Cosmetic

Abstract

Provided is a cosmetic material containing particles which can be degraded in the environment after use, do not remain as particles (solids), and can exhibit high flexibility, smoothness, and light diffusivity when blended in the cosmetic material. The cosmetic contains particles of at least one of the following (i) and (ii). (i) elastomer spherical particles which are crosslinked particles of a copolymer having a polyester structure and a polyether structure and have a volume average particle size of 1.0-100 [mu] m; (ii) elastomer composite particles having a polyorganosilsesquioxane or silica on the surface of the elastomer spherical particles (i).

Description

Technical Field

[0001] This invention relates to a cosmetic material containing elastomeric spherical particles comprising copolymers having polyester and polyether structures as constituent units, and / or elastomeric composite particles having polyorganosilsesquioxane or silica on the surface of the elastomeric spherical particles. Background Technology

[0002] Foundation and other color cosmetics are used to conceal skin imperfections such as wrinkles, pores, and roughness of texture, as well as tones such as blemishes and freckles, making the skin appear silky and radiant. In recent years, the natural, unartificial finish (the look of bare skin) has gained importance. Furthermore, a natural finish is considered to be achieved when a cosmetic has no unnatural sheen, excellent evenness of film adhesion, and high transparency.

[0003] In the past, various proposals for new raw materials and technologies have been put forward in order to achieve a natural, refined finish while maintaining the effects of the aforementioned makeup materials. In particular, makeup materials incorporating various diffusion-reflective powders are known as a method for concealing imperfections.

[0004] Patent Document 1 discloses a multi-layer cosmetic for concealing wrinkles, which combines a first layer of makeup base containing an adhesive substance and a second layer of makeup essence containing a light-diffusing and reflective powder. In this multi-layer cosmetic for concealing wrinkles, for example, a light-diffusing and reflective composite powder containing talc particles coated with an acrylic polymer is used.

[0005] However, this cosmetic has the following drawback: when the cosmetic film is maintained on the skin for a long time, the mixture of sebum and adhesive substances causes it to deviate from the optimal mixing range of the powder and adhesive substances, thus reducing its effectiveness.

[0006] Patent Document 2 discloses a sheet-like micropowder formed by coating the surface of sheet-like materials such as natural mica with spherical silica microparticles. Since this sheet-like micropowder uses spherical microparticles with a high surface diffusion and scattering effect of light, if it is used as a cosmetic additive, it can achieve the following technical effects: "It can achieve a so-called soft-focus effect, such as reducing the excessive luster of the mica matrix while making fine wrinkles less noticeable; in addition, it can also produce cosmetics with further improved silkiness and feel during use."

[0007] However, due to the excellent silkiness of the aforementioned flake-shaped micro-powders, cosmetics incorporating these powders tend to wrinkle during application, making it difficult to achieve an even finish and resulting in a lack of natural, refined texture. Furthermore, the silica microparticles used as a coating agent reduce the contact area between the composite powder and the skin, leading to decreased adhesion and making the composite powder prone to detachment from the skin due to physical impacts such as friction from clothing, thus reducing the longevity of the cosmetic effect. Additionally, if the proportion of silica microparticles in the flake-shaped micro-powder is reduced, it becomes difficult to effectively address morphological defects if the goal of improving the composite powder's adhesion to the skin is to be achieved.

[0008] In addition, as a technique similar to these aimed at avoiding morphological defects or creating a natural, refined feel, there are the following techniques: cosmetics containing a core-shell structure pigment that uses a thin sheet-like base pigment as a core material, coats these core materials with titanium dioxide containing colored pigment, and further coats them with a light-diffusing powder (Patent Document 3); techniques that incorporate a composite powder coated with an inorganic metal hydroxide such as aluminum hydroxide onto the surface of clay minerals into the cosmetic (Patent Documents 4, 5); cosmetics containing a powder with a refractive index of 1.6 to 1.7 such as barium sulfate, having a layer coated with a metal oxide of a high refractive index, and having a layer on the layer coated with one or more of iron oxide yellow, black iron oxide, and red lead (Patent Document 6); and cosmetics incorporating a silica / zinc oxide composite obtained by combining silica sol and zinc oxide (Patent Document 7), etc.

[0009] However, since these composite powders achieve a certain degree of soft, hazy effect through their light diffusion, and are composed of inorganic metal oxides or inorganic metal hydroxides, from the perspective of the user experience of cosmetics, the hardness of the composite powder itself does not fully satisfy the requirements of softness, moistness, and silkiness.

[0010] On the other hand, in order to improve the feel of cosmetic powder, that is, to give it a smooth, silky feel, spreadability, and adhesion, Patent Document 8 discloses that the particles on the surface of the scaly inorganic particles are coated with polyurethane, butadiene-styrene copolymer, silicone elastomer or polyolefin elastomer, thereby being believed to obtain a soft and moist feel.

[0011] Other literature discloses particles on which organosilicon elastomers are attached or coated, and methods for manufacturing them.

[0012] For example, Patent Document 9 discloses a method for pulverizing and mixing an organosilicon elastomer with reactive functional groups and silica. However, since the silica particles used as masterbatch are pulverized, it is impossible to obtain particles that retain their initial shape and particle size. That is, it is impossible to obtain particles with specific shapes such as granules, plates, or rods. In addition, there is a drawback that it is difficult to control the particle size.

[0013] Patent Document 10 discloses a method for curing silicone by mixing masterbatch and a curable silicone to be used as a silicone elastomer, but the resulting particles contain multiple masterbatch particles. Patent Document 11 discloses a method for curing silicone by emulsifying and dispersing a mixture of silica particles (as masterbatch) and a curable silicone to be used as a silicone elastomer in water; Patent Document 12 discloses a method for curing silicone by emulsifying and dispersing a mixture of an aqueous dispersion of silica particles and a curable silicone to be used as a silicone elastomer in water. However, in both methods, multiple masterbatch particles are present in the particles, or particles without masterbatch particles are produced.

