ε-caprolactone)-polyether copolymer.

[0057] The obtained polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule is preferably liquid, and the weight-average molecular weight (Mw.) measured by gel permeation chromatography (GPC) is preferably in the range of 100 to 100,000, more preferably 500 to 50,000. If the weight-average molecular weight is less than the lower limit mentioned above, the crosslink density of the elastomer in the obtained elastomer spherical / composite particles will be high, which is undesirable as it may result in poor degradability, whereas if it is greater than the upper limit mentioned above, the viscosity of the copolymer will be high, which may make it difficult to prepare the elastomer spherical particles.

[0058] In the filtration step, the crude reaction product may be diluted with a hydrophobic organic solvent to adjust its viscosity. The hydrophobic organic solvent to be used is not particularly limited, but toluene, hexane, ethyl acetate, etc. are preferred from the viewpoint of solubility and affinity for the polyester-polyether copolymer.

[0059] The adsorption treatment step is carried out for the purpose of removing hydrochlorides that cannot be completely removed by washing with water, and for the purpose of dehydration, decolorization, and deodorization. Any conventionally known adsorbent may be used, and a combination of multiple adsorbents may be used. Preferable adsorbents include desiccants such as magnesium sulfate and sodium sulfate, activated carbon, silica gel, and Kyoward series (manufactured by Kyowa Chemical Industry Co., Ltd.).

[0060] [Method for producing elastomeric spherical particles] Next, a method for producing elastomeric spherical particles using the polyester-polyether copolymer obtained by the above method will be described. The elastomeric spherical particles can be produced by a known method via a dispersion state of the elastomeric spherical particles. The elastomeric spherical particles can be produced, for example, by a method comprising the following steps i) to iii): i) A step of preparing an emulsion (suspension) composition by stirring, emulsifying, and suspending the following components (A), (B), (C), and (D): (A) a copolymer having a polymerizable group and having a polyester structure and a polyether structure; (B) an aqueous phase component or an oil phase component that is insoluble or poorly soluble in the component (A); (C) a surfactant or suspending agent; and (D) a polymerization initiator. ii) A step of obtaining a dispersion of elastomeric spherical particles by (radical) polymerizing the component (A) in the emulsion (suspension) composition obtained in the step i) using an external stimulus such as heat, light, or ultraviolet light; and iii) A step of obtaining elastomeric spherical particles by washing and drying to remove the component (B), which is the continuous phase, from the dispersion of elastomeric spherical particles obtained in the step ii).

[0061] When elastomer spherical particles are obtained by the above-described production method in which an emulsion (suspension) composition is prepared and then a (radical) polymerization reaction is carried out, the shape of the obtained particles is spherical.

[0062] Step i) In step i), the following components (A), (B), (C), and (D) are stirred, emulsified, and suspended to prepare an emulsion (suspension) composition. The components used in step i) are as follows:

[0063] Component (A) is a copolymer having a polymerizable group and a polyester structure and a polyether structure, preferably a polyester-polyether copolymer having a radically polymerizable unsaturated group. The constituent units of the elastomer spherical particles are derived from a copolymer having a polyester structure and a polyether structure, and preferably a polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule. Specific examples of component (A) include polyester-polyether copolymers represented by the general formula (1) or (2), and more preferably polyester-polyether copolymers represented by the general formula (5) or (6).

[0064] The content of component (A) in the emulsion (suspension) composition prepared in step i) is preferably 1.0 to 80 parts by mass per 100 parts by mass of the composition. If the amount of component (A) is less than the above lower limit, production efficiency may decrease, while if it is more than the above upper limit, poor emulsification (suspension) may occur, making it difficult to obtain a dispersion of the elastomer spherical particles, which is undesirable.

[0065] Component (B) is a component that becomes a continuous phase in the emulsion (suspension) composition, and is an aqueous phase component in which component (A) is insoluble or poorly soluble, or an oil phase component.

[0066] When component (B) is an aqueous phase component, specific examples of the water contained in the aqueous phase component include distilled water, ion-exchanged water, pure water, and ultrapure water.

[0067] The aqueous phase component may contain any additives as long as they do not impair the function of the continuous phase. Specific examples include, but are not limited to, preservatives, salts, pH adjusters, chelating agents, vitamins, amino acids, moisturizers, and antioxidants. To achieve a composition in which component (A) is insoluble or slightly soluble, the water content of the aqueous phase component is preferably 90 to 100% by mass.

[0068] When component (B) is an oil phase component, examples of the oil phase component include silicone oil, hydrocarbon oil, higher fatty acid, ester oil, liquid oil, etc., and these may be used alone or in appropriate combination of two or more types, but are not limited to these.

[0069] Examples of silicone oils include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane.

[0070] Examples of hydrocarbon oils include liquid paraffin, α-olefin oligomer, isododecane, isohexadecane, squalane, ozokerite, squalene, ceresin, paraffin, isoparaffin, paraffin wax, polyethylene wax, polyethylene-polypropylene wax, pristane, polyisobutylene, petrolatum, and microcrystalline wax.

[0071] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0072] Examples of ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, isononyl isononanoate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid esters, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, penta-2-ethylhexanoate, Erythritol, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-hexyl palmitate butylundecyl, diisobutyl adipate, N-lauroyl-L-glutamic acid 2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, and the like.

[0073] Examples of liquid oils and fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, camellia oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, Japanese kaya oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, and triglycerin.

[0074] Component (B) has a kinematic viscosity of 100,000 mm at 25°C. 2 / s or less, and more preferably 10,000 mm 2 If the kinematic viscosity is greater than the above upper limit, emulsification (suspension) in step i) becomes difficult, and it may become difficult to obtain an emulsified (suspension) composition and elastomer spherical particles having a narrow particle size distribution.

[0075] When a surfactant is used as component (C), the type thereof is not particularly limited, and any conventionally known nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant may be used. These surfactants may be used alone or in appropriate combination of two or more.

[0076] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes. Examples of polyoxyethylene-modified organopolysiloxanes include linear polyether-modified silicones (trade names: KF-6011, KF-6011P, KF-6043, manufactured by Shin-Etsu Chemical Co., Ltd.), linear alkyl-co-modified polyether-modified silicones (trade name: KF-6048, manufactured by Shin-Etsu Chemical Co., Ltd.), branched polyether-modified silicones (trade names: KF-6028, KF-6028P, manufactured by Shin-Etsu Chemical Co., Ltd.), and branched alkyl-co-modified polyether-modified silicones (trade name: KF-6038, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0077] Examples of anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkanesulfonates, N-acyltaurate salts, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylate salts, N-acylamino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, and the like.

[0078] Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0079] Examples of amphoteric surfactants include alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, and alkylcarboxymethylhydroxyethylimidazolinium betaine.

[0080] As the surfactant, a nonionic surfactant or an anionic surfactant is preferred, since a small amount is sufficient to emulsify (suspend) the component (A) and obtain fine elastomer spherical particles.

[0081] When water or an aqueous phase component containing water is used as component (B), the surfactant (C) preferably has an HLB value, a parameter indicating the balance between hydrophobicity and hydrophilicity, of 6.0 to 18.0, more preferably 9.0 to 18.0.When an oil phase component is used as component (B), the surfactant (C) preferably has an HLB value of 2.0 to 13.0, more preferably 2.0 to 9.0.

[0082] The amount of surfactant (C) added is preferably 0.01 to 25 parts by mass, more preferably 0.05 to 15 parts by mass, per 100 parts by mass of the emulsion (suspension) composition. Addition of the surfactant in an amount less than the lower limit described above is undesirable, as it may result in poor emulsification or failure to obtain fine elastomer spherical particles. Addition of an amount greater than the upper limit described above is undesirable, as it may result in an increase in the viscosity of the entire composition, making it impossible to obtain fine elastomer spherical particles and resulting in insufficient particle dispersibility.

[0083] When a suspending agent is used as component (C), the type thereof is not particularly limited, and examples thereof include water-soluble polymer compounds such as conventionally known natural polymer compounds, semi-synthetic polymer compounds, and synthetic polymer compounds, or polymer compounds used as thickeners. These may be used alone or in appropriate combination of two or more types.

[0084] Examples of natural polymeric compounds include xanthan gum, cellulose, tamarind gum, tamarind seed gum, locust bean gum, gellan gum, HM pectin, carrageenan, guar gum, amaryllis seed gum, gum arabic, pullulan, agarose, agaropectin, alginic acid, karaya gum, succinoglycan, starch, dextrin, gelatin, and casein.

[0085] Examples of semi-synthetic polymer compounds include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, cationized xanthan gum, LM pectin (acid-treated / alkali-treated), cationized guar gum, alginate, soluble starch, and cellulose nanofiber.

[0086] Examples of synthetic polymer compounds include polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, polyacrylic acid amide, polyethylene glycol, polypropylene glycol, and polyethylene-polypropylene glycol.

[0087] As the suspending agent, xanthan gum, tamarind gum, carrageenan, guar gum, gum arabic, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, cationized xanthan gum, cationized guar gum, polyvinyl alcohol, and polyvinylpyrrolidone are preferred, since a small amount of the suspending agent is sufficient to suspend (emulsify) component (A) and to obtain fine elastomeric spherical particles.

[0088] The amount of suspending agent added is preferably 0.01 to 25 parts by mass, more preferably 0.05 to 15 parts by mass, per 100 parts by mass of the emulsion (suspension) composition. Addition of less than the lower limit of the above range is undesirable, as this may result in poor emulsification or failure to obtain fine elastomeric spherical particles. Addition of more than the upper limit of the above range is undesirable, as this may result in a significant increase in the viscosity of the composition, making it impossible to obtain fine elastomeric spherical particles and resulting in insufficient particle dispersibility.

[0089] The polymerization initiator of component (D) may be a conventionally known radical polymerization initiator. In the presence of the polymerization initiator, an external stimulus such as heating, light irradiation, or UV irradiation is applied to generate radicals, which can cause reaction and curing (crosslinking).

[0090] Specific examples of the polymerization initiator (D) that can be used include peroxides, azo initiators, photoinitiators, and redox initiators that combine an oxidizing agent and a reducing agent.

[0091] Examples of peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, t-butyl perbenzoate, hydrogen peroxide, etc. Perchlorates such as potassium perchlorate and sodium perchlorate may also be used.

[0092] Examples of azo initiators include 2,2'-azobis-isobutyronitrile, 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobis-(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis-(2-methylpropionate), dimethyl 2,2'-azobis-isobutyrate, t-butylperoxy-2-ethylhexanoate, and 2,2-azobis-(2-aminodipropane) dihydrochloride.

[0093] Examples of the photoinitiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, phenyl glyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide. Benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can also be used.

[0094] Examples of redox initiators include a combination of ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide, and a combination of ferrous sulfate, disodium ethylenediaminetetraacetic acid, Rongalite, and hydroperoxide. These redox initiators may also be used in combination with azo initiators or photoinitiators.

[0095] As the polymerization initiator, peroxides, azo-based initiators, and photoinitiators used in a heating method or a light irradiation method are preferred from the viewpoints of stability during the (radical) polymerization reaction of the emulsion (suspension) composition, ease of handling, and the like.

[0096] The amount of polymerization initiator added is preferably in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A). If the amount of polymerization initiator added is less than the above lower limit, curing (crosslinking) may be poor, while if it is more than the above upper limit, contamination from reaction residues may occur, resulting in odors, bleeding, and the like, which is undesirable.

[0097]

[0039] In the method for producing elastomer spherical particles, when preparing the emulsion (suspension) composition in step i), various additives may be added as needed in addition to the components (A), (B), (C), and (D). Examples of additives include thickeners, pH adjusters, preservatives, antioxidants, and polymerization inhibitors. These additives may be used singly or in appropriate combinations of two or more, in an appropriate amount within a range that does not impair the effects of the present invention.

[0098] The order of adding and mixing the components in step i) is not particularly limited, but for example, the emulsion (suspension) composition may be prepared by previously mixing component (A) and component (D) and then adding component (B) and component (C), or the emulsion (suspension) composition may be prepared from component (A), component (B), and component (C) and then component (D) may be added. Also, after preparing an emulsion (suspension) composition from component (A), component (B), component (C), and component (D), the emulsion (suspension) composition may be diluted by further adding component (B) to a desired concentration before being subjected to step ii).

[0099] Furthermore, when the polyester-polyether copolymer having a radically polymerizable unsaturated group as component (A) has a cloud point (when the solubility of component (A) rapidly decreases upon heating, resulting in phase separation at a certain temperature), or when the component (A) is temperature-dependent, the emulsion (suspension) composition in step i) may be prepared at a temperature appropriate for the temperature characteristics of component (A), for example, by stirring, emulsifying, and suspending the component under heating. The temperature conditions for heating and heating are, for example, 100°C or lower, preferably 30 to 90°C, and more preferably 40 to 70°C. When the continuous phase is an aqueous phase component, a temperature higher than the upper limit mentioned above during heating and heating is undesirable because of the risk of water evaporation and bumping.

[0100] In preparing the emulsion (suspension) composition in step i), a conventionally known emulsifying / dispersing machine may be used. Examples of common emulsifying / dispersing machines include a high-speed rotary shear type agitator such as a homomixer, a high-speed centrifugal radial type agitator such as a homodisper, a combination mix emulsifying / dispersing machine combining a homomixer and a homodisper, a mixing / emulsifying agitator (adihomomomixer) combining a homomixer or a homodisper and an anchor mixer, a high-pressure jet type emulsifying / dispersing machine such as a homogenizer, a colloid mill, an ultrasonic emulsifier, and a propeller agitator.

[0101] Step ii) Step ii) is a step of reacting and curing (crosslinking) the component (A) in the emulsion (suspension) composition prepared in step i) by (radical) polymerization to obtain a dispersion of elastomer spherical particles.

[0102] In step ii), the polymerization reaction conditions can be appropriately determined depending on the type of polymerization initiator (D). For example, when a peroxide or azo-based initiator is used, a heating method in which the reaction is carried out at a temperature of 30 to 80°C for 10 to 24 hours can be used, and when a redox-based initiator is used, a redox method in which the reaction is carried out at a temperature of 30 to 70°C for 2 to 24 hours can be used. When a photoinitiator is used, a photoirradiation method in which the reaction is carried out under light irradiation can be used, and the light source and wavelength range used for light or UV irradiation may be any of those known in the art.

[0103] Step iii) Step iii) is a step of obtaining elastomer spherical particles by washing and drying to remove the continuous phase component (B) from the dispersion of elastomer spherical particles obtained in step ii).

[0104] In step iii), when the continuous phase (dispersion medium) of component (B) is an aqueous phase component, specific methods for step iii) include concentrating the dispersion by methods such as thermal dehydration, (pressure) filtration, centrifugation, and decantation, followed by a water washing operation, if necessary, by adding pure water or the like. Finally, methods such as heat drying at normal pressure or reduced pressure, spray drying in which the dispersion is sprayed into a heated air stream and then heat dried (spray drying), heat drying using a fluid heat medium, and freeze drying in which the dispersion is solidified, then reduced pressure, and the dispersion medium is removed, are included, thereby obtaining elastomeric spherical particles. Note that if the elastomeric spherical particles obtained by washing and drying to remove the dispersion medium are aggregated, they may be crushed using a mortar, ball mill, jet mill, etc.

[0105] In step iii), when the continuous phase (dispersion medium) of component (B) is an oil phase component, specific methods for step iii) include, for example, adding a hydrophobic organic solvent to a dispersion of elastomer spherical particles, stirring for a certain period of time, and then filtering under pressure to wash and remove component (B) and to replace the solvent. By repeating this washing procedure multiple times, component (B) can be sufficiently removed and the solvent can be replaced. Examples of hydrophobic organic solvents that can be used in this process include toluene and hexane. Finally, elastomer spherical particles can be obtained by heat drying at normal or reduced pressure, spraying the dispersion into a heated air stream and then heat drying (spray drying), heat drying using a fluidized heat medium, or freeze drying, in which the dispersion is solidified, then reduced pressure is applied, and the dispersant is removed.

[0106] II. Elastomer Composite Particles and Method for Producing Elastomer Composite Particles The elastomer composite particles incorporated in the cosmetic of the present invention have polyorganosilsesquioxane or silica on the surface of elastomer spherical particles, which are crosslinked particles of a copolymer having a polyester structure and a polyether structure, and preferably have spherical fine particles of polyorganosilsesquioxane or spherical fine particles of silica adhered to or coated on the particle surface of the elastomer spherical particles.

[0107] The shape of the elastomer composite particles is preferably spherical. The shape of the elastomer composite particles can be confirmed using an optical microscope or an electron microscope, similar to the case of the above-mentioned elastomer spherical particles.

[0108] In the present invention, the volume average particle size of the elastomer composite particles is in the range of 1.0 to 100 μm, preferably in the range of 1.0 to 50 μm, and more preferably in the range of 2.0 to 20 μm. If the volume average particle size is greater than 100 μm, the fluidity of the particles decreases and the tendency to aggregate increases, making it impossible to impart sufficient smoothness and light diffusion properties to the particles. Furthermore, if the volume average particle size is less than 1.0 μm, the dryness and smoothness of the particles decrease, and a rough feeling may occur, resulting in reduced light diffusion properties. The volume average particle size of the elastomer composite particles can be measured by the electrical resistance method or the laser diffraction / scattering method, as described above.