[0014] Therefore, Patent Document 13 discloses a composite particle that can attach silicone elastomer to the surface of a core powder using silicone resin as a binder by adding an acidic or alkaline substance and a compound selected from alkoxysilanes, silanes containing silanol groups, and their partial condensates to a mixed aqueous dispersion of powder and silicone elastomer, and causing the compound to undergo hydrolysis and condensation reactions. Cosmetics containing these composite particles have the unique looseness of silicone elastomers, exhibiting a soft and moist feel, and have good spreadability, softness, adhesion, and mixing properties, which can provide a shape-repairing effect to the skin.

[0015] In addition, silicone rubber spherical particles are used in a wide range of cosmetics and cosmetic materials, such as foundation and color makeup bases, skin care cosmetics such as creams and lotions, and sunscreens, to give cosmetics a soft and silky feel, to create a natural finish that scatters light, and to make pores and wrinkles less visible.

[0016] For example, cosmetics containing polymethylsilsesquioxane particles and powders have been disclosed (Patent Document 14), color cosmetics having spherical silicone rubber particles and powders have been disclosed (Patent Document 15), and cosmetics containing silicone composite particles and powders containing polymethylsilsesquioxane resin coated on silicone rubber spherical particles have been disclosed (Patent Document 16). These silicone rubber spherical particles or composite particles formed by coating polymethylsilsesquioxane resin on silicone rubber spherical particles, as described above, can also impart a soft touch and silky smoothness to the cosmetics.

[0017] Existing technical documents

[0018] Patent documents

[0019] Patent Document 1: Japanese Patent Application Publication No. 6-128122

[0020] Patent Document 2: International Publication No. 92 / 03119

[0021] Patent Document 3: Japanese Patent Application Publication No. 8-188723

[0022] Patent Document 4: Japanese Patent Application Publication No. 9-20609

[0023] Patent Document 5: Japanese Patent Application Publication No. 2002-146238

[0024] Patent Document 6: Japanese Patent Application Publication No. 2003-40737

[0025] Patent Document 7: Japanese Patent No. 3702072

[0026] Patent Document 8: Japanese Patent No. 3963635

[0027] Patent Document 9: Japanese Patent Application Publication No. 8-3451

[0028] Patent Document 10: Japanese Patent Application Publication No. 3-294357

[0029] Patent Document 11: Japanese Patent Application Publication No. 2-232263

[0030] Patent Document 12: Japanese Patent Application Publication No. 3-281536

[0031] Patent Document 13: Japanese Patent Application Publication No. 2011-1332

[0032] Patent Document 14: Japanese Patent Application Publication No. 63-297313

[0033] Patent Document 15: Japanese Patent Application Publication No. 8-12524

[0034] Patent Document 16: Japanese Patent Application Publication No. 9-20631 Summary of the Invention

[0035] The problem the invention aims to solve

[0036] However, when these organosilicon rubber spherical particles or polymethyl silsesquioxane particles, as well as organosilicon composite particles that coat organosilicon rubber spherical particles with polyorganosilsesquioxane resin, are released or flow out of natural environments such as soil, inland water systems, or seawater and ocean, they may not be degradable and may continue to remain in the environment because they do not contain a skeleton or unit with degradability in their particle structure.

[0037] In addition, plastics flowing into the ocean and microplastics that have degraded and been miniaturized to the millimeter to micrometer scale are also being restricted. Because they have the ability to adsorb harmful substances and pathogens in the environment, they are being ingested by marine life, raising concerns that they may have adverse effects on the ecosystem. Therefore, restrictions on these microplastics have also begun to be implemented.

[0038] On the other hand, although silica or biodegradable cellulose powder is present in spherical particles that do not conform to microplastics incorporated in various cosmetics, they are inferior in terms of softness, silkiness, and light diffusion compared to silicone rubber spherical particles, polymethylsilsesquioxane particles, and silicone composite particles in which silicone rubber spherical particles are coated with polyorganosilsesquioxane resin.

[0039] For this reason, people are looking for elastomeric spherical particles that degrade in the environment after use, do not leave as particles (solids), and exhibit high softness, silkiness, and light diffusion when incorporated into cosmetics.

[0040] In view of the above-mentioned problems, the purpose of the present invention is to provide a cosmetic material comprising elastomeric spherical particles and / or elastomeric composite particles that are highly degradable (copolymer) polymers as structural units in natural environments including soil, inland water systems, oceans, and seawater, and are subjected to external stimuli such as light, heat, acid, alkali and the action of microorganisms and fungi.

[0041] Methods for solving problems

[0042] In order to achieve the above-mentioned objectives, the inventors have repeatedly conducted in-depth research and found that cosmetics containing elastomeric spherical particles and / or elastomeric composite particles that are crosslinked particles of copolymers having specific polyester and polyether structures can solve the above-mentioned problems, thereby completing the present invention.

[0043] Therefore, the present invention provides the following cosmetic material.

[0044] [1]. A cosmetic containing at least one of the particles described in (i) and (ii).

[0045] (i) Elastomer spherical particles, which are cross-linked particles of copolymers with polyester and polyether structures, with a volume average particle size of 1.0~100 μm;

[0046] (ii) Elastomer composite particles having polyorganosilsesquioxane or silica on the surface of the (i) elastomeric spherical particles.

[0047] [2]. According to the cosmetic of [1], wherein the copolymer is a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule.

[0048] [3]. According to the cosmetic of [2], wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (1) or general formula (2).

[0049] [Chemical Formula 1]

[0050]

[0051] (In general formula (1), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following formulas (3a), (3b) or (3c) represents an organic group containing a free radical polymerizable functional group, where k is a number that is 1 ≤ k ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and n is a number that is 1 ≤ n ≤ 100.

[0052] In general formula (2), R 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the following general formulas (4a) and (4b) independently represents an organic group containing a free radical polymerizable functional group, where p is a number that is 1 ≤ p ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and q is a number that is 1 ≤ q ≤ 100.

[0053] [Chemical Formula 2]

[0054]

[0055] (In general formulas (3a), (3b), (3c), (4a), and (4b), R) 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0056] [4]. The cosmetic according to [2], wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (5).

[0057] [Chemical Formula 3]

[0058]

[0059] (In general formula (5), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following can be represented independently as an organic group containing a free radical polymerizable functional group, represented by general formula (3a), general formula (3b), or general formula (3c), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and r is a number 1 ≤ r ≤ 100.

[0060] [Chemical Formula 4]

[0061]

[0062] (In general formulas (3a), (3b) and (3c), R) 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0063] [5]. The cosmetic according to any one of [1] to [4], wherein the elastomeric spherical particles are elastomeric spherical particles having a rubber hardness of 10 to 80 as measured by a type A hardness tester specified by JIS K 6253.

[0064] [6]. The cosmetic material according to any one of [1] to [5], wherein the cosmetic material is a skin care cosmetic material.

[0065] [7]. The cosmetic material according to any one of [1] to [5], wherein the cosmetic material is a color cosmetic material.

[0066] [8]. The cosmetic material according to any one of [1] to [5], wherein the cosmetic material is a sunscreen cosmetic material.

[0067] The effects of the invention

[0068] The cosmetic material of the present invention, comprising elastomeric spherical particles and / or elastomeric composite particles, can provide a cosmetic material with good spreadability, softness, adhesion, and mixing properties, and excellent skin morphology repair effect.

[0069] Furthermore, elastomeric composite particles formed by attaching polyorganosilsesquioxanes or silica to the surface of elastomeric spherical particles are elastomeric composite particles that exhibit excellent spreadability, usability, adhesion, dispersibility, shape restoration effect, water resistance, and sebum resistance. Cosmetics of the present invention using such composite particles provide a gentle spreadability, enabling soft and even application; excellent dispersibility, sebum resistance, and makeup retention; and exhibits exceptional stability regardless of the cosmetic composition, remaining unchanged with temperature and time.

[0070] Furthermore, the elastomeric spherical particles and / or elastomeric composite particles, due to the presence of a degradable polyester structure within the particles' unit backbone, exhibit degradability because the cross-linking structure of the particles is broken in the presence of moisture. In particular, particles with a poly-ε-caprolactone structure as the polyester structure within the particles, providing a framework for microbial recognition, are expected to exhibit both environmental and biodegradability.

[0071] Therefore, the cosmetic containing elastomeric spherical particles and / or elastomeric composite particles of the present invention is expected to be used and utilized as a material that reduces environmental burden. Attached Figure Description

[0072] [ Figure 1 [Image of an electron microscope image of the elastomeric spherical particles obtained in Preparation Example 1.]

[0073] [ Figure 2 [Image of an electron microscope image of the elastomeric spherical particles obtained in Preparation Example 3.]

[0074] [ Figure 3 [Electron microscope image (magnification × 1000) of the elastomer composite particles (silica-coated elastomer spherical particles) obtained in Preparation / Manufacturing Example 3.]

[0075] [ Figure 4 [Electron microscope image (magnification × 7500) of the elastomer composite particles (silica-coated elastomer spherical particles) obtained in Preparation / Manufacturing Example 3.] Detailed Implementation

[0076] The cosmetic material of the present invention is characterized by containing,

[0077] (i) Elastomeric spherical particles with a volume average particle size of 1.0~100 μm, which are cross-linked particles of copolymers with polyester and polyether structures, and / or

[0078] (ii) The surface of the elastomeric spherical particles has elastomeric composite particles of polyorganosilsesquioxane or silica.

[0079] The present invention will now be described in detail in the following order.

[0080] I. Elastomer spherical particles and methods for manufacturing elastomeric spherical particles,

[0081] II. Elastomer composite particles and methods for manufacturing elastomeric composite particles,

[0082] III. A method for manufacturing cosmetics using elastomeric spherical particles and elastomeric composite particles.

[0083] IV. Cosmetics containing elastomeric spherical particles and elastomeric composite particles.

[0084] I. Elastomeric spherical particles and methods for manufacturing elastomeric spherical particles

[0085] The elastomeric spherical particles incorporated in the cosmetics of the present invention refer to polymers (crosslinked particles) of copolymers having polyester and polyether structures.

[0086] The shape of the spherical elastomer particles is preferably spherical.

[0087] In this invention, "spherical" does not refer to a particle shape that is only a sphere, but also includes a deformed ellipsoid with an average aspect ratio (length of the longest axis / length of the shortest axis), which is usually in the range of 1 to 4, preferably in the range of 1 to 2, more preferably in the range of 1.0 to 1.6, and even more preferably in the range of 1.0 to 1.4.

[0088] As shown in the manufacturing method described later, when crosslinking is achieved by emulsifying, suspending and dispersing copolymers having polyester and polyether structures using surfactants or suspending agents, the resulting particles are spherical in shape.

[0089] The shape of the elastomeric spherical particles can be confirmed by observation using, for example, an optical microscope and an electron microscope, with the aspect ratio calculated as the average of the lengths of the longest and shortest axes of 50 particles arbitrarily measured from the microscope images.