[0109] [Polyorganosilsesquioxane] In the present invention, the polyorganosilsesquioxane on the surface of the elastomer spherical particles is R 7 SiO 3 / 2 It is a resin-like solid material in which units represented by are crosslinked in a three-dimensional network.

[0110] R in the above formula 7 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 7Examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; and hydrocarbon groups in which some or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with atoms such as halogen atoms (fluorine, chlorine, bromine, and iodine atoms) and / or substituents such as amino, acryloyloxy, methacryloyloxy, epoxy, glycidoxy, mercapto, and carboxyl. In order to adhere polyorganosilsesquioxane to the surface of the elastomer spherical particles by the method described below, 7 Preferably, 50 mol % or more of R are methyl groups, vinyl groups, or phenyl groups, 7 More preferably, 80 mol % or more of R are methyl groups, vinyl groups, or phenyl groups, 7 More preferably, 90 mol % or more of the groups are methyl groups, vinyl groups, or phenyl groups.

[0111] The polyorganosilsesquioxane may be selected from the group consisting of polyorganosilsesquioxane, ... 7 SiO 3 / 2 In addition to units, R 7 2SiO 2 / 2 Unit, R 7 3SiO 1 / 2 units, and SiO 4 / 2 In such polyorganosilsesquioxanes, at least one of R 7 SiO 3 / 2 The content of the units in the total siloxane units is preferably 70 to 100 mol %, more preferably 80 to 100 mol %.

[0112] [Silica] In the present invention, the silica on the surface of the elastomer spherical particles is R 8 SiO 4 / 2 It is an inorganic solid in which units represented by the formula (I) are crosslinked in a three-dimensional network.

[0113] R in the above formula 8 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. 8 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0114] Silica is obtained by the hydrolysis and polycondensation reaction of tetraalkoxysilane and is mainly composed of SiO2 units. In addition to the structure consisting of SiO2 units, silica may also contain alkoxy groups derived from the raw material tetraalkoxysilane and silanol groups that have not undergone condensation reaction.

[0115] In the present invention, the shape of the polyorganosilsesquioxane or silica is preferably spherical. The particle sizes of the polyorganosilsesquioxane and silica are each preferably 10 to 500 nm, more preferably 20 to 200 nm. If the particle sizes of the polyorganosilsesquioxane and silica are less than 10 nm, the light scattering properties of the resulting elastomer composite particles may be reduced. If the particle sizes of the polyorganosilsesquioxane and silica are greater than 500 nm, the resulting elastomer composite particles may lack a soft feel and have reduced light scattering properties. The polyorganosilsesquioxane or silica may be attached to a portion of the particle surface of the elastomeric spherical particles, or may be attached over the entire particle surface, i.e., cover the entire particle surface; however, it is preferred that the polyorganosilsesquioxane or silica be coated over the entire surface of the elastomeric spherical particles with almost no gaps. The particle size, shape, and adhesion density of polyorganosilsesquioxane and silica on the surface of the elastomer spherical particles can be confirmed by observing the particle surfaces of the obtained elastomer composite particles with an electron microscope. The particle sizes of polyorganosilsesquioxane and silica are calculated as the average value of the particle sizes of 50 randomly selected particles from an electron microscope photograph of the particle surfaces of the obtained elastomer composite particles.

[0116] In the elastomer composite particles, the amount of polyorganosilsesquioxane or silica attached to the surfaces of the elastomer spherical particles is preferably 0.2 to 200 parts by mass, more preferably 0.5 to 50 parts by mass, per 100 parts by mass of the elastomer spherical particles. If the amount of polyorganosilsesquioxane or silica is less than the above lower limit, the particles may become highly cohesive and poorly dispersible, resulting in reduced light scattering and a poor smooth feel. If the amount of polyorganosilsesquioxane or silica is greater than the above upper limit, the elastomer composite particles may become less soft to the touch.

[0117] [Method for Producing Elastomer Composite Particles] The elastomer composite particles can be produced, for example, by a method including the following step iv): iv) a step of adding the following component (I) to a liquid phase containing the following components (E), (F), (G), and (H), and subjecting the component (I) to a hydrolysis / polymerization reaction: (E) elastomer spherical particles (F) alkaline substance (G) one or more selected from cationic surfactants and cationic water-soluble polymer compounds (H) water (I) trialkoxysilane or tetraalkoxysilane

[0118] Step iv) In step iv), the following component (I) is added to a liquid phase containing the following components (E), (F), (G), and (H), and the component (I) is subjected to a hydrolysis and polymerization reaction. The components used in step iv) are as follows:

[0119] The elastomer spherical particles of component (E) are the elastomer spherical particles obtained in the above-described steps i) to ii) or i) to iii). When component (B) used in step i) is an aqueous phase component, the aqueous dispersion of elastomer spherical particles obtained in steps i) and ii) may be subjected to step iv) as a mixture of component (E) and component (H) without going through step iii).

[0120] The amount of the elastomer spherical particles (E) is preferably 1.0 to 150 parts by mass, and more preferably 3.0 to 70 parts by mass, per 100 parts by mass of water (H) in the liquid phase containing components (E) to (H). If the amount of component (E) is less than the above lower limit, the production efficiency of the desired elastomer composite particles may decrease, while if it is more than the above upper limit, it becomes difficult to coat the surfaces of the elastomer spherical particles with polyorganosilsesquioxane or silica, which may cause aggregation or fusion of the particles, which is undesirable.

[0121] The alkaline substance (F) acts as a catalyst for the hydrolysis and polycondensation reaction of trialkoxysilane or tetraalkoxysilane. The alkaline substances may be used alone or in appropriate combination of two or more.

[0122] The alkaline substance is not particularly limited, and examples thereof include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine, trimethylamine, triethanolamine, and ethylenediamine. These alkaline substances may be used alone or in appropriate combination of two or more.

[0123] The most preferred alkaline substance is ammonia, since it can be easily removed from the powder of the elastomer composite particles obtained by volatilization. As the ammonia, commercially available aqueous ammonia solutions of various concentrations may be used.

[0124] The amount of alkaline substance (F) added is preferably an amount that results in a liquid phase containing components (E) to (H) with a pH of 9.0 to 13.0 at 25° C., more preferably an amount that results in a pH in the range of 10.0 to 12.0. Adding an amount that results in a pH of 9.0 to 13.0 allows the hydrolysis and polycondensation reaction of the trialkoxysilane or tetraalkoxysilane to proceed satisfactorily, and the surfaces of the elastomer spherical particles are sufficiently coated with polyorganosilsesquioxane or silica.

[0125] (G) Cationic surfactants and cationic water-soluble polymer compounds have the effect of accelerating the condensation reaction of hydrolyzed trialkoxysilanes or tetraalkoxysilanes to produce resin or silica. They also have the effect of adsorbing the produced resin or silica onto the surfaces of the elastomer spherical particles. The cationic surfactants and cationic water-soluble polymer compounds can be used alone or in appropriate combinations of two or more.

[0126] Examples of the cationic surfactant include the same as those exemplified above as the cationic surfactant for the component (C).

[0127] Examples of the cationic water-soluble polymer compound include polymers of dimethyldiallylammonium chloride, polymers of vinylimidazoline, polymers of methylvinylimidazolium chloride, polymers of ethyl acrylate trimethylammonium chloride, polymers of ethyl methacrylate trimethylammonium chloride, polymers of acrylamidopropyl trimethylammonium chloride, polymers of methacrylamidopropyl trimethylammonium chloride, epichlorohydrin / dimethylamine polymers, polymers of ethyleneimine, quaternized polymers of ethyleneimine, polymers of allylamine hydrochloride, polylysine, cationic starch, cationized cellulose, chitosan, copolymers of these with monomers having a nonionic group or an anionic group, and derivatives thereof.

[0128] As component (G), alkyltrimethylammonium salts of cationic surfactants are preferred, and among these, lauryltrimethylammonium salts and cetyltrimethylammonium salts are more preferred.

[0129] The amount of cationic surfactant and cationic water-soluble polymer compound added is preferably 0.01 to 2.0 parts by mass, and more preferably 0.1 to 1.0 part by mass, per 100 parts by mass of water in the liquid phase containing (E) to (H). If the amount of component (G) added is less than the above lower limit, polyorganosilsesquioxane or silica that is not coated on the surface of the elastomeric spherical particles may be produced, and if the amount added is more than the above upper limit, polyorganosilsesquioxane or silica that is not coated on the surface of the elastomeric spherical particles may be produced.

[0130] The water (H) is not particularly limited, and may be, for example, purified water, ion-exchanged water, pure water, or the like. When the component (B) is an aqueous phase component and the aqueous dispersion of elastomer spherical particles obtained in the step ii) is subjected to the step iv) without going through the step iii), the water (H) includes the water in the aqueous dispersion and water added as needed.

[0131] (I) The trialkoxysilane and tetraalkoxysilane are not particularly limited, and conventionally known ones may be used. From the viewpoint of reactivity, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane are preferred, and methyltrimethoxysilane and tetramethoxysilane are more preferred. The tetraalkoxysilane may be one in which some or all of the alkoxy groups are hydrolyzed, or one in which some of the alkoxy groups are condensed.

[0132] The amount of trialkoxysilane added is preferably such that the amount of polyorganosilsesquioxane is 1.0 to 50 parts by mass, more preferably 2 to 25 parts by mass, per 100 parts by mass of the elastomer spherical particles (E).The amount of tetraalkoxysilane added is preferably such that the amount of silica is 0.5 to 200 parts by mass, more preferably 1.0 to 50 parts by mass, per 100 parts by mass of the elastomer spherical particles (E).

[0133] Hydrolysis and Polycondensation Reaction: (I) trialkoxysilane or tetraalkoxysilane is added to a liquid phase containing (E) to (H), and these are subjected to a hydrolysis and polycondensation reaction. Specifically, (I) trialkoxysilane or tetraalkoxysilane is added to an aqueous dispersion in which (E) elastomer spherical particles are dispersed in (H) water and (F) an alkaline substance, (G) one or more selected from cationic surfactants and cationic water-soluble polymer compounds are dissolved, and hydrolysis and polycondensation are carried out. Through the hydrolysis and polycondensation, polyorganosilsesquioxane or silica is attached to the surface of the elastomer spherical particles as a condensate of the trialkoxysilane or tetraalkoxysilane, thereby coating the surfaces of the elastomer spherical particles with polyorganosilsesquioxane or silica.

[0134] The trialkoxysilane and tetraalkoxysilane are preferably added under stirring using a conventional stirrer such as a propeller blade or flat blade. They may be added all at once, but it is preferable to add them over a period of time. The dropwise addition time is preferably in the range of 1 minute to 6 hours, more preferably 10 minutes to 3 hours.

[0135] The temperature of the liquid phase at this time is preferably 0 to 60°C, more preferably 0 to 40°C. If the temperature is within the above range, the polyorganosilsesquioxane or silica can be successfully attached to and coated on the surfaces of the elastomer spherical particles in the liquid phase. Stirring is continued after the addition of the trialkoxysilane or tetraalkoxysilane until the hydrolysis and polycondensation reactions are complete. To complete the hydrolysis and polycondensation reactions, the reaction may be carried out at room temperature or under heating at about 40 to 100°C, and an alkaline substance may also be added as appropriate.

[0136] Dehydration Step / Powdering Step After the hydrolysis / polycondensation reaction in step iv), water is optionally removed from the resulting aqueous dispersion of elastomer composite particles. Water removal can be achieved by heating the post-reaction aqueous dispersion under normal pressure or reduced pressure. Specific examples include a method of heat drying under normal pressure or reduced pressure, a method of spraying the dispersion into a heated air stream and then heat drying (spray drying), a method of heat drying using a fluidized heat medium, or a freeze-drying method in which the dispersion is solidified, then reduced pressure is applied, and the dispersion medium is removed. This method yields elastomer composite particles. As a pretreatment step for this operation, the dispersion may be concentrated by methods such as heat dehydration, filtration, centrifugation, and decantation, and the aqueous dispersion may be washed with water or alcohol, if necessary.

[0137] If the powder of elastomer composite particles obtained by removing water from the aqueous dispersion after the reaction is aggregated, it may be pulverized using a pulverizer such as a jet mill, a ball mill, or a hammer mill.

[0138] III. Method for Producing Cosmetics Using Elastomer Spherical Particles and Elastomer Composite Particles The cosmetics of the present invention can be produced using at least one of (i) elastomer spherical particles and (ii) elastomer composite particles produced by the method described above. More specifically, the desired cosmetics can be produced by mixing, emulsifying, etc., the elastomer spherical particles and / or elastomer composite particles with various other cosmetic ingredients described below.

[0139] IV. Cosmetic Preparations Containing Elastomer Spherical Particles and Elastomer Composite Particles The cosmetic preparations of the present invention are characterized by containing at least one of (i) elastomer spherical particles and (ii) elastomer composite particles. The blending ratio of the elastomer composite particles is not particularly limited and can be appropriately selected depending on the formulation.

[0140] The present invention is applicable to various types of cosmetics, but is particularly preferably applied to cosmetics applied externally to the skin, such as skin care cosmetics, makeup cosmetics, antiperspirant cosmetics, and sun care cosmetics, as well as to cosmetics applied externally to the hair, such as hair cosmetics, and nail cosmetics.

[0141] In the cosmetics of the present invention, the blending amount of the elastomeric spherical particles and the elastomeric composite particles of the present invention is not limited. Examples of skin care cosmetics include lotions, emulsions, creams, cleansers, packs, oil liquids, massage products, beauty serums, beauty oils, detergents, deodorants, hand creams, lip balms, and wrinkle concealers. In skin care cosmetics, the combined blending amount of (i) the elastomeric spherical particles and (ii) the elastomeric composite particles relative to the total mass of the blended ingredients is, for example, preferably 0.1 to 99% by mass, more preferably 1 to 70% by mass. Examples of makeup cosmetics include makeup bases, foundations, concealers, face powders, blushers, eye colors, eye shadows, mascaras, eyeliners, eyebrow pencils, and lipsticks. In makeup cosmetics, the combined blending amount of (i) the elastomeric spherical particles and (ii) the elastomeric composite particles relative to the total mass of the blended ingredients is, for example, preferably 0.1 to 100% by mass, more preferably 1 to 90% by mass. Examples of antiperspirant cosmetics include roll-on, cream, solution, and stick types. In antiperspirant cosmetics, the total amount of (i) elastomer spherical particles and (ii) elastomer composite particles relative to the total mass of the ingredients is, for example, preferably 0.1 to 80% by mass, and more preferably 1 to 70% by mass. Examples of suncare cosmetics include sunscreen oils, sunscreen emulsions, and sunscreen creams. In suncare cosmetics, the total amount of (i) elastomer spherical particles and (ii) elastomer composite particles relative to the total mass of the ingredients is, for example, preferably 0.1 to 90% by mass, and more preferably 0.1 to 80% by mass. Examples of hair cosmetics include shampoos, rinses, treatments, and setting agents. In the hair cosmetic, the combined amount of (i) elastomer spherical particles and (ii) elastomer composite particles relative to the total mass of the ingredients is, for example, preferably 0.1 to 80 mass%, more preferably 1 to 70 mass%.

[0142] The cosmetic of the present invention may be in any form, for example, a powder, an oily liquid, a water-in-oil emulsion, an oil-in-water emulsion, a non-aqueous emulsion, or a multiple emulsion such as a W / O / W type or an O / W / O type. The cosmetic of the present invention may be in any form, such as a liquid, emulsion, cream, solid, paste, gel, powder, pressed, multi-layered, mousse, spray, stick, or pencil.

[0143] The cosmetic of the present invention can contain various components used in ordinary cosmetic preparations to the extent that the effects of the present invention are not impaired. For example, it may contain (1) an oil, (2) an aqueous component, (3) a surfactant, (4) a powder other than the above-mentioned elastomer spherical particles and elastomer composite particles, (5) a composition consisting of a crosslinked organopolysiloxane and an oil that is liquid at room temperature, (6) a film-forming agent, (7) an ultraviolet absorbing / scattering agent, and (8) other additives. These may be used alone or in appropriate combinations of two or more.

[0144] (1) Oils The oils may be volatile or non-volatile and may be solid, semi-solid, or liquid at room temperature (25°C). Examples of oils include silicone oils, silicone waxes, natural animal and vegetable oils and fats, semi-synthetic oils and fats, hydrocarbon oils, higher alcohols, fatty acids, ester oils, fluorine-based oils, and ultraviolet absorbers.

[0145] Silicone Oil Examples of silicone oils include alkyl-modified silicones such as dimethicone (INCI), trisiloxane (INCI), methyl trimethicone (INCI), ethyl trisiloxane (INCI), ethyl methicone (INCI), and hexyl dimethicone (INCI), long-chain alkyl-modified silicones such as caprylyl methicone (INCI), low-viscosity to high-viscosity linear or branched organopolysiloxanes such as phenyl trimethicone (INCI), diphenyl dimethicone (INCI), diphenylsiloxy phenyl trimethicone (INCI), tetraphenyldimethyldisiloxane (INCI), and methylhydrogen polysiloxane, cyclotetrasiloxane (INCI), and cyclopentasiloxane. Examples of the organic organosiloxane include cyclic organopolysiloxanes such as cyclohexasiloxane (INCI) and cyclohexasiloxane (INCI), amino-modified organopolysiloxanes such as amodimethicone (INCI) and aminopropyl dimethicone (INCI), pyrrolidone-modified organopolysiloxanes such as PCA dimethicone (INCI), pyrrolidone carboxylic acid-modified organopolysiloxanes, silicone rubbers such as gummy dimethylpolysiloxanes with a high degree of polymerization, gummy amino-modified organopolysiloxanes, and gummy dimethylsiloxane-methylphenylsiloxane copolymers, as well as low-viscosity organopolysiloxane solutions of silicone gums and rubbers, amino acid-modified silicones, fluorine-modified silicones, silicone resins, and dissolved silicone resins. Examples of commercially available silicone oils include KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, KF-96A-6cs, KF-4422, KF-4418, KF-54, KF-54HV, KF-56A, and KF-995 manufactured by Shin-Etsu Chemical Co., Ltd.