[0090] In this invention, the volume average particle size of the elastomeric spherical 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.

[0091] When the volume average particle size is greater than 100 μm, the particles become less mobile and more cohesive, which prevents them from fully imparting the smoothness and light diffusivity they should possess. Conversely, when the volume average particle size of the elastomer composite particles is less than 1.0 μm, the smoothness and looseness of the particles may decrease, resulting in a rougher feel and reduced light diffusivity.

[0092] The volume average particle size of the elastomeric spherical particles is expressed as the volume average particle size measured by the following method. Before measuring the volume average particle size, the particle size of 50 particles is randomly measured from a microscopic photograph of the elastomeric spherical particles, and the average value is determined to be either greater than or less than 1 µm. A dispersion of the elastomeric spherical particles in water is prepared using various surfactants. If the previously determined value is greater than 1 µm, the volume average particle size is expressed as the value measured by the resistance method; if the determined value is less than 1 µm, the volume average particle size is expressed as the value measured by laser diffraction / scattering.

[0093] The rubber (elastomer) containing spherical elastomeric particles is preferably a non-sticky or non-adhesive rubber. The hardness of the rubber (elastomer) containing spherical elastomeric particles, when measured using a Type A hardness tester as specified in JIS K 6253, is preferably in the range of 10 to 80, more preferably in the range of 20 to 70. Furthermore, when measuring the hardness of the rubber using a Type C ASKER rubber hardness tester as specified in the Japan Rubber Industry Association Standard Specification (SRIS), the hardness of the rubber (elastomer) containing spherical elastomeric particles is preferably in the range of 10 to 90, more preferably in the range of 20 to 90, and even more preferably in the range of 40 to 90.

[0094] When the rubber hardness value in each measurement is below 10, the particle cohesion increases and the dispersibility decreases. Furthermore, when the rubber hardness value in the measurement using a Type A durometer is greater than 80, the softness to the touch decreases, making it less desirable.

[0095] The elastomeric spherical particles are more preferably particles composed of a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule, that is, cross-linked particles of a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule.

[0096] A polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule, preferably a copolymer represented by the following general formula (1) or general formula (2).

[0097] [Chemical Formula 5]

[0098]

[0099] (In general formula (1), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2Organic groups containing free radical polymerizable functional groups, represented independently by the following general formulas (3a), (3b) or (3c), where k is a number that is 1 ≤ k ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and n is a number that is 1 ≤ n ≤ 100.

[0100] In general formula (2), R 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the following general formulas (4a) and (4b) independently represents an organic group containing a free radical polymerizable functional group, where p is a number that is 1 ≤ p ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and q is a number that is 1 ≤ q ≤ 100.

[0101] [Chemical Formula 6]

[0102]

[0103] (In general formulas (3a), (3b), (3c), (4a), and (4b), R) 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0104] As R 1 Examples of such alkylene compounds include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene, with methylene, ethylene, trimethylene, and tetramethylene being preferred.

[0105] As R 3 Examples of such alkylene compounds include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene, with methylene, ethylene, trimethylene, and tetramethylene being preferred.

[0106] R 2 R represents an organic group containing a free radical polymerizable functional group, represented by general formula (3a), general formula (3b) or general formula (3c). 4 It represents an organic group containing a free radical polymerizable functional group, represented by general formula (4a) or general formula (4b).

[0107] In general formulas (3b), (3c), (4a), and (4b), as R 5Examples of such compounds include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, and other alkylene compounds; preferably methylene, ethylene, trimethylene, or tetramethylene.

[0108] In general formulas (3a), (3b), (3c), (4a), and (4b), as R 6 Examples of such elements include hydrogen atoms, alkyl groups with 1 to 3 carbon atoms such as methyl, ethyl, and propyl, with hydrogen atoms or methyl atoms being preferred.

[0109] These organic groups containing free radical polymerizable functional groups, represented by general formulas (3a), (3b), (3c), (4a), and (4b), are residues derived from polymerizable monomers. Specifically, examples of polymerizable monomers include (meth)acrylates containing hydroxyl groups, (meth)acrylates containing isocyanate groups, and methacryloyl chloride.

[0110] Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates with 2 to 8 carbon atoms; and carboxylated (meth)acrylates such as carboxyethyl (meth)acrylate, methacryloyloxyethyl succinate, and methacryloyloxyethyl phthalate.

[0111] Examples of (meth)acrylates containing isocyanate groups include, for example, ethyl isocyanate (meth)acrylate, propyl isocyanate (meth)acrylate, butyl isocyanate (meth)acrylate, and hexyl isocyanate (meth)acrylate.

[0112] Examples of methacryloyl chloride include acryloyl chloride, methacryloyl chloride, acryloyl bromide, and methacryloyl bromide.

[0113] The polyester structure (unit) of a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule is preferably an aliphatic polyester with degradation ability or improved degradation ability.

[0114] Examples of aliphatic polyesters include poly-ε-caprolactone, poly-β-propiolactone, γ-butyrolactone, polylactic acid, polyhydroxybutyrate, polyglycolic acid, polyethylene adipate, polyhydroxybutyric acid, polybutylene succinate, and polybutylene succinate. In particular, from the viewpoint of degradability and ease of handling, a poly-ε-caprolactone structure is preferred.

[0115] In general formula (1), k is independently a number that is 1≤k≤10, preferably a number that is 1≤k≤6.

[0116] In general formula (2), p can be a number that is 1≤p≤10, preferably a number that is 1≤p≤6.

[0117] In general formula (1), n ​​can be a number that is 1≤n≤100, preferably a number that is 1≤n≤50, and even more preferably a number that is 2≤n≤20.

[0118] In general formula (2), q can be a number that is 1≤q≤100, preferably a number that is 1≤q≤50, and even more preferably a number that is 2≤q≤20.

[0119] When n and q are greater than the above upper limits, the crystallinity increases due to the intramolecular / intermolecular interactions of the polymer generated by the ester structure (unit). Therefore, if the flowability of the copolymer is too low, it may affect the processability in the preparation process of the emulsified (suspension) composition described later.

[0120] In general formulas (1) and (2), l is a number that is 1≤l≤1000, preferably a number that is 2≤l≤100.

[0121] In general formulas (1) and (2), m is a number that is 1 ≤ m ≤ 1000, preferably a number that is 10 ≤ m ≤ 500.

[0122] When the value of l is greater than the aforementioned upper limit, the crystallinity of the polymer, generated by the intramolecular / intermolecular interactions of the polymer produced by the ethylene oxide (EO) structural (unit), may increase, thereby potentially reducing the flowability of the copolymer. In this case, as described above, the processability may be affected in the preparation process of the emulsified (suspension) composition, which is described later, and is therefore not preferred.

[0123] A polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule is preferably a copolymer represented by the following general formula (5) or general formula (6) from the viewpoint of raw material handling and ease of manufacturing.

[0124] [Chemical Formula 7]

[0125]

[0126] (In general formula (5), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following can be represented independently as an organic group containing a free radical polymerizable functional group, represented by general formula (3a), (3b), or (3c), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and r is a number 1 ≤ r ≤ 100.

[0127] (In general formula (6), R) 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the above represents an organic group containing a free radical polymerizable functional group, represented by general formula (4a) or general formula (4b), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and s is a number 1 ≤ s ≤ 100.

[0128] [Manufacturing method of polyester-polyether copolymer]

[0129] Before explaining the manufacturing method of the elastomeric spherical particles, the manufacturing method of the polyester-polyether copolymer constituting the elastomeric spherical particles will be explained first.

[0130] Examples of methods for manufacturing polyester-polyether copolymers include using various polyethers containing active hydrogen, such as hydroxyl-containing polyethers, carboxyl-modified polyethers, and amino-modified polyethers, as starting materials, and obtaining poly-ε-caprolactone-modified polyethers and poly-γ-butyrolactone-modified polyethers by ring-opening polymerization of cyclic ε-caprolactone, γ-butyrolactone, etc., and then introducing polymerizable monomers with unsaturated groups capable of free radical polymerization through ester bonds, ether bonds, urethane bonds, amide bonds, etc.

[0131] It should be noted that, from the perspective of reactivity during manufacturing, the terminal structure of various polyethers is preferably a structure in which reactive functional groups are bonded to primary carbon atoms.

[0132] In the above manufacturing method, the reaction conditions can be exemplified by, for example, the following reaction conditions, but are not limited to these reaction conditions.

[0133] For example, 3.0 to 4.0 equivalents (functional group equivalent ratio) of cyclic ε-caprolactone are added to 1.0 equivalents of polyether or carboxyl-modified polyether containing active hydrogen, and the reaction is carried out at 120°C for 4 to 6 hours in the presence of a known ring-opening polymerization catalyst to obtain poly-ε-caprolactone modified polyether.

[0134] Next, for example, 1.0 to 1.25 mol (functional group equivalent ratio) of (meth)acryloyl chloride or (meth)acrylate containing isocyanate groups, such as isocyanate ethyl ester of (meth)acrylate, is added to the hydroxyl groups of 1.0 mol of the obtained poly-ε-caprolactone modified polyether, and a reaction catalyst is added as needed, and the reaction is carried out at 40 to 100 °C for more than 4 hours.

[0135] After the reaction, the crude product is rapidly cooled with alcohol or the like, and byproducts are removed by filtration, washing with water and / or adsorption treatment. Finally, the solvent is removed by distillation, thereby obtaining acrylic acid-modified poly-ε-caprolactone polyether (polyester-polyether copolymer).

[0136] When a polyether having hydroxyl groups is used as the starting material, examples of polyester-polyether copolymers can be cited, for example, those represented in general formulas (7a) and (7b) (only the one-sided structure is described due to the symmetrical structure).

[0137] [Chemical Formula 8]

[0138]

[0139] In general formulas (7a) and (7b), R 5 R is a divalent hydrocarbon group with 1 to 8 carbon atoms. 6 It consists of hydrogen atoms or hydrocarbon groups with 1 to 3 carbon atoms.

[0140] l, m, and r are 1≤l≤1000, 1≤m≤1000, and 1≤r≤30, respectively, with the preferred values ​​being 2≤l≤100, 10≤m≤500, and 2≤r≤10, respectively.

[0141] When carboxyl-modified polyether is used as the starting material, examples of polyester-polyether copolymers can be cited, for example, those represented in general formulas (8a) and (8b) (only single-end copolymers are described due to their symmetrical structure).

[0142] [Chemical Formula 9]

[0143]

[0144] In general formulas (8a) and (8b), R 5 R is a divalent hydrocarbon group with 1 to 8 carbon atoms. 6 It consists of hydrogen atoms or hydrocarbon groups with 1 to 3 carbon atoms.

[0145] In addition, l, m, s and t are 1≤l≤1000, 1≤m≤1000, 1≤s≤30 and 0≤t≤10 respectively, and preferably 2≤l≤100, 10≤m≤500, 2≤s≤10 and 1≤t≤10 respectively.

[0146] As a catalyst for the ring-opening polymerization of cyclic ε-caprolactone, conventionally known catalysts can be used, but are not limited thereto.

[0147] Specifically, examples include organotitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, and tetran-butoxytitanium; organotin compounds such as di-n-butyltin dilaurate, diisobutyltin oxide, and dibutyltin diacetate; acetates of magnesium, calcium, zinc, etc.; antimony oxide; stannous halides; and perchloric acid.