[0146] In the present invention, when it is desired to solidify the cosmetic, it is preferable to blend an oily component that is solid at 25° C. The oily component that is solid at 25° C. is preferably one that has a melting point of 40° C. or higher, more preferably 60 to 110° C., and examples thereof include waxes, hydrocarbons, esters, higher alcohols, and higher fatty acids. There are no particular restrictions on the oily component as long as it is a raw material that can normally be blended into cosmetics. Specific examples of such waxes include carnauba wax (INCI: Copernicia Cerifera (Carnauba) Wax), sugarcane wax, candelilla wax (INCI: Euphorbia Cerifera (Candelilla) Wax), refined candelilla wax, rice wax, Japan wax, jojoba wax, kapok wax, rice bran wax, white bayberry fruit wax, shea butter, cacao butter, Japan wax (INCI: Rhus Succedanea Fruit Wax), montan wax (INCI: Montan Wax), vegetable waxes such as hydrogenated castor oil isostearate, beeswax, beef tallow, beef bone fat, lard (INCI: Lard), and horse fat (INCI: Horse Fat). Fat), sheep tallow, lanolin (INCI: Lanolin), animal waxes such as butterbur, shellac wax, and spermaceti; semi-synthetic waxes such as lanolin esters, lanolin fatty acid esters, and beeswax acid esters; hydrogenated oils such as hydrogenated castor oil and hydrogenated coconut oil; hydrocarbon waxes such as solid paraffin, polyethylene, ceresin, ozokerite, and microcrystalline wax; wax esters such as synthetic beeswax; amino acid stearyl alcohols such as dioctyldodecyl lauroyl glutamate, dioctyldodecyl lauroyl glutamate, and dioctyldodecyl lauroyl glutamate; fatty acids such as stearic acid and behenic acid; and silicone waxes such as acrylic silicone resins of acrylic-silicone graft or block copolymers (manufactured by Shin-Etsu Chemical Co., Ltd.: acrylic-silicone graft copolymers: KP-561P, KP-562P, etc.), or derivatives thereof, and it is preferable to use one or more selected from these.

[0147] Natural Animal and Vegetable Oils and Semi-Synthetic Oils Examples of natural animal and vegetable oils and semi-synthetic oils include avocado oil (labeled name (INCI: Persea Gratissima (Avocado) Oil)), linseed oil (labeled name (INCI: Linum Usitatissimum (Linseed) Seed Oil)), almond oil (labeled name (INCI: Prunus Amygdalus Dulcis (Sweet Almond) Oil)), perilla oil (labeled name), olive oil (labeled name (INCI: Olea Europaea (Olive) Fruit Oil)), and American grass oil (labeled name (INCI: Torreya California (California Nutmeg) Oil)), Cymbopogon Nardus (Citronella) Oil)), Kaya Seed Oil (: Display name (INCI: Torreya)) Nucifera Seed Oil), Kyounin Yu (INCI: Kyounin Yu)), Wheat Germ Oil (INCI: Triticum Vulgare (Wheat) Germ Sesame oil (Indication name (INCI: Sesamum Indicum (Sesame) Seed) Wheat Germ Oil (INCI: Triticum Vulgare (Wheat) Germ Oil) Oil)), rice bran oil (INCI: Oryza Sativa (Rice) Bran Oil)), sasanqua oil (INCI: Camellia Kissi Seed Oil)), safflower oil (INCI: Carthamus Tinctorius (Saffflower Seed Oil)), Soybean oil (Indication name (INCI: Glycine) Soja (Soybean Oil)), tea seed oil (: display name (INCI: Camellia Sinensis Seed Oil))), camellia oil (: display name (INCI: Camellia Japonica Seed Oil)),Evening primrose oil (: Indicated name (INCI: Oenothera Biennis (Evening Primrose) Oil)), rapeseed oil (Indicated name), corn germ oil (: Indicated name (INCI: Zea Mays (Corn) Germ Oil)), wheat germ oil (: Indicated name (INCI: Triticum Vulgare (Wheat) Germ Oil)) and other germ oils, persic oil (Indicated name), palm oil (: Indicated name (INCI: Elaeis Guineensis (Palm) Oil)), palm kernel oil (: Indicated name (INCI: Elaeis Guineensis (Palm) Kernel Oil)), castor oil (: Indicated name (INCI: Ricinus Communis (Castor) Seed Oil)), sunflower oil (: Indicated name (INCI: Helianthus Annuus (Sunflower) Seed Oil)), grape seed oil (: Indicated name (INCI: Vitis Vinifera (Grape) Seed Oil)), jojoba seed oil (: Indicated name (INCI: Simmondsia Chinensis (Jojoba) Seed Oil)), macadamia seed oil (: Indicated name (INCI: Macadamia Ternifolia Seed Oil)), meadowfoam oil (: Indicated name (INCI: Limnanthes Alba (Meadowfoam) Seed Oil)), cottonseed oil (: Indicated name (INCI: Gossypium Herbaceum (Cotton) Seed Oil)), coconut oil (: Indicated name (INCI: Cocos Nucifera (Coconut) Oil)), peanut oil (: Indicated name (INCI: Arachis Hypogaea (Peanut) Oil)) and other natural vegetable oils, shark liver oil (: Indicated name (INCI: Shark Liver Oil)), cod liver oil (: Indicated name (INCI: Cod Liver Oil)), fish liver oil (: Indicated name (INCI: Fish Liver Oil)), turtle oil (: Indicated name (INCI: Turtle Oil)), mink oil (: Indicated name (INCI: Mink Oil)), egg yolk oil (: Indicated name (INCI: Egg Oil)) and other natural animal oils,Examples of such oils include semi-synthetic oils and fats such as hydrogenated coconut oil (labeled as INCI: Hydrogenated Coconut Oil) and liquid lanolin (labeled as INCI: Lanolin Oil).

[0148] Hydrocarbon Oils Examples of hydrocarbon oils include linear or branched hydrocarbon oils, and may be volatile or non-volatile hydrocarbon oils. Specific examples include isoparaffins such as olefin oligomers (INCI), (C13,14) isoparaffin (INCI), and alkanes such as isododecane (INCI), undecane (INCI), dodecane (INCI), isohexadecane (INCI), hydrogenated polyisobutene (display name (INCI: Hydrogenated Polyisobutene)), squalane (INCI), mineral oil (INCI), palm alkanes (INCI), and (C13-15) alkanes (INCI).

[0149] Higher Alcohols Examples of higher alcohols include linear saturated alcohols having 6 or more carbon atoms, such as lauryl alcohol (INCI), hexyldecanol (INCI), oleyl alcohol (INCI), isostearyl alcohol (INCI), octyldodecanol (INCI), decyltetradecanol (INCI), myristyl alcohol (INCI), cetyl alcohol (INCI), stearyl alcohol (INCI), and behenyl alcohol (INCI), as well as batyl alcohol (INCI). Further examples include sterols, such as cholesterol (INCI), sitosterol (display name (INCI: Beta-Sitosterol)), phytosterols (INCI), and lanosterol (INCI).

[0150] Ester Oils Examples of ester oils include n-alkyl glycol monoisostearates such as diisobutyl adipate (labeled as INCI: Diisobutyl Adipate), dihexyldecyl adipate (labeled as INCI: Diheptylundecyl Adipate), and isostearyl isostearate (labeled as INCI: Isostearyl Isostearate), isocetyl isostearate (labeled as INCI: Isocetyl Isostearate), and trimethylolpropane triisostearate (labeled as INCI: Trimethylolpropane). Triisostearate), Glycol Diethylhexanoate (InCI: Glycol Diethylhexanoate), Cetyl Ethylhexanoate (InCI: Cetyl Ethylhexanoate), Trimethylolpropane Triethylhexanoate (InCI: Trimethylolpropane Triethylhexanoate), Pentaerythrityl Tetraethylhexanoate (InCI: Pentaerythrityl Tetraethylhexanoate), Cetyl Octanoate (InCI: Cetyl octyldodecyl esters such as octyldodecyl stearoyloxystearate (Inci: Octyldodecyl Stearoyl Stearate), oleyl oleate (Inci: Oleyl Oleate), octyldodecyl oleate (Inci: Octyldodecyl Oleate), decyl oleate (Inci: Decyl Oleate), neopentyl glycol dioctanoate (Inci: Neopentyl Glycol Diethylhexanoate), neopentyl glycol dicaprate (Inci: Neopentyl Glycol Dicaprate), diisostearyl malate (: display name (INCI: Diisostearyl Malate)),Triethyl citrate (InCI: Triethyl Citrate), diethylhexyl succinate (InCI: Diethylhexyl Succinate), amyl acetate (InCI: Amyl Acetate), ethyl acetate (InCI: Ethyl Acetate), butyl acetate (InCI: Butyl Acetate), isocetyl stearate (InCI: Isocetyl Stearate), butyl stearate (InCI: Butyl Stearate), diisopropyl sebacate (InCI: Diisopropyl Sebacate), diethylhexyl sebacate (InCI: Diethylhexyl Sebacate), cetyl lactate (InCI: Cetyl Lactate), myristyl lactate (InCI: Myristyl Lactate), isononyl isononanoate (InCI: Isononyl Isononanoate), isotridecyl isononanoate (InCI: Isotridecyl Isononanoate), isopropyl palmitate (InCI: Isopropyl Palmitate), ethylhexyl palmitate (InCI: Ethylhexyl palmitic acid esters such as cholesteryl (INCI: Cholesteryl Hydroxystearate), isopropyl myristate (INCI: Isopropyl Myristate), octyldodecyl myristate (INCI: Octyldodecyl Myristate), and myristyl myristate (INCI: Myristyl Myristate); Laurate), hexyl laurate (INCI: Hexyl Laurate),Examples thereof include dioctyldodecyl lauroyl glutamate (labeled as Dioctyldodecyl Lauroyl Glutamate (INCI: Dioctyldodecyl Lauroyl Glutamate)), lauroyl sarcosine isopropyl ester (labeled as Isopropyl Lauroyl Sarcosinate (INCI: Isopropyl Lauroyl Sarcosinate)), and coco-caprylate / caprate (labeled as Coco-Caprylate / Caprate (INCI: Coco-Caprylate / Caprate)).

[0151] Furthermore, among the ester oils, examples of glyceride oils include triethylhexanoin (INCI), tri(caprylic / capric)glyceryl (labeled as INCI: Caprylic / Capric Triglyceride), cocoglyceryl (INCI), (caprylic / capric / succinic) triglyceryl (labeled as INCI: Caprylic / Capric / Succinic Triglyceride), and (caprylic / capric) glycerides (labeled as INCI: Caprylic / Capric Glycerides).

[0152] Fluorine-Based Oils Examples of fluorine-based oils include perfluorodecalin (INCI), perfluorononyl dimethicone (INCI), and perfluoromethylcyclopentane (INCI).

[0153] Ultraviolet Absorbers Examples of ultraviolet absorbers include oxybenzone-1 (display name (INCI: Benzophenone-1)), oxybenzone-2 (display name (INCI: Benzophenone-2)), oxybenzone-3 (display name (INCI: Benzophenone-3)), oxybenzone-4 (display name (INCI: Benzophenone-4)), oxybenzone-5 (display name (INCI: Benzophenone-5)), oxybenzone-6 (display name (INCI: Benzophenone-6)), oxybenzone-9 (display name (INCI: Benzophenone-9)), homosalate (INCI), octocrylene (INCI), t-butyl methoxydibenzoylmethane (display name (INCI: Butyl Methoxydibenzoylmethane), Ethylhexyl salicylate (InCI: Ethylhexyl Salicylate), Diethylaminohydroxybenzoylhexyl benzoate (InCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), Polysilicone-15 (InCI), Octyl Dimethoxybenzylidene dioxoimidazolidinepropionate (InCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate), Terephthalylidene Dicamphor Sulfonic Acid (InCI: Terephthalylidene Dicamphor Sulfonic Acid), Ethylhexyl Triazone (InCI), Methyl Bis(trimethylsiloxy)silylisopentyl Trimethoxycinnamate (InCI: Isopentyl Trimethoxycinnamate Trisiloxane), Drometrizole Trisiloxane (InCI), Ethylhexyl Dimethyl PABA (InCI: Ethylhexyl Dimethyl PABA), Isopropyl Paramethoxycinnamate (InCI: Isopropyl Methoxycinnamate),Ethylhexyl methoxycinnamate (Inci: Ethylhexyl Methoxycinnamate), Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Inci), Phenylbenzimidazole Sulfonic Acid (Inci: Phenylbenzimidazole Sulfonic Acid), Methylenebisbenzotriazolyltetramethylbutylphenol (Inci), Glyceryl Dimethoxycinnamate Ethylhexanoate (Inci: Glyceryl Ethylhexanoate Dimethoxycinnamate), Glyceryl PABA (Inci), Methyl Diisopropylcinnamate (Inci: Diisopropyl Methyl Examples of such absorbents include cinnamate (INCI), cinoxate (INCI), and ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate). It is also possible to use a UVA absorber (e.g., diethylaminohydroxybenzoyl hexyl benzoate, etc.) and a UVB absorber (e.g., ethylhexyl methoxycinnamate, etc.) in combination, and these can also be combined in any desired manner.

[0154] (2) Aqueous Component The aqueous component is not particularly limited as long as it is an aqueous component that can be typically incorporated into cosmetics. Specific examples include water, lower alcohols preferably having 2 to 5 carbon atoms, such as ethanol (INCI: Alcohol) and isopropanol (INCI: Isopropyl Alcohol), and sugar alcohols such as sorbitol (INCI), maltose (INCI), and xylitol (INCI). Further, polyhydric alcohols such as BG (: Display Name (INCI: Butylene Glycol)), PG (: Display Name (INCI: Propylene Glycol)), DPG (: Display Name (INCI: Dipropylene Glycol)), pentylene glycol (INCI), 1,10-decanediol (INCI), octanediol (INCI), 1,2-hexanediol (INCI), erythritol (INCI), glycerin (INCI), diglycerin (INCI), and polyethylene glycol; glucose (INCI), glyceryl glucoside (INCI), betaine (INCI), chondroitin sulfate sodium (: Display Name (INCI: Sodium Chondroitin Sulfate)), PCA-Na (: Display Name (INCI: Sodium PCA), methyl gluceth-10 (INCI), methyl gluceth-20 (INCI), hyaluronic acid, egg yolk lecithin, soybean lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipids, and the like.

[0155] (3) Surfactants Surfactants include nonionic, anionic, cationic, and amphoteric surfactants, but are not particularly limited, and any surfactants commonly used in cosmetics can be used. Among these surfactants, one or more selected from non-crosslinked silicone surfactants or crosslinked silicone surfactants are preferred, as they allow for the production of stable cosmetics. In either case, the amount of surfactant blended is preferably 0.1 to 20% by mass of the total cosmetic. A content of 0.1% or more allows for sufficient dispersion and emulsification functions, while a content of 20% by mass or less is preferred, as it prevents the cosmetic from feeling sticky after use. The HLB value of the surfactant is not particularly limited, but is preferably 2.0 to 14.5 in order to maintain the water resistance of the cosmetic.

[0156] The non-crosslinked silicone surfactant is one in which some of the methyl groups in a linear or branched silicone main chain have been substituted with a hydrophilic group such as polyethylene glycol or polyglycerin, and specifically, preferred are linear or branched polyoxyethylene-modified organopolysiloxanes, linear or branched polyoxyethylene-polyoxypropylene-modified organopolysiloxanes, linear or branched polyoxyethylene-alkyl-co-modified organopolysiloxanes, linear or branched polyoxyethylene-polyoxypropylene-alkyl-co-modified organopolysiloxanes, linear or branched polyglycerin-modified organopolysiloxanes, linear or branched polyglycerin-alkyl-co-modified organopolysiloxanes, and linear or branched pyrrolidone-modified organopolysiloxanes. Examples of non-crosslinked silicone surfactants include PEG-11 methyl ether dimethicone (INCI), PEG / PPG-20 / 22 butyl ether dimethicone (INCI), PEG-3 dimethicone (INCI), PEG-10 dimethicone (INCI), PEG-9 polydimethylsiloxyethyl dimethicone (INCI), lauryl PEG-9 polydimethylsiloxyethyl dimethicone (INCI), cetyl PEG / PPG-10 / 1 dimethicone (INCI), polyglyceryl-3 disiloxane dimethicone (INCI), polyglyceryl-3 polydimethylsiloxyethyl dimethicone (INCI), lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (INCI), bis-butyl dimethicone polyglyceryl-3 (INCI), and the like. Examples of commercially available products include KF-6011, KF-6011P, KF-6012, KF-6015, KF-6017, KF-6043, KF-6028, KF-6038, KF-6048, KF-6100, KF-6104, KF-6105, KF-6106, and KF-6115 manufactured by Shin-Etsu Chemical Co., Ltd.

[0157] Examples of crosslinked silicone surfactants include crosslinked polyether-modified silicones such as (dimethicone / (PEG-10 / 15)) crosspolymer (INCI), (PEG-15 / lauryl dimethicone) crosspolymer (INCI), (PEG-10 / lauryl dimethicone) crosspolymer (INCI), and (PEG-15 / lauryl polydimethylsiloxyethyl dimethicone) crosspolymer (INCI), and crosslinked polyglycerin-modified silicones such as (dimethicone / polyglycerin-3) crosspolymer (INCI), (lauryl dimethicone / polyglycerin-3) crosspolymer (INCI), and (polyglycerin-3 / lauryl polydimethylsiloxyethyl dimethicone) crosspolymer (INCI). Furthermore, when a crosslinked silicone surfactant is used, in a composition comprising the surfactant and an oil that is liquid at room temperature, it is preferable that the crosslinked silicone surfactant swell with the liquid oil by absorbing an amount of the liquid oil equal to or greater than its own weight.

[0158] As the liquid oil agent, liquid silicone oil, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil, or fluorine-based oil in the optional component (1) oil agent can be used, and examples thereof include cyclopentasiloxane (INCI), dimethicone (INCI), mineral oil (INCI), isododecane (INCI), isohexadecane (INCI), triethylhexanoin (INCI), isotridecyl isononanoate (display name (INCI: Isotridecyl Isononanoate)), squalane (INCI), and the like.

[0159] Examples of commercially available cross-linked silicone surfactants that swell when exposed to a liquid oil include KSG-210, KSG-240, KSG-270, KSG-310, KSG-320, KSG-330, KSG-340, KSG-320Z, KSG-350Z, KSG-710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-820Z, and KSG-850Z, all manufactured by Shin-Etsu Chemical Co., Ltd.

[0160] (4) Powders other than the elastomer spherical particles and elastomer composite particles Powders other than the elastomer spherical particles and elastomer composite particles can be blended. Examples of powders include color pigments, inorganic powders, metal powders, organic powders, and inorganic-organic composite powders. Specific examples are as follows:

[0161] Coloring Pigments The coloring pigment is not particularly limited as long as it is a pigment that is normally used for the purpose of coloring cosmetics, and examples thereof include red iron oxide (: display name (INCI: Iron Oxides)), yellow iron oxide (: display name (INCI: Iron Oxides)), white titanium oxide (: display name (INCI: Titanium Dioxide)), black iron oxide (: display name (INCI: Iron Oxides)), ultramarines (: display name (INCI: Ultramarines)), ferric iron oxide (: display name (INCI: Ferric Ferrocyanide, Ferric Ammonium Ferrocyanide)), manganese violet (: display name (INCI: Manganese Violet)), and cobalt titanate (: display name (INCI: Cobalt Titanium Oxide), chromium hydroxide (: Display name (INCI: Chromium Hydroxide Green)), chromium oxide (: Display name (INCI: Chromium Oxide Greens)), aluminum / cobalt oxide (: Display name (INCI: Cobalt Aluminum Oxide)), cobalt titanate (: Display name (INCI: Cobalt Titanium Oxide)), titanium / titanium oxide baked product (: Display name (INCI: Titanium / Titanium Dioxide)), lithium / cobalt titanate (: Display name (INCI: Lithium Cobalt Any of the following pigments can be used: composites doped with different metals, such as cobalt titanate (display name (INCI: Cobalt Titanate)), cobalt titanate (display name (INCI: Cobalt Titanium Oxide)), (iron oxide / titanium oxide) sinter (display name), and iron oxide-doped titanium oxide (display name (INCI: Iron Oxides, Titanium Dioxide)); inorganic brown pigments, such as titanium nitride (display name (INCI: Titanium Nitride)), ferrous hydroxide (display name (INCI: Iron Hydroxide)), γ-iron oxide; inorganic yellow pigments, such as ochre; and colored pigments, such as lakes of tar-based pigments and lakes of natural pigments.Furthermore, the shape of the pigment may be any shape, such as spherical, approximately spherical, rod-like, spindle-like, petal-like, strip-like, or irregular, and there is no limitation on its geometric form as long as it is capable of imparting color to the cosmetic.

[0162] Inorganic Powder Examples of inorganic powders include zirconium oxide (display name (INCI: Zirconium Dioxide)), zinc oxide (display name (INCI: Zinc Oxide)), cerium oxide (display name (INCI: Cerium Oxide)), magnesium oxide (display name (INCI: Magnesium Oxide)), barium sulfate (display name (INCI: Barium Sulfate)), calcium sulfate (display name (INCI: Calcium Carbonate)), magnesium sulfate (display name (INCI: Magnesium Sulfate)), calcium carbonate (display name (INCI: Calcium Carbonate)), magnesium carbonate (display name (INCI: Magnesium Carbonate), Talc (INCI), Mica (INCI), Kaolin (INCI), Synthetic Fluorphlogopite (InCI: Synthetic Fluorphlogopite), Synthetic Iron Phlogopite (InCI: Biotite), Biotite (InCI: Biotite), Potassium Silicate (InCI: Potassium Silicate), Silica (INCI), Aluminum Silicate (InCI: Aluminum Silicate), Magnesium Silicate (InCI: Magnesium Silicate), Aluminum / Magnesium Silicate (InCI: Magnesium Aluminum Silicate), Calcium Silicate (InCI: Calcium Silicate (aluminum / calcium / sodium) (: display name (INCI: Aluminum Calcium Sodium Silicate)), Silicate (lithium / magnesium / sodium) (: display name (INCI: Lithium Magnesium Sodium Silicate)), Silicate (sodium / magnesium) (: display name (INCI: Sodium Magnesium Silicate)), Borosilicate (calcium / aluminum) (: display name (INCI: Calcium Aluminum Borosilicate)),Examples of the fine particles include fine particles made of borosilicate (calcium / sodium) (display name (INCI: Calcium Sodium Borosilicate)), hydroxyapatite (INCI), bentonite (INCI), montmorillonite (INCI), hectorite (INCI), zeolite (INCI), alumina (INCI), aluminum hydroxide (display name (INCI: Aluminum Hydroxide)), boron nitride (display name (INCI: Boron Nitride)), glass (display name (INCI: Glass)), and the like. Examples of inorganic colored pearl pigments include pearl agents such as mica (INCI) coated with titanium dioxide (display name (INCI: Titanium Dioxide)), synthetic fluorophlogopite (INCI: Synthetic Fluorophlogopite) coated with titanium dioxide (display name (INCI: Titanium Dioxide)), bismuth oxychloride (INCI: Bismuth Oxychloride), bismuth oxychloride (INCI: Bismuth Oxychloride) coated with titanium dioxide (display name (INCI: Titanium Dioxide)), and titanium dioxide (DI: Titanium Dioxide). Examples of pearl pigments include talc (INCI) coated with titanium dioxide (INCI: Titanium Dioxide), fish scale foil (display name), and colored mica coated with titanium dioxide (display name (INCI: Titanium Dioxide)), and there is no particular limitation on the surface treatments which may be untreated or may have been subjected to known surface treatments commonly used in cosmetics.

[0163] Metal Powder Examples of the metal powder include fine metal particles made of aluminum (display name (INCI: Aluminum, Aluminum Powder)), copper (display name (INCI: Copper Powder)), silver (display name (INCI: Silver Powder)), gold (display name (INCI: Gold)), etc.

[0164] Organic Powders Examples of organic powders include powders made of silicone, polyamide, polyacrylic acid / acrylic acid ester, polyester, polyethylene (INCI), polypropylene (INCI), polystyrene (INCI), styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, polyurethane, vinyl resin, urea resin, melamine resin, benzoguanamine, polymethylbenzoguanamine, tetrafluoroethylene, polymethyl methacrylate, cellulose (INCI), silk (INCI), nylon (display name), phenolic resin, epoxy resin, polycarbonate, etc. In particular, examples of silicones include silicone resin particles, polymethylsilsesquioxane (INCI), silicone rubber powder, silicone resin-coated silicone rubber powder, (vinyl dimethicone / methicone silsesquioxane) crosspolymer (INCI), (diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer (INCI), polysilicone-1 crosspolymer (INCI), polysilicone-22 (INCI), etc. Examples of commercially available silicone powders include KMP-590, KMP-591, KMP-592, KMP-597, KMP-598, KSP-100, KSP-101, KSP-102, KSP-105, KSP-300, KSP-411, KSP-441, KM-9729, and KM-440 manufactured by Shin-Etsu Chemical Co., Ltd. Further, metal soaps and the like can also be mentioned, and specific examples thereof include zinc stearate (display name (INCI: Zinc Stearate)), aluminum stearate (display name (INCI: Aluminum Stearate)), calcium stearate (display name (INCI: Calcium Stearate)), magnesium stearate (display name (INCI: Magnesium Stearate)), zinc myristate (display name (INCI: Zinc Myristate)), magnesium myristate (display name (INCI: Magnesium Myristate)), zinc / sodium cetyl phosphate (display name (INCI: Sodium Zinc Cetyl Phosphate)),Examples include powders made of potassium cetyl phosphate (labeled INCI: Potassium Cetyl Phosphate). Further, organic dyes and the like can also be mentioned, and specific examples thereof include Red 3, Red 104 (1) (: display name (INCI: Red 28, Red 28 Lake)), Red 106, Red 201 (: display name (INCI: Red 6)), Red 202 (: display name (INCI: Red 7)), Red 204, Red 205, Red 220 (: display name (INCI: Red 34)), Red 226 (: display name (INCI: Red 30)), Red 227 (: display name (INCI: Red 33, RED 33 Lake)), Red 228 (: display name (INCI: Red 36)), Red 230 (1) (: display name (INCI: Red 22, Red 22 Lake)), Red 230 (2) (Display name), Red 401 (Display name), Red 505 (Display name), Yellow 4 (: Display name (INCI: Yellow 5)), Yellow 5 (: Display name (INCI: Yellow 6, Yellow 6) Yellow 202 (1) (: Display name (INCI: Yellow 8)), Yellow 203 (: Display name (INCI: Yellow 10, Yellow 10 Lake)), Yellow 204 (: Display name (INCI: Yellow) 11)), yellow 401, blue 1 (:display name (INCI:Blue 1, Blue 1 Lake))), blue 2, blue 201, blue 205 (:display name (INCI:Blue 4)), Blue 404 (Display name), Green 3 (:Display name (INCI: Green 3, Green 3 Lake)), Green 201 (:Display name (INCI: Green 5)), Green 202 (:Display name (INCI: Green 6)), Green 204 (:Display name (INCI: Green 8)), Green 205 (Display name), Orange 201 (:Display name (INCI: Orange 5)), Orange 203 (:Display name (INCI: Pigment Orange 5)), Orange 204 (Display name), Orange 205 (:Display name (INCI: Orange 4, Orange 4 Lake)), Orange 206 (:Display name (INCI: Orange 10)), Orange 207 (:Display name (INCI: Orange 11)), cochineal (INCI), laccaic acid (INCI: Laccaic Acid),Examples of natural pigments include safflower red (labeled as INCI: Carthamus Tinctorius (Safflor) Flower Extract), purple root extract (labeled as INCI: Lithospermum Officinale Root Extract), gardenia yellow (labeled as INCI: Hydrolyzed Gardenia Florida Extract), and gardenia blue (labeled as INCI: Hydrolyzed Gardenia Florida Extract).

[0165] Inorganic-organic composite powder Examples of the inorganic-organic composite powder include composite powders in which the surface of an inorganic powder is coated with an organic powder by a known method.

[0166] The above-mentioned powders may also be surface-treated. From the viewpoint of water resistance of the cosmetic, the surface treatment agent is preferably one that can impart hydrophobicity. The treatment agent for imparting hydrophobicity is not particularly limited, and examples thereof include silicone treatment agents, waxes, paraffins, organic fluorine compounds such as perfluoroalkyl phosphates, surfactants, amino acids such as N-acyl glutamic acid, and metal soaps such as aluminum stearate and magnesium myristate. More preferred are silicone treatment agents, and examples thereof include silanes or silylating agents such as triethoxycaprylylsilane (INCI), dimethicone (INCI), methicone (INCI), hydrogen dimethicone (INCI), triethoxysilylethyl polydimethylsiloxyethyl dimethicone (INCI), triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (INCI), and (acrylates / tridecyl acrylate / triethoxysilylpropyl methacrylate / dimethicone methacrylate) copolymer (labeled name (INCI): Acrylates / Tridecyl Acrylate / Triethoxysilylpropyl Methacrylate / Dimethicone Methacrylate Copolymer). Specific examples of these silicone treatment agents include AES-3083, KF-99P, KF-9901, KF-9908, KF-9909, KP-574, and KP-541, all manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, the above surface hydrophobic treatment agents may be used alone or in combination of two or more. Specific examples of surface-treated color pigments include the KTP-09 series, particularly KTP-09W, KTP-09R, KTP-09Y, and KTP-09B, all manufactured by Shin-Etsu Chemical Co., Ltd.

[0167] (5) Composition Comprising a Crosslinked Organopolysiloxane and an Oil That Is Liquid at Room Temperature In a composition comprising a crosslinked organopolysiloxane and an oil that is liquid at room temperature, the crosslinked organopolysiloxane preferably swells with the liquid oil in an amount equal to or greater than its own weight. The liquid oil may be a liquid silicone oil, hydrocarbon oil, ester oil, natural animal or vegetable oil, semi-synthetic oil, or fluorine-containing oil, as included in the optional component (1) oil. Examples of the liquid oil include cyclopentasiloxane (INCI), dimethicone (INCI), mineral oil (INCI), isododecane (INCI), isohexadecane (INCI), triethylhexanoin (INCI), isotridecyl isononanoate (INCI: Isotridecyl Isononanoate), and squalane (INCI). Unlike the crosslinked silicone surfactant of component (3) described above, component (5) is a compound that does not have a polyether or polyglycerin structure in its molecular structure, and specific examples include (dimethicone / vinyl dimethicone) crosspolymer (INCI), (dimethicone / phenyl vinyl dimethicone) crosspolymer (INCI), (vinyl dimethicone / lauryl dimethicone) crosspolymer (INCI), (lauryl polydimethylsiloxyethyl dimethicone / bis vinyl dimethicone) crosspolymer (INCI), etc. Examples of commercially available compositions comprising a crosslinked organopolysiloxane and an oil that is liquid at room temperature include KSG-15, KSG-1510, KSG-16, KSG-1610, KSG-19, KSG-016F, KSG-18A, KSG-41A, KSG-42A, KSG-43, KSG-44, KSG-042Z, KSG-045Z, and KSG-048Z, all manufactured by Shin-Etsu Chemical Co., Ltd.

[0168] (6) Film-Forming Agent The film-forming agent is blended mainly for the purpose of further maintaining the durability of the cosmetic effect. There are no particular limitations, but from the viewpoint of imparting water repellency, a silicone-based composition is preferable. Specific examples that can be used include trimethylsiloxysilicate, acrylic-silicone film-forming agents, silicone-modified norbornene, silicone-modified pullulan, and silicone-modified polyvinyl alcohol. Examples of film-forming agents for silicone-based compositions include trimethylsiloxysilicate (labeled as Trimethylsiloxysilicate (INCI)), acrylates / dimethicone copolymer (INCI), norbornene / tris(trimethylsiloxy)silylnorbornene copolymer (INCI), and tri(trimethylsiloxy)silylpropylcarbamate pullulan (labeled as Trimethylsiloxysilylcarbamoyl Pullulan (INCI). The film-forming agent may be dissolved in a liquid oil at room temperature before blending into the cosmetic. Examples of the liquid oil include liquid silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils, semi-synthetic oils, and fluorine-based oils, which are included in the optional component (1) oil. Specific examples of commercially available silicone film-forming agents include KF-7312J, KP-545, KP-549, KP-543, NBN-30-ID, TSPL-30-ID, and TSPL-30-D5, all manufactured by Shin-Etsu Chemical Co., Ltd.

[0169] (7) Ultraviolet-Absorbing / Scattering Agents Examples of ultraviolet-absorbing / scattering agents include particles that absorb and scatter ultraviolet light, such as titanium oxide microparticles, iron-containing titanium oxide microparticles, zinc oxide microparticles, cerium oxide microparticles, and composites thereof. Dispersions in which these ultraviolet-absorbing / scattering particles are pre-dispersed in an oil agent can also be used. Examples of the oil agent include liquid silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils, semi-synthetic oils, and fluorine-based oils, which are included in the optional component (1) oil agent. Specific examples of dispersions in which ultraviolet-absorbing / scattering particles are pre-dispersed in an oil agent include, for example, SPD-T5, SPD-T5L, SPD-Z5, SPD-Z5L, SPD-T6, SPD-Z6, SPD-T7, and SPD-Z7L from the SPD series (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.

[0170] (8) Other additives Examples of other additives include oil-soluble gelling agents, preservatives / disinfectants, antiperspirants, fragrances, salts, antioxidants, pH adjusters, chelating agents, refreshing agents, anti-inflammatory agents, skin-beautifying ingredients (skin-whitening agents, cell activators, skin roughness improving agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, and inclusion compounds.