[0148] The amount of the above-mentioned ring-opening polymerization catalyst added, relative to the ε-caprolactone monomer (cyclic ε-caprolactone), can be in the range of 1 to 10,000 ppm, preferably in the range of 10 to 1,000 ppm.

[0149] As a method for introducing polymerizable monomers with unsaturated groups capable of free radical polymerization into poly-ε-caprolactone-modified polyethers, the reaction matrix (reactive functional group) of the polymerizable monomer and various catalysts corresponding to the formation of the framework can be used. Conventionally known catalysts can be used as catalysts.

[0150] Examples of (esterification) catalysts for esterification reactions in which the reaction of polymerizable monomers with poly-ε-caprolactone-modified polyethers is an esterification reaction include Lewis acid catalysts such as alkoxides of titanium, zirconium, tin, aluminum, and zinc; carboxylates of titanium, zirconium, tin, aluminum, and zinc; chelates of titanium, zirconium, tin, aluminum, and zinc; and boron trifluoride and boron trifluoride ethers; 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), 1,4,7-trimethyl-1,4,7-triazacyclononane (TACN), triethylamine (TEA), 4-N,N-dimethylaminopyridine (DMAP), 1,4-diazabicyclo(2,2,2)octane (DABCO), and tetramethylethylenediamine (TMEDA). Among these, amine catalysts are preferred from the viewpoint of the stability and economy of the product obtained by the esterification reaction.

[0151] It should be noted that, when using amine-based catalysts, dehydrating condensing agents can also be added to improve reaction efficiency. Commonly known dehydrating condensing agents include, for example, 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), but are not limited to these.

[0152] Examples of catalysts for carbamate reactions in which the reaction of polymeric monomers with poly-ε-caprolactone-modified polyethers is a carbamate reaction include, for example, 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); and amines such as dibutyltin dilaurate, diisobutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate (DBTL), and dioctyl dinedecyltin oxide. Organotin compounds such as dineodecanoate; organotitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetraoctyloxytitanium, acetylacetone titanium, tetraacetylacetone titanium, dodecylbenzenesulfonate titanium compounds, phosphate titanium complexes, triethanolamine titanium, diisopropoxybis(acetoethyl acetoethyl) titanium, etc.; organozirconium compounds such as n-propylzirconate, n-butylzirconate, tetraacetylacetone zirconium, dibutoxybis(acetoethyl acetoethyl) zirconium, zirconium octanoate compounds, etc.; organoiron compounds such as tri(2,4-pentanedione)iron(III), etc.

[0153] The amount of catalyst added when introducing these polymerizable monomers with unsaturated groups capable of free radical polymerization can be in the range of 1 to 10,000 ppm, preferably in the range of 10 to 1,000 ppm, relative to the polymerizable monomer.

[0154] In order to inhibit the polymerization of (meth)acrylate groups during the above reaction, polymerization inhibitors and antioxidants can be used.

[0155] Examples of polymerization inhibitors or antioxidants include, but are not limited to, hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,4-dimethyl-6-tert-butylphenol, p-benzoquinone, dibutylhydroxytoluene, 2,5-dihydroxy-p-benzoquinone, p-methoxyphenol, etc.

[0156] As a method for manufacturing polyester-polyether copolymers, when carboxyl-modified polyether is used as the starting material, an example is a method of manufacturing by esterifying the above-mentioned carboxyl-modified polyether with poly-ε-caprolactone-modified (meth)acrylate represented by the following formula (9).

[0157] Commercially available products of poly-ε-caprolactone-modified (meth)acrylates include, for example, PLACEL FA2D, PLACEL FA10L, PLACEL FN2D, and PLACEL FM4 (manufactured by Daicel Corporation).

[0158] [Chemical Formula 10]

[0159]

[0160] In general formula (9), R 7 It is a monovalent hydrocarbon group with 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. v is 1 ≤ v ≤ 50, preferably 1 ≤ v ≤ 30.

[0161] Examples of manufacturing methods for the aforementioned polyester-polyether copolymers include, but are not limited to, the manufacturing methods shown below.

[0162] Relative to 1.0 mole of the carboxyl group of the carboxyl-modified polyether, 1.0 to 1.25 moles (functional group equivalent ratio) of poly-ε-caprolactone-modified (meth)acrylate (general formula (9)) were added and mixed, and further 0.1 to 5.0 moles of esterification catalyst were added and mixed, and stirred at 15 to 150 °C for 10 to 30 minutes. Optionally, 1.0 to 1.25 moles of dehydrating condensing agent were added, and the mixture was reacted at 15 to 150 °C for 4 to 20 hours.

[0163] After the reaction, byproducts are removed by filtering, washing and / or adsorption of the crude product, and finally the solvent is removed by distillation, thereby obtaining an acrylic-modified polyester (poly-ε-caprolactone)-polyether copolymer.

[0164] A polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule, preferably in liquid form, with a weight-average molecular weight (M) determined by gel permeation chromatography (GPC). W The value of .) is preferably in the range of 100 to 100,000, more preferably in the range of 500 to 50,000.

[0165] If the weight-average molecular weight is less than the lower limit mentioned above, the crosslinking density of the elastomer in the obtained elastomer spherical particles / composite particles may become higher, and the degradation performance may become worse, which is not preferred; if the weight-average molecular weight is greater than the upper limit mentioned above, the viscosity of the copolymer may increase, and the preparation of elastomer spherical particles may become difficult.

[0166] In the filtration process, hydrophobic organic solvents can also be used for dilution to adjust the viscosity of the crude reaction product.