[0171] Oil-soluble gelling agents include, for example, metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as lauroyl glutamic acid (labeled as "Lauroyl Glutamic Acid" in C1H2O3 and "α,γ-di-n-butylamine" in C1H2O3); dextrin palmitate (labeled as "Dextrin Palmitate" in C1H2O3); dextrin isostearate (labeled as "Dextrin Isostearate" in C1H2O3); dextrin myristate (labeled as "Dextrin Myristate" in C1H2O3); inulin stearate (labeled as "Stearoyl Inulin" in C1H2O3); and dextrin (palmitate / ethylhexanoate) (labeled as "Dextrin" in C1H2O3). dextrin fatty acid esters such as dextrin palmitate / ethylhexanoate); sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; fructooligosaccharide fatty acid esters such as fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate; benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol; disteardimonium hectorite (INCI), stearalkonium hectorite (INCI), organically modified clay minerals of hectorite; and stearalkonium bentonite (INCI).

[0172] Preservatives and disinfectants Examples of preservatives and disinfectants include alkyl parahydroxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, carbolic acid, parachlormetacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, iodopropynyl butylcarbamate, polylysine, photosensitizers, silver, and plant extracts.

[0173] Antiperspirants include, for example, aluminum hydroxyhalides such as aluminum chlorohydrate, aluminum halides such as aluminum chloride, aluminum allantoin, tannic acid, persimmon tannin, aluminum / potassium sulfate, zinc oxide, zinc paraphenolsulfonate, burnt alum, tetrachloro(aluminum / zirconium) hydrate, trichlorohydrex glycine (aluminum / zirconium), etc. Particularly preferred components that exhibit high effectiveness are aluminum hydroxyhalides, aluminum halides, and their complexes or mixtures with zirconyl oxyhalides and zirconyl hydroxyhalides (for example, tetrachloro(aluminum / zirconium) hydrate, trichlorohydrex glycine (aluminum / zirconium)).

[0174] Fragrances Fragrances include natural fragrances and synthetic fragrances. Natural fragrances include, for example, plant-based fragrances isolated from flowers, leaves, wood, and peels; and animal-based fragrances such as musk and civet. Synthetic fragrances include, for example, hydrocarbons such as monoterpenes; alcohols such as aliphatic alcohols and aromatic alcohols; aldehydes such as terpene aldehydes and aromatic aldehydes; ketones such as alicyclic ketones; esters such as terpene esters; lactones; phenols; oxides; nitrogen-containing compounds; and acetals.

[0175] Salts Examples of salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. Examples of inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid; examples of organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid; examples of amine salts and amino acid salts include salts of amines such as triethanolamine, and salts of amino acids such as glutamic acid. Other examples that can be used include salts of hyaluronic acid, chondroitin sulfate, aluminum-zirconium-glycine complexes, and even acid-alkali neutral salts used in cosmetic formulations.

[0176] Antioxidants Examples of antioxidants include, but are not limited to, carotenoids, ascorbic acid and salts thereof, ascorbyl stearate, tocopherol, tocopherol acetate, tocopherol, p-t-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfites, erythorbic acid and salts thereof, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, quercetin, etc. Antioxidants may be used alone or in combination of two or more.

[0177] pH Adjusting Agents Examples of pH adjusting agents include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, and ammonium hydrogen carbonate.

[0178] Chelating Agents Examples of chelating agents include alanine, edetate sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid, and the like.

[0179] Cooling Agents Examples of cooling agents include L-menthol, camphor, menthyl lactate, and the like.

[0180] Anti-inflammatory Agents Examples of anti-inflammatory agents include allantoin, glycyrrhizinic acid and salts thereof, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, and azulene.

[0181] Skin-beautifying ingredients Examples of skin-beautifying ingredients include whitening agents such as arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extract; rough skin improving agents; blood circulation promoters such as nonylic acid valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantharides tincture, ichthammol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, and γ-oryzanol; skin astringents such as zinc oxide and tannic acid; and antiseborrheic agents such as sulfur and thianthrol.

[0182] Vitamins Examples of vitamins include vitamin A oil, retinol, retinol acetate, retinol palmitate, and other vitamin A compounds; riboflavin, riboflavin butyrate, flavin adenine nucleotide, and other vitamin B2 compounds; pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmitate, and other vitamin B6 compounds; vitamin B12 and its derivatives; vitamin B15 and its derivatives; L-ascorbic acid, L-ascorbic acid dipalmitate, sodium L-ascorbic acid-2-sulfate, and dipotassium L-ascorbic acid phosphate diester. vitamin C such as calcium; vitamin D such as ergocalciferol and cholecalciferol; vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, and dl-α-tocopherol succinate; nicotinic acids such as nicotinic acid, benzyl nicotinate, and nicotinamide; vitamin H, vitamin P, pantothenic acids such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, and acetylpantothenyl ethyl ether; and biotin.

[0183] Amino Acids Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan.

[0184] Nucleic Acids Examples of nucleic acids include deoxyribonucleic acid.

[0185] Hormones Examples of hormones include estradiol and ethenylestradiol.

[0186] Clathrate Compounds Examples of the clathrate compounds include cyclodextrins.

[0187] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise specified, "%" indicating concentration and content refers to "% by mass" and "parts" refers to "parts by mass." The kinematic viscosity indicates a value measured at 25°C. In the following examples, the volume average particle size and aspect ratio of the elastomer spherical particles and elastomer composite particles indicate values ​​measured by the above-mentioned methods. The hardness of the cured rubber (elastomer) is a value measured in accordance with the Society of Rubber Science and Technology Standards of Japan (SRIS).

[0188] The molecular weight of a copolymer having a polyester structure and a polyether structure (a polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule) is the weight-average molecular weight (Mw.) measured by GPC under the following conditions, using polystyrene as the standard. [Measurement conditions] Developing solvent: tetrahydrofuran (THF) Flow rate: 0.60 mL / min Detector: differential refractive index detector (RI) Column: TSK Guard column Super H-H, TSKgel Super HM-N, TSKgel Super H2500 (all manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (THF solution with a concentration of 0.5% by mass)

[0189] [Method for measuring and evaluating biodegradability] Biodegradability was measured using a method using activated sludge as a microbial (degradation) source in accordance with OECD Guidelines for the Testing of Chemicals, No. 301F, July 17, 1992, "Ready Biodegradability: MANOMETRIC RESPIROMETRY TEST," and evaluated based on the degree of biodegradability. Activated sludge used was from a municipal sewage treatment plant, and the suspended solids concentration was 2,400 mg / L. Sodium benzoate was used as a reference (control) substance. The degree of biodegradation was measured by measuring the amount of oxygen consumed (biochemical oxygen consumption (BOD)) in a closed system in an incubator using a BOD meter, and calculating the degree of biodegradation according to the following formula: Biodegradation (%) = BOD - B / TOD x 100 BOD: Biochemical oxygen consumption of the test suspension or operation control (measured value: mg) B: Average biochemical oxygen consumption of the plant-source blank (measured value: mg) TOD: Theoretical oxygen consumption required for complete oxidation of the test substance or sodium benzoate (calculated value: mg)

[0190] Synthesis Example 1: Acrylic-modified poly-ε-caprolactone / polyether copolymer 1 A 2-L separable flask equipped with a stirrer, thermometer, condenser, and dropping funnel was charged with 500 g of primary-terminated EO (ethylene oxide) / PO (propylene oxide) polyether (molecular weight: approximately 2,000, OH group equivalent: 0.09-0.10 mol / 100 g), 183.6 g of ε-caprolactone (molecular weight: 114.1), and 350 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After reaching the target temperature, 0.68 g of tetra-n-butoxytitanium (molecular weight: 340.0) was added as a catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above operation was cooled to near room temperature, and then 60.7 g of triethylamine (molecular weight 101.2), 100 g of dehydrated toluene, and 0.22 g of dibutylhydroxytoluene (BHT) (molecular weight 220.4) as a polymerization inhibitor were added, and the mixture was stirred for a certain period of time to achieve uniform dissolution. Then, 49.7 g of acrylic acid chloride (molecular weight 90.5) was added dropwise using a dropping funnel, and after confirming the generation of heat, the mixture was aged for 4 hours at 60° C. The resulting crude product was pressure filtered, washed with an aqueous sodium chloride solution using a separatory funnel, centrifuged, and then magnesium sulfate, silica gel, activated carbon, etc. were added, and powder treatment was performed by shaking to adsorb and remove impurities. After removing the various powders by pressure filtration, 0.22 g of dibutylhydroxytoluene (BHT) was added again, and the solvent was then distilled off at 60 to 70°C and 50 mmHg or less, thereby obtaining an acrylic-modified poly-ε-caprolactone / polyether copolymer 1 (formula (11) below, weight-average molecular weight: 2,880).

[0191] Synthesis Example 2: Acrylic-modified poly-ε-caprolactone / polyether copolymer 2 A 1 L separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with 300 g of the same primary-terminated EO / PO polyether as in Synthesis Example 1, 110.2 g of ε-caprolactone, and 200 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After the target temperature was reached, 0.41 g of tetra-n-butoxytitanium was added as a catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above procedure was cooled to near room temperature, and then 100 g of dehydrated toluene, 0.96 g of dioctyltin dineodecanoate (molecular weight: 687.7) as a catalyst, and 0.12 g of dibutylhydroxytoluene (BHT) were added. The mixture was stirred for a certain period of time to achieve a uniform solution, and then 44.4 g of 2-isocyanatoethyl acrylate (molecular weight: 141.1) was added dropwise using a dropping funnel. After confirming the generation of heat, the mixture was aged at 60°C for 4 hours. The resulting crude product was cooled to below 40°C, and 0.8 g of ethanol was added to react with unreacted (residual) isocyanate groups, resulting in a quenching treatment. Next, magnesium sulfate, silica gel, activated carbon, etc. were added, and the mixture was subjected to powder treatment by shaking to adsorb and remove impurities. After removing the various powders by pressure filtration, 0.12 g of dibutylhydroxytoluene (BHT) was added again, and the solvent was then distilled off at 60 to 70°C and 50 mmHg or less, thereby obtaining an acrylic-modified poly-ε-caprolactone / polyether copolymer 2 (formula (12) below, weight-average molecular weight: 3,120).

[0192] Synthesis Example 3: Acrylic-modified poly-ε-caprolactone / polyether copolymer 3 A 1 L separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with 300 g of primary-terminated EO / PO polyether (molecular weight: approximately 2,600, OH group equivalent: 0.09 to 0.10 mol / 100 g), 115.2 g of ε-caprolactone, and 200 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After reaching the target temperature, 0.42 g of tetra-n-butoxytitanium was added to the catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above procedure was cooled to near room temperature, and then 70 g of dehydrated toluene, 0.18 g of tris(2,4-pentanedionato)iron(III) (also known as iron(III) acetylacetonate, molecular weight: 353.2) as a catalyst, and 0.13 g of dibutylhydroxytoluene (BHT) were added, and the mixture was stirred for a certain period of time to achieve a uniform solution. Then, 46.4 g of 2-isocyanatoethyl acrylate was added dropwise using a dropping funnel, and after confirming heat generation, the mixture was aged for 4 hours at 60° C. The obtained crude product was subjected to post-treatment and purification steps in the same manner as in Synthesis Example 2 above, to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 3. The acrylic-modified poly-ε-caprolactone / polyether copolymer 3 had a structure of formula (12), where l≈18-21, m≈34-38, r≈3-4, and the weight average molecular weight was 4,870.

[0193] Synthesis Example 4: Acrylic-modified poly-ε-caprolactone / polyether copolymer 4 A 1 L separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with 300 g of the same primary-terminated EO / PO polyether as in Synthesis Example 3, 115.2 g of ε-caprolactone, and 200 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After the target temperature was reached, 0.42 g of tetra-n-butoxytitanium was added as a catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above procedure was cooled to near room temperature, and then 70 g of dehydrated toluene, 2.77 g of zirconium tetraacetylacetonate (molecular weight: 487.7) as a catalyst, and 0.13 g of dibutylhydroxytoluene (BHT) were added. The mixture was stirred for a certain period of time to achieve a uniform solution, and then 46.4 g of 2-isocyanatoethyl acrylate was added dropwise using a dropping funnel. After confirming the generation of heat, the mixture was aged at 60°C for 4 hours. The obtained crude product was subjected to post-treatment and purification steps similar to the method described in Synthesis Example 2 above, thereby obtaining acrylic-modified poly-ε-caprolactone / polyether copolymer 4. Acrylic-modified poly-ε-caprolactone / polyether copolymer 4 had a structure represented by formula (12), where l≈18-21, m≈34-38, and r≈3-4, and had a weight-average molecular weight of 4,990.

[0194] Synthesis Example 5: Acrylic-modified poly-ε-caprolactone / polyether copolymer 5 A 1 L separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with 300 g of primary-terminated EO / PO polyether (molecular weight: approximately 3,200, OH group equivalent: 0.062 mol / 100 g), 106.3 g of ε-caprolactone, and 200 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After reaching the target temperature, 0.41 g of tetra-n-butoxytitanium was added as a catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above procedure was cooled to around room temperature, and then 70 g of dehydrated toluene, 1.01 g of dioctyltin dineodecanoate as a catalyst, and 0.13 g of dibutylhydroxytoluene (BHT) were added, and the mixture was stirred for a certain period of time to achieve a uniform solution. 28.4 g of 2-isocyanatoethyl acrylate was then added dropwise using a dropping funnel, and after confirming the generation of heat, the mixture was aged for 4 hours at 60° C. The obtained crude product was subjected to post-treatment and purification steps in the same manner as in the method described in Synthesis Example 2 above, to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 5 (formula (13), weight average molecular weight: 7,940).

[0195] Synthesis Example 6: Acrylic-modified poly-ε-caprolactone / polyether copolymer 6 A 1 L separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with 300 g of primary-terminated EO / PO polyether (molecular weight: approximately 1,100, OH group equivalent: 0.182 mol / 100 g), 311.6 g of ε-caprolactone, and 250 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After reaching the target temperature, 0.61 g of tetra-n-butoxytitanium was added as a catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above procedure was cooled to near room temperature, and then 100 g of dehydrated toluene, 2.77 g of catalyst zirconium tetraacetylacetonate (molecular weight: 487.7), and 0.21 g of dibutylhydroxytoluene (BHT) were added thereto, and the mixture was stirred for a certain period of time to achieve a uniform solution. Then, 80.84 g of 2-isocyanatoethyl acrylate (molecular weight: 141.1) was added dropwise using a dropping funnel, and after confirming the generation of heat, the mixture was aged for 4 hours at 60° C. The obtained crude product was subjected to post-treatment and purification steps in the same manner as in Synthesis Example 2 above, to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 6 (formula (14), weight average molecular weight: 2,530).

[0196] Synthesis Example 7: Acrylic-modified poly-ε-caprolactone / polyether copolymer 7 A 1 L separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel was charged with 300 g of primary-terminated EO / PO polyether (molecular weight: approximately 7,200, OH group equivalent: 0.028 mol / 100 g), 31.4 g of ε-caprolactone, and 200 g of dehydrated toluene, and heated to 90° C. under a nitrogen flow. After reaching the target temperature, 0.33 g of tetra-n-butoxytitanium was added as a catalyst, and the mixture was aged at 120° C. for 4 to 6 hours. Next, the poly-ε-caprolactone / polyether copolymer obtained by the above procedure was cooled to near room temperature, and then 50 g of dehydrated toluene, 1.37 g of zirconium tetraacetylacetonate (molecular weight: 487.7) as a catalyst, and 0.11 g of dibutylhydroxytoluene (BHT) were added, and the mixture was stirred for a certain period of time to achieve a uniform solution. Then, 12.3 g of 2-isocyanatoethyl acrylate (molecular weight: 141.1) was added dropwise using a dropping funnel, and after confirming the generation of heat, the mixture was aged for 4 hours at 60° C. The obtained crude product was subjected to post-treatment and purification steps in the same manner as in Synthesis Example 2 above, to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 7 (formula (15), weight average molecular weight: 8,250).

[0197] [Biodegradability Evaluation] In accordance with the evaluation method described above, the biodegradability of acrylic-modified poly-ε-caprolactone / polyether copolymer 1 was evaluated at an incubation temperature of 22±1°C for 60 days. As a result, the degree of biodegradation of acrylic-modified poly-ε-caprolactone / polyether copolymer 1 averaged 62% after 28 days and 73% after 60 days, satisfying the criterion of 60% biodegradation after 28 days, and was therefore determined to be a "readily biodegradable substance." Therefore, it is presumed that the elastomer spherical particles, which are crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymer 1, and the elastomer composite particles will eventually decompose without remaining as particles in the environment if they are used and then released directly into the ocean via land waters or the like.

[0198] The biodegradability of acrylic-modified poly-ε-caprolactone / polyether copolymers 2 to 4 was measured at an incubation temperature of 22±1°C for 60 days. The biodegradability of acrylic-modified poly-ε-caprolactone / polyether copolymers 2 to 4 averaged 40% after 28 days and 65% after 60 days, satisfying the criterion of 60% biodegradation after 60 days. Since these copolymers were deemed to be "essentially biodegradable," they were deemed to be "essentially biodegradable substances." Therefore, it is presumed that the elastomeric spherical particles and elastomeric composite particles, which are crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymers 2 to 4, and the elastomeric spherical particles and elastomeric composite particles, which are crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymers 5 to 7, which have the same repeating unit structure as acrylic-modified poly-ε-caprolactone / polyether copolymers 2 to 4 but a different number of repeating units, will ultimately decompose without persisting as particles in the environment if they are used and then released directly into the ocean via land waters or the like.

[0199] Preparation Example 1: Elastomer spherical particles 1 A 1-L container of an AdiHomomixer was charged with 250 g of a 2.6% aqueous solution of hydroxypropyl methylcellulose (trade name: Metrose 60SH-4,000, manufactured by Shin-Etsu Chemical Co., Ltd.), and while operating the Homomixer and Anchor Mixer, the mixture was stirred and mixed under heating at 55 to 60° C. Simultaneously, 100 g of the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 from Synthesis Example 4 described above and 1.0 g of dimethyl 2,2′-azobis-(2-methylpropionate) (molecular weight: 230.3) were charged into a descup, and the mixture was premixed in a Disper Mixer and preheated to 60 to 65° C. Next, the premixed acrylic-modified poly-ε-caprolactone / polyether copolymer was added to a 1 L AdiHomomixer containing a heated aqueous hydroxypropyl methylcellulose solution, and the mixture was stirred at 55-60°C for 10 minutes or more at a homomixer rotation speed of 4,500 rpm to suspend and emulsify the mixture, yielding an O / W emulsion (suspension) composition. The resulting emulsion (suspension) composition was then stirred and aged for 8 hours at 70°C at a rotation speed of 200 rpm using a paddle-type stirring impeller, after which 50 g of pure water was added and the mixture was further aged for 6 hours at 80°C at the same rotation speed to obtain a dispersion of elastomer spherical particles 1.

[0200] The shape of the elastomer spherical particles 1 in the obtained dispersion was observed under an optical microscope and found to be spherical. The volume average particle size was measured using an electrical resistance particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.) and found to be 5 μm.

[0201] The obtained dispersion of elastomer spherical particles 1 was filtered through a mesh filter (#100) to check for the presence of aggregates. If aggregates were found, they were removed, and then the continuous phase, pure water, was removed by solid-liquid separation through pressure filtration. The above washing and separation procedure was repeated three times with pure water to remove water. Note that if solid-liquid separation is not successful in the pressure filtration step, centrifugation may be used. Finally, the obtained concentrate of elastomer spherical particles 1 was allowed to stand and dried for 8 hours or more to obtain the desired white to pale yellow powder of elastomer spherical particles 1.

[0202] The resulting powder of elastomer spherical particles 1 was observed using an electron microscope (scanning microscope S-4700, manufactured by Hitachi High-Technologies Corporation), and was confirmed to be spherical particles with a particle size of approximately 5 μm. The aspect ratio of the resulting elastomer spherical particles 1 was 1.0. The resulting elastomer spherical particles 1 were redispersed in water using polyoxyethylene lauryl ether as a surfactant, and the resulting dispersion was measured and evaluated by an electrical resistance method, confirming that the volume average particle size was 5 μm.

[0203] The hardness of the elastomer (rubber) constituting the elastomer spherical particles 1 was measured as follows. 30 g of the synthesized acrylic-modified poly-ε-caprolactone / polyether copolymer 4 and 0.24 g of 2'-azobis-(2,4-dimethylvaleronitrile) (molecular weight: 248.4) were stirred and mixed, and poured into an aluminum petri dish to a thickness of 10 mm. After leaving the mixture in an air thermostatic chamber at 70°C for 1 to 2 hours, a flat rubber without stickiness (tack) was obtained. The rubber hardness of the obtained flat rubber was measured, and it was found to be 72 using an Asker C hardness scale and 55 using an Asker A hardness scale.

[0204] Preparation Example 2: Elastomeric spherical particles 2 Elastomeric spherical particles 2 were produced in the same manner as in Preparation Example 1, except that 250 g of the 2.6% aqueous solution of hydroxypropyl methylcellulose was changed to 173 g of a 3.8% aqueous solution. As a result, elastomeric spherical particles with a volume average particle size of 2 μm were obtained.

[0205] Preparation Example 3: Elastomeric spherical particles 3 Elastomeric spherical particles 3 were produced in the same manner as in Preparation Example 1, except that the hydroxypropyl methylcellulose (trade name: Metrose 60SH-4,000, manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with the same hydroxypropyl methylcellulose (trade name: Metrose 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.) as in Preparation Example 1. As a result, elastomeric spherical particles having a volume average particle size of 11 μm were obtained.

[0206] Preparation Example 4: Elastomeric spherical particles 4 Elastomeric spherical particles 4 were produced in the same manner as in Preparation Example 1, except that 250 g of a 5.2% aqueous solution of xanthan gum was used instead of 250 g of a 2.6% aqueous solution of hydroxypropyl methylcellulose (trade name: Metrose 60SH-4,000, manufactured by Shin-Etsu Chemical Co., Ltd.). As a result, elastomeric spherical particles having a volume average particle size of 20 μm were obtained.

[0207] [Preparation Example 5: Elastomeric Spherical Particles 5] Elastomeric spherical particles 5 were produced in the same manner as in Preparation Example 1, except that the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 in Preparation Example 1 was replaced with acrylic-modified poly-ε-caprolactone / polyether copolymer 6. As a result, elastomeric spherical particles having a volume average particle size of 5 μm were obtained. Furthermore, the hardness of the elastomer (rubber) constituting the elastomeric spherical particles 5 was measured in the same manner as described above. As a result, a flat rubber without stickiness (tack) was obtained, and it showed a hardness of 78 on an Asker A hardness scale.

[0208] [Preparation Example 6: Elastomeric Spherical Particles 6] Elastomeric spherical particles 6 were produced in the same manner as in Preparation Example 1, except that acrylic-modified poly-ε-caprolactone / polyether copolymer 4 in Preparation Example 1 was replaced with acrylic-modified poly-ε-caprolactone / polyether copolymer 7. As a result, elastomeric spherical particles with a volume average particle size of 5 μm were obtained. Furthermore, the hardness of the elastomer (rubber) constituting the elastomeric spherical particles 6 was measured in the same manner as described above. As a result, a flat rubber without stickiness (tack) was obtained, and it showed a hardness of 22 on the Asker A hardness scale.

[0209] Comparative Example 1: Cellulose Powder Cellulose powder CELLULOBEADS D-5 (average particle size 5 μm) manufactured by Daito Kasei Kogyo Co., Ltd. was used.

[0210] Comparative Example 2: Spherical Silica Particles Spherical silica, Silica Microbead P-1500 (average particle size 5 μm) manufactured by JGC Catalysts and Chemicals Co., Ltd. was used.

[0211] Preparation / Manufacturing Example 1: Elastomer Composite Particles 1 A 500 ml glass flask equipped with a paddle-type stirring blade was charged with 100 g of the 20% solids dispersion of elastomer spherical particles 1 obtained in Preparation Example 1, 184.9 g of pure water, and 0.2 g of a 30% aqueous solution of lauryltrimethylammonium chloride. After adjusting the temperature of the aqueous dispersion to 5-10°C, 0.75 g of 5.0% aqueous ammonia was added. While maintaining the aqueous dispersion at 5-10°C, 11.2 g of tetramethoxysilane (an amount sufficient to provide 22.0 parts of silica after the hydrolysis and polycondensation reaction per 100 parts of elastomer spherical particles) was added dropwise over 15-30 minutes. The liquid temperature was maintained at 5-10°C during this period, and stirring was continued for 1 hour. The mixture was then heated to 55-60°C, and stirred and aged for 1 hour while maintaining the temperature, completing the hydrolysis and condensation reaction of the tetramethoxysilane.

[0212] A dispersion of elastomer spherical particles 1, in which tetramethoxysilane was subjected to a hydrolysis and condensation reaction, was dehydrated to a water content of approximately 30% using a pressure filter. The dehydrated product was then transferred to a 1 L glass flask equipped with an anchor-type impeller stirrer, 500 g of water was added, and the mixture was stirred for 30 minutes, after which it was dehydrated by pressure filtration. This washing and dehydration procedure was repeated three times, and the dehydrated product was dried in a hot air fluidized dryer at 105°C. The dried product was then crushed in a jet mill to obtain flowable particles.

[0213] Observation of the resulting particles under an electron microscope confirmed that the entire particle surface of the elastomer spherical particles was coated with spherical silica, and that silica-coated elastomer spherical particles (elastomer composite particles 1) were obtained. The aspect ratio of the resulting silica-coated elastomer spherical particles (elastomer composite particles 1) was 1.0.

[0214] The obtained silica-coated elastomer spherical particles (elastomer composite particles 1) were dispersed in water using a surfactant (polyoxyethylene lauryl ether), and the dispersion was measured using an electrical resistance particle size distribution analyzer (Multisizer 3, manufactured by Beckman Coulter, Inc.). As a result, it was confirmed that the particle size distribution was equivalent to that of the aqueous dispersion of the above-mentioned elastomer spherical particles 1, and the volume average particle size was approximately 5 μm.

[0215] [Preparation / Production Example 2: Elastomer Composite Particles 2] Elastomer composite particles were produced in the same manner as in Preparation / Production Example 1, except that elastomer spherical particles 2 (Preparation Example 2) were used instead of elastomer spherical particles 1. As a result, silica-coated elastomer spherical particles (elastomer composite particles 2) with a volume average particle size of about 2 μm were obtained.

[0216] Preparation / Production Example 3: Elastomer Composite Particles 3 Elastomer composite particles were produced in the same manner as Preparation / Production Example 1, except that elastomer spherical particles 1 in Preparation / Production Example 1 were replaced with elastomer spherical particles 3 (Preparation Example 3). As a result, silica-coated elastomer spherical particles (elastomer composite particles 3) with a volume average particle size of about 11 μm were obtained.

[0217] Preparation / Production Example 4: Elastomer Composite Particles 4 Elastomer composite particles were produced in the same manner as Preparation / Production Example 1, except that elastomer spherical particles 1 in Preparation / Production Example 1 were replaced with elastomer spherical particles 4 (Preparation Example 4). As a result, silica-coated elastomer spherical particles (elastomer composite particles 4) with a volume average particle size of about 20 μm were obtained.

[0218] Preparation / Production Example 5: Elastomer Composite Particles 5 Elastomer composite particles were produced in the same manner as Preparation / Production Example 1, except that the elastomer spherical particles 1 in Preparation / Production Example 1 were replaced with elastomer spherical particles 5 (Preparation Example 5). As a result, silica-coated elastomer spherical particles (elastomer composite particles 5) with a volume average particle size of about 5 μm were obtained.

[0219] Preparation / Production Example 6: Elastomer Composite Particles 6 Elastomer composite particles were produced in the same manner as Preparation / Production Example 1, except that the elastomer spherical particles 1 in Preparation / Production Example 1 were replaced with elastomer spherical particles 6 (Preparation Example 6). As a result, silica-coated elastomer spherical particles (elastomer composite particles 6) with a volume average particle size of approximately 5 μm were obtained.

[0220] Preparation / Production Example 7: Elastomer Composite Particles 7 A 500 ml glass flask equipped with a paddle-type stirring blade was charged with 100 g of the 20% solids dispersion of elastomer spherical particles 3 obtained in Preparation Example 3, 184.9 g of pure water, and 0.2 g of a 30% aqueous solution of lauryltrimethylammonium chloride. After adjusting the temperature of the aqueous dispersion to 5-10°C, 0.84 g of 5.0% aqueous ammonia was added. While maintaining the aqueous dispersion at 5-10°C, 12.5 g of methyltrimethoxysilane (an amount sufficient to provide 22.0 parts of silane per 100 parts of elastomer spherical particles after the hydrolysis and polycondensation reaction) was added dropwise over 15-20 minutes. The liquid temperature was maintained at 5-10°C during this period, and the mixture was stirred for 1 hour. Subsequent operations were similar to those in Preparation / Production Example 1, yielding particles with good flowability.

[0221] Observation of the resulting particles under an electron microscope confirmed that the entire particle surface of the elastomer spherical particles was coated with spherical polyorganosilsesquioxane, and polyorganosilsesquioxane-coated elastomer spherical particles (elastomer composite particles 7) were obtained. The aspect ratio of the resulting polyorganosilsesquioxane-coated elastomer spherical particles (elastomer composite particles 7) was 1.0.

[0222] The obtained polyorganosilsesquioxane-coated elastomer spherical particles (elastomer composite particles 7) were dispersed in water using a surfactant (polyoxyethylene lauryl ether), and the volume average particle size was measured using an electrical resistance particle size distribution analyzer (Multisizer 3, manufactured by Beckman Coulter, Inc.), confirming that the volume average particle size was approximately 11 μm.

[0223] Preparation / Production Example 8: Elastomer Composite Particles 8 Elastomer composite particles were produced in the same manner as in Preparation / Production Example 1, except that the amount of tetramethoxysilane added was changed from 11.2 g (an amount that would result in 22.0 parts of silica after the hydrolysis and polycondensation reaction per 100 parts of the elastomer spherical particles) to 5.6 g (an amount that would result in 11.0 parts of silica after the hydrolysis and polycondensation reaction per 100 parts of the elastomer spherical particles). As a result, silica-coated elastomer spherical particles (elastomer composite particles 8) having a volume average particle size of about 5 μm were obtained.

[0224] [Preparation / Production Example 9: Elastomer Composite Particles 9] Elastomer composite particles were produced in the same manner as in Preparation / Production Example 7, except that elastomer spherical particles 3 were replaced with elastomer spherical particles 4, and the amount of methyltrimethoxysilane added was changed from 12.5 g (an amount that would result in 22.0 parts of silane after the hydrolysis and polycondensation reaction per 100 parts of the elastomer spherical particles) to 0.51 g (an amount that would result in 0.9 parts of silane after the hydrolysis and polycondensation reaction per 100 parts of the elastomer spherical particles). As a result, polyorganosilsesquioxane-coated elastomer spherical particles (elastomer composite particles 9) with a volume average particle size of approximately 20 μm were obtained.

[0225] Comparative Example 3: Silica-coated mica Silica-coated mica Velvet Veil 310 (composite powder in which 10% of mica is coated with silica having an average particle size of 300 nm) manufactured by JGC Catalysts and Chemicals Co., Ltd. was used.

[0226] The particle sizes of the spherical silica or polyorganosilsesquioxane particles attached to and coated on the surfaces of the elastomer spherical particles obtained in each example were as shown in the table below.

[0227] (1) Usability Evaluation The particles of each of Preparation Examples 1 to 6, Preparation and Manufacturing Examples 1 to 9, and Comparative Examples 1 to 3 were blended into cosmetics, and usability was evaluated. For water-in-oil creams formulated as in Formulation Examples 1 to 15 and Formulation Comparative Examples 1 to 3, usability upon application (spreadability, even application to skin) and usability after application (transparency, softness, concealment of pores and wrinkles) were evaluated. For powder foundations formulated as in Formulation Examples 16 to 30 and Formulation Comparative Examples 4 to 6, moldability and usability upon application (powder removal, spreadability, even application to skin) and usability after application (softness, concealment of pores and wrinkles) were evaluated. For water-in-oil sunscreen creams formulated as in Formulation Examples 31 to 45 and Formulation Comparative Examples 7 to 9, usability upon application (spreadability, even application to skin) and usability after application (transparency, concealment of pores and wrinkles, absence of oily film feeling) were evaluated. Each usability item was evaluated by 10 expert panelists. The evaluation was carried out according to the evaluation criteria shown in Table 1, and the results were judged according to the following criteria based on the average of the 10 judges. The results for the water-in-oil (liquid emulsion) cream are shown in Table 2 below, the results for the powder foundation are shown in Table 3 below, and the results for the water-in-oil sunscreen cream are shown in Table 4 below.

[0228]

[0229] (2) Usability evaluation criteria: ◎: Average score is 4.0 points or more; ○: Average score is 3.0 points or more and less than 4.0 points; △: Average score is 2.0 points or more and less than 3.0 points; ×: Average score is less than 2.0 points.

[0230] (Note 1) Shin-Etsu Chemical Co., Ltd.: Mixture of 70-80% dimethicone + 20-30% (dimethicone / (PEG-10 / 15)) crosspolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: Mixture of 90-96% cyclopentasiloxane + 4-10% (dimethicone / vinyl dimethicone) crosspolymer (Note 3) Shin-Etsu Chemical Co., Ltd.: PEG-10 dimethicone

[0231] (Manufacturing method) A: Components 1 to 6 are mixed uniformly. B: Components 7 to 10 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is defoamed and then filled into a container to obtain a water-in-oil cream.

[0232]

[0233] From the results in Table 2 above, it was confirmed that Formulation Examples 1 to 15 exhibited the effects of providing a transparent finish after application, softness of the applied film, and smoothing of skin irregularities. Among them, Formulation Examples 7 to 15 were particularly excellent in terms of spreadability upon application and uniform application to the skin. On the other hand, Formulation Comparative Examples 1 to 3 were inferior in terms of providing a transparent finish after application, softness of the applied film, and smoothing of skin irregularities.

[0234] (Note 1) Shin-Etsu Chemical Co., Ltd.: Triethoxycaprylylsilane (Note 2) Shin-Etsu Chemical Co., Ltd.: KF-9909 treated colored inorganic pigment, W: White, R: Red, Y: Yellow, B: Black (Note 3) Shin-Etsu Chemical Co., Ltd.: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone (Note 4) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl Trimethicone

[0235] (Manufacturing Method) A: Components 1 to 5 are mixed uniformly in a Henschel mixer. B: Components 6 to 10 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A, and mixed uniformly in a Henschel mixer. D: The product obtained in step C is passed through a sieve and then stamped into a metal dish using a mold to obtain a powder foundation.