[0167] There are no particular limitations on the hydrophobic organic solvent used, but from the viewpoint of solubility or affinity for polyester-polyether copolymers, toluene, hexane, ethyl acetate, etc. are preferred.

[0168] The adsorption treatment process is a process performed to remove hydrochloric acid that cannot be completely removed by water washing, and to dehydrate, decolorize, and deodorize.

[0169] As for the adsorbent material used, any conventionally known adsorbent material is acceptable, and multiple adsorbent materials can be used in combination. Preferred adsorbent materials include, for example, desiccants such as magnesium sulfate and sodium sulfate; activated carbon; silica gel; and the KYOWAAD series (manufactured by Kyowa Chemical Industry Co., Ltd., Japan).

[0170] [Manufacturing method of elastomeric spherical particles]

[0171] Next, a method for manufacturing elastomeric spherical particles using a polyester-polyether copolymer obtained by the aforementioned method will be described.

[0172] Elastomer spherical particles can be manufactured by passing through a dispersion of elastomeric spherical particles using known methods.

[0173] Elastomer spherical particles can be manufactured, for example, by a method having the steps described in i) to iii).

[0174] i) The process of stirring, emulsifying, and suspending the following components (A), (B), (C), and (D) to prepare an emulsified (suspended) suspension composition.

[0175] (A) A copolymer having polymerizable groups and having both polyester and polyether structures.

[0176] (B) The aqueous or oil phase components in which component (A) is insoluble or sparingly soluble

[0177] (C) Surfactants or suspending agents

[0178] (D) Polymerization initiator

[0179] ii) A process of obtaining a dispersion of elastomeric spherical particles by (free radical) polymerization of component (A) in the emulsion (suspension) composition obtained in step i) through external stimulation such as heat, light, or ultraviolet light.

[0180] iii) A process of obtaining elastomeric spherical particles by washing and drying the dispersion of elastomeric spherical particles obtained by step ii) above to remove component (B) as the continuous phase.

[0181] When an emulsified (suspension) composition is prepared and then subjected to a (free radical) polymerization reaction, and spherical elastomer particles are obtained using the manufacturing method described above, the obtained particles are spherical in shape.

[0182] Project i)

[0183] In step i), the following components (A), (B), (C) and (D) are stirred, emulsified, and suspended to prepare an emulsified (suspended) composition.

[0184] The components used in engineering i) are as follows.

[0185] (A) The component is a copolymer having polymerizable groups and having a polyester structure and a polyether structure, preferably a polyester-polyether copolymer having unsaturated groups that can be free radical polymerized.

[0186] The constituent units of the elastomeric spherical particles are derived from the constituent units of copolymers having polyester and polyether structures, and preferably polyester-polyether copolymers having at least two unsaturated groups capable of free radical polymerization in the molecule can be used.

[0187] As a specific example of component (A), examples include polyester-polyether copolymers represented by the above general formula (1) or general formula (2), and more preferably polyester-polyether copolymers represented by the general formula (5) or general formula (6).

[0188] The content of component (A) in the emulsified (suspension) composition prepared in step i) is preferably 1.0 to 80 parts by mass relative to 100 parts by mass of the composition. Since production efficiency may decrease if the amount of component (A) is less than the lower limit mentioned above, and if the amount of component (A) is greater than the upper limit mentioned above, it may sometimes lead to poor emulsification (suspension) and make it difficult to obtain a dispersion of elastomeric spherical particles, it is not preferred.

[0189] (B) is a component that forms a continuous phase in the emulsion (suspension) composition, and (A) is an aqueous or oil phase component that is insoluble or sparingly soluble therein.

[0190] When component (B) is an aqueous phase, the water contained in the aqueous phase can be exemplified by, for example, distilled water, ion-exchanged water, pure water, ultrapure water, etc.

[0191] In the aqueous phase, additives may be optionally incorporated to the extent that their function as a continuous phase is not impaired. Examples of additives include, but are not limited to, preservatives, salts, pH adjusters, chelating agents, vitamins, amino acids, humectants, and antioxidants. Since component (A) is an insoluble or poorly soluble component, the water content in the aqueous phase is preferably 90-100% by mass.

[0192] When component (B) is an oil phase component, examples of oil phase components include silicone oil, hydrocarbon oil, higher fatty acids, ester oil, liquid fats, etc. They can be used alone or in combination of two or more appropriately, but are not limited thereto.

[0193] Examples of silicone oils include, for example, dimethylpolysiloxane, methylhydropolysiloxane, methylphenylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane.

[0194] Examples of hydrocarbon oils include, for example, liquid paraffin, α-olefin oligomers, isododecane, isohexadecane, squalane, crude ceresin, squalene, refined ceresin, alkanes, isoalkanes, paraffin, polyethylene wax, polyethylene-polypropylene wax, squalane, polyisobutylene, petrolatum, and microcrystalline wax.

[0195] Examples of high-grade fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, benzolic acid, undecenoic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0196] Examples of ester oils include, for example, isopropyl myristate, cetyl octanoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, isononyl isononanoate, cholesterol 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol didecanoate, diisostearate malate, glyceryl di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2-ethylhexanoate, etc. Pentaerythritol ester, tri-2-ethylhexanoate glyceryl ester, trioctanoate glyceryl ester, triisopalmitoate glyceryl ester, trimethylolpropane triisostearate, hexadecyl 2-ethylhexyl hexanoate, 2-ethylhexyl palmitate, trimyristic acid glyceryl ester, tri-2-heptylundecanoate glyceryl ester, castor oil fatty acid methyl ester, oleic acid oleyl alcohol ester, acetylglycine ester, 2-heptylundecyl palmitate, 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, and triethyl citrate, etc.