[0236]

[0237] From the results in Table 3 above, it was confirmed that Formulation Examples 16 to 30 exhibited the effects of softening the applied film after application and correcting skin irregularities. Among them, Formulation Examples 22 to 30 were particularly excellent in terms of formability, spreadability upon application, and uniform application to the skin. On the other hand, Formulation Comparative Examples 4 to 6 were inferior in terms of softness of the applied film after application and correcting skin irregularities.

[0238] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 75-85% cyclopentasiloxane + 15-25% (dimethicone / (PEG-10 / 15)) crosspolymer. (Note 2) Shin-Etsu Chemical Co., Ltd.: A mixture of 80-90% diphenylsiloxyphenyl trimethicone + 10-20% (dimethicone / phenylvinyl dimethicone) crosspolymer. (Note 3) Shin-Etsu Chemical Co., Ltd.: Cetyl PEG / PPG-10 / 1 dimethicone. (Note 4) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone. (Note 5) Shin-Etsu Chemical Co., Ltd.: A dispersion of 45% fine titanium dioxide particles in a cyclopentasiloxane solvent. (Note 6) Shin-Etsu Chemical Co., Ltd.: A dispersion of 60% fine zinc oxide particles in a cyclopentasiloxane solvent.

[0239] (Manufacturing method) A: Components 1 to 10 are mixed uniformly. B: Components 13 to 17 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Components 11 and 12 are added to the product obtained in step C and mixed uniformly. E: The product obtained in step D is degassed and then filled into a container to obtain a water-in-oil sunscreen cream.

[0240]

[0241] From the results in Table 4 above, it was confirmed that Formulation Examples 31 to 45 were effective in providing a transparent finish after application, correcting skin irregularities, and eliminating the feeling of an oily film. Among them, Formulation Examples 37 to 45 were particularly excellent in terms of spreadability upon application and uniform application to the skin. On the other hand, Formulation Comparative Examples 7 to 9 were inferior in terms of providing a transparent finish after application, correcting skin irregularities, and eliminating the feeling of an oily film.

[0242] (Note 1) Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 Disiloxane Dimethicone

[0243] (Manufacturing method) A: Components 1 to 3 are mixed uniformly. B: Components 4 to 10 are mixed uniformly. C: The product obtained in step A is added to the product obtained in step B and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain an aqueous gel.

[0244] The aqueous gel of the present invention obtained in the above manner had an excellent fresh feeling when applied, was non-sticky, spread easily, had excellent adhesion, and had a matte finish with good settling and reduced gloss.

[0245] (Note 1) Shin-Etsu Chemical Co., Ltd.: Mixture of 80-90% dimethicone + (dimethicone / vinyl dimethicone) crosspolymer 10-20%) (Note 2) Shin-Etsu Chemical Co., Ltd.: Mixture of 90-96% cyclopentasiloxane + (dimethicone / vinyl dimethicone) crosspolymer 4-10% (Note 3) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone

[0246] (Production Method) A: Components 1 to 5 were mixed uniformly. B: The mixture obtained in step A above was degassed and then filled into a container to obtain an oily gel.

[0247] The oily gel of the present invention obtained in the above manner was smooth when applied, non-sticky, spread easily, had excellent adhesion, and provided a matte finish with good settling and reduced gloss.

[0248] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 65-75% mineral oil + 25-35% (PEG-15 / lauryl dimethicone) crosspolymer. (Note 2) Shin-Etsu Chemical Co., Ltd.: A mixture of 65-75% squalane + 25-35% (vinyl dimethicone / lauryl dimethicone) crosspolymer. (Note 3) Shin-Etsu Chemical Co., Ltd.: Cetyl PEG / PPG-10 / 1 dimethicone.

[0249] (Manufacturing method) A: Components 1 to 5 are mixed uniformly. B: Components 6 to 10 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain a water-in-oil cream.

[0250] The water-in-oil cream of the present invention obtained in this manner was smooth when applied, non-sticky, spread easily, had excellent adhesion, and gave a natural finish with a good settling effect and reduced oily shine.

[0251] (Note 1) Shin-Etsu Chemical Co., Ltd.: Diphenyl Dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: PEG / PPG-20 / 22 Butyl Ether Dimethicone

[0252] (Manufacturing method) A: Components 1 to 5 are mixed uniformly. B: Components 6, 7, and 9 are mixed and dissolved. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Component 8 is added to the product obtained in step C and mixed uniformly. E: The product obtained in step D is defoamed and then filled into a container to obtain a water-in-oil cream.

[0253] The water-in-oil cream obtained in this manner was confirmed to have a fine texture, spread easily, and be neither sticky nor oily, and to have excellent stability, being unaffected by temperature changes or the passage of time.

[0254] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 65-75% squalane + (PEG-10 / lauryl dimethicone) crosspolymer, 25-35% (PEG-15 / lauryl dimethicone) crosspolymer. (Note 2) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. (Note 3) Shin-Etsu Chemical Co., Ltd.: (vinyl dimethicone / methicone silsesquioxane) crosspolymer.

[0255] (Manufacturing method) A: Mix components 1 to 6. B: Mix and dissolve components 7 to 10 and 12. C: Add the product obtained in step B to the product obtained in step A and mix uniformly. D: Add component 11 to the product obtained in step C and mix uniformly. E: After defoaming the product obtained in step D, fill into a container to obtain a water-in-oil cream.

[0256] The water-in-oil cream obtained in this manner was confirmed to have a fine texture, spread easily, and be neither sticky nor oily, and to have excellent stability, being unaffected by temperature changes or the passage of time.

[0257] (Note 1) Shin-Etsu Chemical Co., Ltd.: PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) Scutellaria root extract: 50% extracted with BG water (Note 3) Gentian extract: 20% extracted with ethanol water

[0258] (Manufacturing method) A: Mix ingredients 1 to 8. B: Mix ingredients 9 to 14 and dissolve. C: Add the product obtained in step B to the product obtained in step A and mix uniformly. D: After defoaming the product obtained in step C, fill into a container to obtain a water-in-oil cream.

[0259] The water-in-oil cream obtained in this way not only had a fine texture and was non-sticky, but also spread easily, had excellent adhesion, and lasted for a long time. It was also confirmed that it was stable and did not change with temperature or time.

[0260] (Note 1) Shin-Etsu Chemical Co., Ltd.: Mixture of 65-75% triethylhexanoin + (vinyl dimethicone / lauryl dimethicone) crosspolymer 25-35% (Note 2) Shin-Etsu Chemical Co., Ltd.: Methylcellulose (Note 3) SEPPIC: Sepigel 305

[0261] (Manufacturing method) A: Components 1 to 3 are mixed. B: Components 4 to 10 are mixed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is defoamed and then filled into a container to obtain an oil-in-water cream.

[0262] The oil-in-water cream obtained in this manner was confirmed to have a fine texture, spread easily without stickiness or oiliness, and to have excellent stability without change with temperature or time.

[0263] (Note 1) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone 75-85% + (Dimethicone / (PEG-10 / 15)) Crosspolymer 15-25% Mixture (Note 2) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone 80-90% + (Dimethicone / Phenylvinyldimethicone) Crosspolymer 10-20% Mixture (Note 3) Shin-Etsu Chemical Co., Ltd.: Cetyl PEG / PPG-10 / 1 Dimethicone (Note 4) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone (Note 5) Shin-Etsu Chemical Co., Ltd.: Caprylyl methicone (Note 6) Shin-Etsu Chemical Co., Ltd.: Ethyl trimethicone

[0264] (Manufacturing Method) A: Components 1 to 11 are mixed uniformly. B: Components 12 to 15 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain a water-in-oil sunscreen emulsion.

[0265] The sunscreen emulsion of the present invention obtained as described above was found to be extremely excellent in that it had excellent smoothness when applied, gave a subdued glossy finish, and provided long-lasting makeup.

[0266] (Note 1) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone 75-85% + (Dimethicone / (PEG-10 / 15)) Crosspolymer 15-25% mixture (Note 2) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: Isododecane 60% + (Acrylates / Dimethicone) Copolymer 40% solution (Note 4) Shin-Etsu Chemical Co., Ltd.: Triethoxycaprylylsilane

[0267] (Manufacturing method) A: Component 3 is added to a portion of component 2 and homogenized, then component 10 is added and dispersed using a bead mill. B: The remainder of component 2 is homogenized with component 1 and components 4 to 9. C: Components 11 to 13 and component 15 are mixed and dissolved. D: The material obtained in step C is added to the material obtained in step B and mixed uniformly. E: The material obtained in step A is added to the material obtained in step D and mixed uniformly. F: Component 14 is added to the material obtained in step E and mixed uniformly. G: The material obtained in step F is degassed and then filled into a container to obtain a water-in-oil sunscreen cream.

[0268] The sunscreen cream obtained in this manner was non-sticky, spread easily, adhered well to the skin, corrected the skin's contours, and lasted for a long time. It was also confirmed to be very stable against temperature changes and changes over time.

[0269] (Note 1) Shin-Etsu Chemical Co., Ltd.: Lauryl PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate (Note 4) Shin-Etsu Chemical Co., Ltd.: (Vinyl dimethicone / methicone silsesquioxane) crosspolymer

[0270] (Manufacturing method) A: Component 2 is added to component 1 and homogenized, then components 8 and 9 are added and dispersed using a bead mill. B: Components 3 to 7 are mixed homogenously. C: Components 10 to 12 and component 14 are mixed and dissolved. D: The product obtained in step C is added to the product obtained in step B and mixed homogenously. E: The product obtained in step A is added to the product obtained in step D and mixed homogenously. F: Component 13 is added to the product obtained in step E and mixed homogenously. G: The product obtained in step F is degassed and then filled into a container to obtain a water-in-oil sunscreen emulsion.

[0271] The sunscreen emulsion obtained in this manner had a fine texture, spread easily, and was not sticky. Furthermore, it was confirmed that the makeup lasted well, so the UV protection effect lasted, and it was also very stable, with no change over time or with temperature changes.

[0272] (Note 1) Shin-Etsu Chemical Co., Ltd.: Dimethicone 70-80% + (Dimethicone / Polyglycerin-3) Crosspolymer 20-30% Mixture (Note 2) Shin-Etsu Chemical Co., Ltd.: Dimethicone 70-80% + (Dimethicone / Vinyl Dimethicone) Crosspolymer 20-30% Mixture (Note 3) Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (Note 4) Shin-Etsu Chemical Co., Ltd.: Dimethicone (2cs) 50% + Trimethylsiloxysilicate 50% Dissolved Product (Note 5) Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (Note 6) Shin-Etsu Chemical Co., Ltd.: Methicone

[0273] (Manufacturing method) A: Components 1 to 7 are mixed. B: Components 8 to 10 are mixed and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Components 11 to 13 and component 15 are mixed and dissolved. E: The product obtained in step D is added to the product obtained in step C and mixed uniformly. F: Component 14 is added to the product obtained in step E and mixed uniformly. G: The product obtained in step F is degassed and then filled into a container to obtain a water-in-oil cream foundation.

[0274] The cream foundation obtained in this manner had excellent smoothness and moisturizing properties when applied, was non-sticky, spread easily, and had excellent adhesion, good settling, and a natural finish with subdued shine.

[0275] (Note 1) Shin-Etsu Chemical Co., Ltd.: PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: (Acrylates / Ethylhexyl acrylate / Dimethicone methacrylate) Copolymer

[0276] (Manufacturing method) A: Components 1 to 5 are mixed. B: Components 6 to 8 are mixed and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Components 9 to 10 and component 12 are mixed and dissolved. E: The product obtained in step D is added to the product obtained in step C and mixed uniformly. F: Component 11 is added to the product obtained in step E and mixed uniformly. G: The product obtained in step F is degassed and then filled into a container to obtain a water-in-oil cream foundation.

[0277] The cream foundation obtained in this manner was confirmed to have a fine texture, spread easily without stickiness or oiliness, last long, and be stable without change due to temperature or time.

[0278] (Note 1) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate (Note 3) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone

[0279] (Manufacturing method) A: Components 1 to 7 are mixed. B: Components 8 to 10 are mixed and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Components 11 to 13 are mixed and dissolved. E: The product obtained in step D is added to the product obtained in step C and mixed uniformly. F: The product obtained in step E is degassed and then filled into a container to obtain a water-in-oil liquid foundation.

[0280] The liquid foundation obtained in this manner was confirmed to have low viscosity, fine texture, spread easily without stickiness or oiliness, have a skin contouring effect, last long, and be stable with no change due to temperature or time.

[0281] (Note 1) Shin-Etsu Chemical Co., Ltd.: Diphenyl Dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: (Methyl / phenyl) Polysilsesquioxane (Note 4) Shin-Etsu Chemical Co., Ltd.: Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (Note 5) Shin-Etsu Chemical Co., Ltd.: Hydrogen Dimethicone

[0282] (Manufacturing method) A: Components 1 to 7 are mixed. B: Components 8 to 11 are mixed and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Components 12 to 14 are mixed and dissolved. E: The product obtained in step D is added to the product obtained in step C and mixed uniformly. F: The product obtained in step E is degassed and then filled into a container to obtain a water-in-oil liquid foundation.

[0283] The liquid foundation obtained in this manner was confirmed to be non-sticky, spread easily, have excellent adhesion, and last for a long time. It was also found to be highly stable, remaining unaffected by temperature and time.

[0284]

[0285] (Manufacturing method) A: Components 1 to 7 are heated to 80°C and mixed uniformly. B: Components 8 to 10 are heated to 80°C, component 11 is added, and mixed uniformly. C: The heated product obtained in step B is added to the heated product obtained in step A and mixed uniformly. D: Components 12 and 13 are mixed and rolled. E: The product obtained in step C is cooled to room temperature, and then components 14 and 15 are added and mixed uniformly. F: The product obtained in step D is added to the product obtained in step E and mixed uniformly. G: The product obtained in step F is defoamed and then filled into a container to obtain an oil-in-water base cream.

[0286] The base cream obtained in this manner had an excellent freshness when applied, was non-sticky, spread easily, and had an excellent adhesion, good settling, and a matte finish with reduced shine.

[0287] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 75-85% isododecane + 15-25% (vinyl dimethicone / lauryl dimethicone) crosspolymer. (Note 2) Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 polydimethylsiloxyethyl dimethicone. (Note 3) Shin-Etsu Chemical Co., Ltd.: Tri(trimethylsiloxy)silylpropylcarbamate pullulan 30% + 70% isododecane solution. (Note 4) Shin-Etsu Chemical Co., Ltd.: (Acrylates / ethylhexyl acrylate / dimethicone methacrylate) copolymer. (Note 5) Shin-Etsu Chemical Co., Ltd.: Hydrogen dimethicone. (Note 6) Shin-Etsu Chemical Co., Ltd.: Triethoxycaprylylsilane.

[0288] (Manufacturing Method) A: Components 1 to 9 are mixed uniformly. B: Components 10 to 14 are mixed uniformly and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain an oil-based cream foundation.

[0289] The cream foundation obtained in this manner spread easily, settled well on the skin, gave a moist finish, and produced a firm makeup film with a subdued sheen, which lasted well, making it an extremely excellent product.

[0290] (Note 1) Shin-Etsu Chemical Co., Ltd.: Dimethicone (2cs) 50% + trimethylsiloxysilicate 50% solution (Note 2) Shin-Etsu Chemical Co., Ltd.: Dimethicone 75-85% + (lauryl polydimethylsiloxyethyl dimethicone / bisvinyl dimethicone) crosspolymer 15-25% mixture (Note 3) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone (Note 4) Shin-Etsu Chemical Co., Ltd.: KF-9909 treated colored inorganic pigment, W: white, R: red, Y: yellow, B: black

[0291] (Manufacturing method) A: A portion of component 1 and components 2 to 9 are mixed uniformly. B: Components 10 to 14 are mixed with the remainder of component 1 and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain an oil-based mousse foundation.

[0292] The mousse foundation obtained in this manner was in a soufflé form, easy to remove, spread easily, and had a texture that was neither oily nor powdery. It was also confirmed that it had good water resistance, water repellency, and sweat resistance, lasted well, was resistant to makeup smearing, and was stable with no change over time or with temperature changes.

[0293] (Note 1) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Polymethylsilsesquioxane (Note 3) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (Note 4) Shin-Etsu Chemical Co., Ltd.: Hydrogen dimethicone (Note 5) Shin-Etsu Chemical Co., Ltd.: KF-9909 treated colored inorganic pigment, W: white, R: red, Y: yellow, B: black

[0294] (Manufacturing method) A: Components 1 to 9 are heated and dissolved. B: Components 12 to 15 are mixed uniformly and roll processed. C: The product obtained in step B above and components 10 and 11 are added to the heated product obtained in step A above and mixed uniformly. D: The product obtained in step C above is degassed while heated, then filled into a container and cooled to room temperature to obtain an oil-based solid foundation.

[0295] The solid foundation obtained in this manner spread easily, settled well on the skin, gave a moist finish, and produced a firm makeup film with a subdued sheen, which lasted well, making it an extremely excellent product.

[0296] (Note 1) Shin-Etsu Chemical Co., Ltd.: Polysilicone-1 Crosspolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl Polydimethylsiloxyethylhexyl Dimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: KF-9909 treated colored inorganic pigment, W: White, R: Red, Y: Yellow, B: Black (Note 4) Shin-Etsu Chemical Co., Ltd.: Caprylyl Methicone

[0297] (Manufacturing Method) A: Components 1 to 7 are mixed uniformly in a Henschel mixer. B: Components 8 to 11 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A, and mixed uniformly in a Henschel mixer. D: The product obtained in step C is passed through a sieve and then stamped into a metal dish using a mold to obtain a powder foundation.

[0298] The powder foundation obtained in the above manner was found to be extremely excellent in that it was smooth to apply, non-sticky, spread easily, had excellent adhesion, gave a finish with good settling and subdued shine, did not smudge, and lasted well.

[0299] (Note 1) Shin-Etsu Chemical Co., Ltd.: (Vinyl dimethicone / methicone silsesquioxane) crosspolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: (Diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer (Note 3) Shin-Etsu Chemical Co., Ltd.: Hydrogen dimethicone

[0300] (Manufacturing method) A: Components 1 to 9 are mixed uniformly in a Henschel mixer. B: Components 10 and 11 are mixed uniformly and dissolved. C: The product obtained in step B is added to the product obtained in step A, and mixed uniformly in a Henschel mixer. D: The product obtained in step C is passed through a sieve and then filled into a container to obtain a loose powder.

[0301] The loose powder obtained in the above manner was found to be extremely excellent in that it was smooth to the touch when applied, had a subdued glossy finish, and lasted for a long time.

[0302] (Note 1) Shin-Etsu Chemical Co., Ltd.: Dimethicone 70-80% + (Dimethicone / Vinyl Dimethicone) Crosspolymer 20-30% Mixture (Note 2) Shin-Etsu Chemical Co., Ltd.: KF-9909 Treated Colored Inorganic Pigment, W: White, R: Red, Y: Yellow, B: Black (Note 3) Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl Polydimethylsiloxyethylhexyl Dimethicone

[0303] (Manufacturing Method) A: Components 1 to 5 are mixed, heated to 80°C, and mixed uniformly. B: Components 6 to 10 are mixed uniformly using a Henschel mixer. C: The product obtained in step B is added to the product obtained in step A, and mixed uniformly at 80°C. D: The product obtained in step C is degassed while heated, then filled into a container and cooled to room temperature, to obtain an oil-based cheek color.

[0304] The cheek color obtained in this manner was sponge-like, easy to apply, spread easily, and had a texture that was neither oily nor powdery. It was also confirmed that it had good water resistance, water repellency, and sweat resistance, lasted well, was resistant to makeup smearing, and had excellent stability, with no change over time or with temperature changes.

[0305] (Note 1) Shin-Etsu Chemical Co., Ltd.: Polysilicone-22 (Note 2) Shin-Etsu Chemical Co., Ltd.: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone

[0306] (Manufacturing method) A: Components 1 to 9 are mixed uniformly in a Henschel mixer. B: Components 10 to 13 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A, and mixed uniformly in a Henschel mixer. D: The product obtained in step C is passed through a sieve and then stamped into a metal plate using a mold to obtain a powder blush.

[0307] The powder blush obtained in the above manner was found to be extremely excellent in that it was smooth to apply, was not sticky, spread easily, had excellent adhesion, gave a finish with good settling and subdued shine, did not smudge, and lasted well.

[0308] (Note 1) Shin-Etsu Chemical Co., Ltd.: PEG-9 polydimethylsiloxyethyl dimethicone

[0309] (Manufacturing Method) A: Components 1 to 4 are mixed uniformly. B: Components 5 and 6 are mixed uniformly using a Henschel mixer. C: Components 7 to 9 and component 11 are mixed uniformly and dissolved. D: The product obtained in step C above is added to the product obtained in step A above and mixed uniformly. E: Component 10 is added to the product obtained in step D above and mixed uniformly. F: The product obtained in step E above is degassed and then filled into a container to obtain a water-in-oil cream eye shadow.

[0310] The cream eye shadow obtained in this manner spread easily and had a texture that was neither oily nor powdery. It was also confirmed that it had good water resistance, water repellency, and sweat resistance, was long-lasting, did not easily smudge, and was stable with no change over time or with temperature changes.

[0311] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 70-80% dimethicone and 20-30% (dimethicone / vinyl dimethicone) crosspolymer

[0312] (Production method) A: Components 1 to 5 were mixed, heated to 90°C, and mixed uniformly. B: Components 6 to 11 were added to the product obtained in step A above, and mixed uniformly at 90°C. C: The product obtained in step B above was degassed while heated, then filled into a container and cooled to room temperature, to obtain an oil-based eye color.

[0313] The eye color obtained in this manner was jelly-like, easy to remove, spread lightly, and had a texture that was neither oily nor powdery. It was also confirmed that it had good water resistance, water repellency, and sweat resistance, lasted well, was resistant to makeup smearing, and had excellent stability, with no change over time or with temperature changes.

[0314] (Note 1) Shin-Etsu Chemical Co., Ltd.: Hydrogen Dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: (Acrylates / Stearyl Acrylate / Dimethicone Methacrylate) Copolymer (Note 3) Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl Trimethicone

[0315] (Production Method) A: Components 1 to 10 are mixed uniformly using a Henschel mixer. B: Components 11 to 13 are mixed uniformly. C: The product obtained in step B is added to the product obtained in step A, and mixed uniformly using a Henschel mixer. D: The product obtained in step C is passed through a sieve and then stamped into a metal dish using a mold to obtain a powder eyeshadow.

[0316] The powder eye shadow obtained in the above manner was found to be extremely excellent in that it was smooth to apply, non-sticky, spread easily, had excellent adhesion, gave a well-balanced finish with a subdued shine, did not smudge, and lasted well.

[0317] (Note 1) Shin-Etsu Chemical Co., Ltd.: (Acrylates / Stearyl Acrylate / Dimethicone Methacrylate) Copolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: Diphenyl Dimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: Triethoxycaprylylsilane

[0318] (Manufacturing Method) A: Components 1 to 6 and a portion of 7 are mixed, heated to 90°C, and mixed uniformly. B: Components 8 and 9 and the remainder of 7 are mixed and rolled. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly at 90°C. D: Components 10 and 11 are added to the product obtained in step C and mixed uniformly at 90°C. E: The product obtained in step D is degassed while heated, then filled into a container and cooled to room temperature to obtain a stick lipstick.

[0319] The stick lipstick obtained in this manner spread easily, was not oily or powdery, had good water resistance and water repellency, was long-lasting, and had excellent stability.

[0320] (Note 1) Shin-Etsu Chemical Co., Ltd.: Mixture of 65-75% triethylhexanoin + 25-35% (vinyl dimethicone / lauryl dimethicone) crosspolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 50% cyclopentasiloxane + 50% trimethylsiloxysilicate (Note 4) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone

[0321] (Manufacturing Method) A: Components 1 to 7 are mixed, heated to 90°C, and mixed uniformly. B: Components 8 to 10 are mixed and rolled. C: Components 11 and 12 are mixed and dissolved uniformly. D: The product obtained in step B is added to the product obtained in step A and mixed uniformly at 90°C. E: The product obtained in step C is added to the product obtained in step D and mixed uniformly at 90°C. F: The product obtained in step E is cooled to room temperature, degassed, and then filled into a container to obtain a water-in-oil cream lipstick.

[0322] The obtained cream lipstick had excellent spreadability and smoothness when applied, was not sticky, had excellent adhesion, was well-fitting, had a beautiful finish with reduced unnatural shine, did not smudge, did not transfer or fade, had long-lasting makeup, and furthermore, did not dry out or roughen the lips, possessing other excellent characteristics.

[0323] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 65-75% squalane + 25-35% (vinyl dimethicone / lauryl dimethicone) crosspolymer. (Note 2) Shin-Etsu Chemical Co., Ltd.: A solution of 60% dimethicone (2cs) + 40% (acrylates / dimethicone) copolymer. (Note 3) Shin-Etsu Chemical Co., Ltd.: PEG-3 dimethicone. (Note 4) Shin-Etsu Chemical Co., Ltd.: Methicone.

[0324] (Manufacturing method) A: Components 1 to 6 are mixed uniformly. B: Components 7 to 11 are mixed uniformly and roll processed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: Component 12 is added to the product obtained in step C and mixed uniformly. E: The product obtained in step E is degassed and then filled into a container to obtain a lip gloss.

[0325] The lip gloss obtained in this manner had excellent spreadability and smoothness upon application, was not sticky, had excellent adhesion, was well-fitting, suppressed unnatural shine while providing a beautiful finish, did not smudge, transfer, or fade, and lasted for a long time, and further did not dry out or roughen the lips, possessing other excellent characteristics.

[0326] (Note 1) Shin-Etsu Chemical Co., Ltd.: PEG-9 polydimethylsiloxyethyl dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Isododecane 70% + norbornene / tris (trimethylsiloxy) silylnorbornene) copolymer 30% solution (Note 3) Shin-Etsu Chemical Co., Ltd.: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (Note 4) Shin-Etsu Chemical Co., Ltd.: KF-9909 treated colored inorganic pigment, W: white, B: black

[0327] (Manufacturing Method) A: Components 1 to 8 are heated and dissolved. B: Components 10 to 12 are mixed uniformly and rolled. C: The product obtained in step B and component 9 are added to the heated product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed, cooled to room temperature, and then filled into a container to obtain an oil-based mascara.

[0328] The oil-based mascara obtained in this manner was found to be extremely excellent in that it was smooth to apply, non-sticky, spread easily, had excellent adhesion, gave a well-fitting finish with a subdued shine, did not smudge, and lasted well.

[0329] (Note 1) Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate (Note 3) Shin-Etsu Chemical Co., Ltd.: Hydrogen Dimethicone

[0330] (Manufacturing method) A: Components 1 to 4 are mixed, and then components 5 and 6 are added and mixed uniformly. B: Components 7 to 9 are mixed and dissolved uniformly. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain a water-in-oil eyeliner.

[0331] The eyeliner obtained in this manner spread easily and was easy to apply, had a refreshing and refreshing feel, and was not sticky when used. It also showed no change with temperature or time, and was very easy to use and stable. It was confirmed that it was excellent in water resistance and sweat resistance, as well as having excellent makeup durability.

[0332] (Note 1) Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone (Note 3) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 70% cyclopentasiloxane + 30% (acrylates / dimethicone) copolymer (Note 4) Shin-Etsu Chemical Co., Ltd.: KF-9909 treated colored inorganic pigment, B: Black

[0333] (Manufacturing method) A: Components 1 to 6 are mixed, and then components 7 and 8 are added and mixed uniformly. B: Components 9 to 11 are mixed and dissolved uniformly. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain a water-in-oil eyeliner.

[0334] The eyeliner obtained in this manner spread easily, was not oily or powdery, and had good water resistance, water repellency, and sweat resistance, lasted well, and was resistant to makeup smudging. It was also confirmed to have excellent stability, with no change over time or with temperature changes.

[0335] (Note 1) Shin-Etsu Chemical Co., Ltd.: Triethoxycaprylylsilane (Note 2) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 40% isododecane and 60% trimethylsiloxysilicate (Note 3) Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone

[0336] (Manufacturing Method) A: Components 1, 2, and 5 to 9 are mixed, and components 3 and 4 are added and mixed uniformly. B: Components 10 to 13 are mixed. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is degassed and then filled into a container to obtain a water-in-oil eyeliner.

[0337] The eyeliner obtained in this manner spreads easily and is easy to apply, has a refreshing, light feel, is non-sticky when used, is water-resistant and sweat-resistant, and has excellent makeup wear. It was also confirmed that it did not change with temperature or over time.

[0338] (Note 1) Shin-Etsu Chemical Co., Ltd.: A mixture of 70-80% dimethicone and 20-30% dimethicone / PEG-10 / 15 crosspolymer. (Note 2) Shin-Etsu Chemical Co., Ltd.: Vinyl dimethicone / methicone silsesquioxane crosspolymer.

[0339] (Manufacturing method) A: Components 1 to 5 are mixed uniformly. B: Components 6 to 10 are mixed uniformly and dissolved. C: The product obtained in step B is added to the product obtained in step A and mixed uniformly. D: The product obtained in step C is defoamed and then filled into a container to obtain a water-in-oil antiperspirant cream.

[0340] The antiperspirant cream obtained in this manner spread easily, was not sticky or oily, did not change with temperature or over time, and was very easy to use and stable.

[0341] (Note 1) Shin-Etsu Chemical Co., Ltd.: Mixture of 70-80% dimethicone + 20-30% (dimethicone / (PEG-10 / 15)) crosspolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: Mixture of 90-96% cyclopentasiloxane + 4-10% (dimethicone / vinyl dimethicone) crosspolymer

[0342] (Manufacturing method) A: Components 1 to 4 are mixed uniformly. B: Components 5 to 7 are added to the material obtained in step A above and mixed uniformly. C: The material obtained in step B above is degassed and then filled into a container to obtain a roll-on type antiperspirant cosmetic.

[0343] The roll-on type antiperspirant cosmetic obtained in this manner spread easily, was not sticky or oily, did not change with temperature or over time, and was very easy to use and stable.

[0344] (Note 1) Shin-Etsu Chemical Co., Ltd.: Ethyl trimethicone (Note 2) Shin-Etsu Chemical Co., Ltd.: Mixture of (Cyclopentasiloxane 90-96% + (Dimethicone / Vinyl dimethicone) Crosspolymer 4-10%)

[0345] (Manufacturing method) A: Components 1 to 6 are heated and mixed uniformly. B: Components 7 to 9 are added to the material obtained in step A above and mixed uniformly. C: Component 10 is added to the material obtained in step B above and mixed uniformly. D: The material obtained in step C above is defoamed and then filled into a container to obtain an oily antiperspirant cream.

[0346] The antiperspirant cream obtained in this manner spread very smoothly and had good spreadability, was not excessively dry or sticky, and had excellent durability of deodorizing effect.

[0347] (Note 1) Shin-Etsu Chemical Co., Ltd.: Dissolved product of 60% methyl trimethicone + 40% (acrylates / dimethicone) copolymer (Note 2) Shin-Etsu Chemical Co., Ltd.: Methyl trimethicone

[0348] (Manufacturing Method) A: Components 7 to 9 are mixed, and then components 4 to 6 are added to the mixture and mixed uniformly. B: Components 1 to 3 are added to the mixture obtained in step A above and mixed uniformly. C: Component 10 is added to the mixture obtained in step B above and mixed uniformly. D: The mixture obtained in step C above is degassed and then filled into a container to obtain nail enamel.

[0349] The nail enamel obtained in this manner spreads easily, gives a visually smooth appearance, is water-resistant and oil-resistant, and lasts well. Furthermore, it was confirmed that the nail enamel is extremely stable, with no pressure on the nail, no yellowing of the nail, and no change in the cosmetic film over time or with temperature.

[0350] Due to their characteristic structural composition, the elastomer spherical particles and elastomer composite particles (polyorganosilsesquioxane- or silica-coated elastomer spherical particles) of the present invention are expected to be particularly useful in cosmetics and the like. Furthermore, because the powder / particle skeleton contains a degradable polyester structure (particularly poly-ε-caprolactone) and a polyether structure, they are expected to exhibit or be highly biodegradable. Therefore, cosmetics containing the elastomer spherical particles and / or elastomer composite particles of the present invention are expected to be used as environmentally friendly materials.

Claims

1. A cosmetic preparation containing at least one type of particle of the following (i) and (ii): (i) Elastomer spherical particles having a volume average particle size of 1.0 to 100 μm, which are crosslinked particles of a copolymer having a polyester structure and a polyether structure, (ii) Elastomer composite particles having polyorganosilsesquioxane or silica on the surface of the elastomer spherical particles of (i).

2. The cosmetic according to claim 1, wherein the copolymer is a polyester-polyether copolymer having at least two radically polymerizable unsaturated groups in one molecule.

3. The cosmetic according to claim 2, wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (1) or (2): (In general formula (1), R 1 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 2 Each independently represents a radical polymerizable functional group-containing organic group represented by the following general formula (3a), (3b), or (3c), each k independently represents a number of 1≦k≦10, each l represents a number of 1≦l≦1,000, each m represents a number of 1≦m≦1,000, and each n independently represents a number of 1≦n≦100. 3 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 4 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (4a) or (4b), each p is independently a number of 1≦p≦10, each l is a number of 1≦l≦1,000, each m is a number of 1≦m≦1,000, and each q is independently a number of 1≦q≦100. (In general formulas (3a), (3b), (3c), (4a) and (4b), R 5 each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms; R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

4. The cosmetic according to claim 2, wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (5): (In general formula (5), R 1 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R 2 each independently represents a radically polymerizable functional group-containing organic group represented by the following general formula (3a), (3b) or (3c), l is a number that satisfies 1≦l≦1,000, m is a number that satisfies 1≦m≦1,000, and each r is independently a number that satisfies 1≦r≦100. (In general formulas (3a), (3b) and (3c), R 5 each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms; R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

5. The cosmetic preparation according to claim 1, wherein the elastomer spherical particles have a rubber hardness of 10 to 80 as measured by a Type A durometer as specified in JIS K 6253.

6. The cosmetic according to claim 1, which is a skin care cosmetic.

7. The cosmetic according to claim 1, which is a makeup cosmetic.

8. The cosmetic according to claim 1, which is a sun care cosmetic.

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