[0197] Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, almond oil, wheat germ oil, camellia oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, torreya nut oil, rice bran oil, tung oil, Japanese tung oil, jojoba oil, wheat germ oil, and triglycerides.

[0198] (B) The kinematic viscosity of component B at 25°C is preferably 100,000 mm³ / s. 2 / s or less, more preferably 10000mm 2 / s or less. When the kinematic viscosity is greater than the above upper limit, emulsification (suspension) in step i) becomes difficult, and it is sometimes difficult to obtain emulsified (suspension) compositions and elastomer spherical particles with narrow particle size distribution.

[0199] When using surfactants in component (C), there are no particular limitations on the type of surfactant used; conventionally known nonionic surfactants, anionic surfactants, cationic surfactants, or amphoteric surfactants may be used. It should be noted that they may be used alone or in appropriate combinations of two or more.

[0200] Examples of nonionic surfactants include, for example, 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 sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene hardened castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene modified organopolysiloxanes, and polyoxyethylene polyoxypropylene modified organopolysiloxanes.

[0201] Examples of polyoxyethylene-modified organopolysiloxanes include linear polyether-modified organosilicon (trade names: KF-6011, KF-6011P, KF-6043, manufactured by Shin-Etsu Chemical Co., Ltd., Japan), linear alkyl co-modified polyether-modified organosilicon (trade name: KF-6048, manufactured by Shin-Etsu Chemical Co., Ltd., Japan), branched polyether-modified organosilicon (trade names: KF-6028, KF-6028P, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) and branched alkyl co-modified polyether-modified organosilicon (trade name: KF-6038, manufactured by Shin-Etsu Chemical Co., Ltd., Japan).

[0202] Examples of anionic surfactants include, for example, sodium lauryl sulfate and other alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyl taurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, and polyoxyethylene alkyl ether phosphate salts.

[0203] Examples of cationic surfactants include, for example, alkyl trimethylammonium salts, dialkyl dimethylammonium salts, polyoxyethylene alkyl dimethylammonium salts, dipolyoxyethylene alkyl methylammonium salts, trimeroxyethylene alkylammonium salts, alkyl benzyl dimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkyl amide amine salts.

[0204] Examples of amphoteric surfactants include alkyl dimethylamine oxide, alkyl dimethyl carboxybetaine, alkyl amide propyl dimethyl carboxybetaine, alkyl hydroxy sulfobetaine, and alkyl carboxymethyl hydroxyethyl imidazoline betaine.

[0205] From the viewpoint that the above-mentioned component (A) can be emulsified (suspended) in small amounts and fine elastomeric spherical particles can be obtained, nonionic surfactants or anionic surfactants are preferred as surfactants.

[0206] When water or an aqueous phase component containing water is used as component (B), the HLB value of the surfactant (C), which represents the balance between hydrophobicity and hydrophilicity, is preferably 6.0 to 18.0, more preferably 9.0 to 18.0. Furthermore, when an oil phase component is used as component (B), the HLB value of the surfactant (C) is preferably 2.0 to 13.0, more preferably 2.0 to 9.0.

[0207] (C) The amount of surfactant added is preferably 0.01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight, relative to 100 parts by weight of the emulsified (suspension) composition. If the amount of surfactant added is less than the lower limit mentioned above, emulsification may be poor or fine elastomeric spherical particles may not be obtained, which is not preferred. Furthermore, if the amount of surfactant added is greater than the upper limit mentioned above, the overall viscosity of the composition increases, which may result in the inability to obtain fine elastomeric spherical particles or insufficient particle dispersion, which is also not preferred.

[0208] When using suspending agents for component (C), there are no particular limitations on their types. Examples include, for instance, water-soluble polymers such as conventionally known natural polymers, semi-synthetic polymers, and synthetic polymers, or polymers used as thickeners. It should be noted that they can be used alone or in appropriate combinations of two or more.

[0209] Examples of natural macromolecular compounds include xanthan gum, cellulose, tamarind gum, tamarind gum, locust bean gum, gellan gum, HM pectin, carrageenan, guar gum, flaxseed gum, gum arabic, pullulan, agarose, agar gum, alginic acid, cannabidiol, succinoglycan, starch, dextrin, gelatin, and casein.

[0210] Examples of semi-synthetic polymers include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, cationic xanthan gum, LM pectin (acid-treated / alkali-treated), cationic guar gum, alginate, soluble starch, and cellulose nanofibers.

[0211] Examples of synthetic polymers include polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymers, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, polyacrylamide, polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol.

[0212] From the viewpoint that the above-mentioned component (A) can be suspended (emulsified) in small amounts to obtain fine elastomeric spherical particles, xanthan gum, tamarind gum, carrageenan, guar gum, gum arabic, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, cationic xanthan gum, cationic guar gum, polyvinyl alcohol, and polyvinylpyrrolidone are preferred as suspending agents.

[0213] The amount of suspending agent added relative to 100 parts by weight of the emulsified (suspended) composition is preferably 0.01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight. If the amount of suspending agent added is less than the lower limit mentioned above, poor emulsification or failure to obtain fine elastomeric spherical particles may occur, which is therefore undesirable. Furthermore, if the amount of suspending agent added is greater than the upper limit mentioned above, the viscosity of the composition increases significantly, and fine elastomeric spherical particles may not be obtained, leading to insufficient particle dispersion, which is also undesirable.

[0214] As the polymerization initiator for component (D), conventionally known free radical polymerization initiators can be used. In the presence of the polymerization initiator, free radicals can be generated by external stimuli such as heating, light irradiation, and UV irradiation, thereby enabling reaction and curing (crosslinking).

[0215] (D) Polymerization initiator, specifically, peroxide, azo initiator, photoinitiator or redox initiator combining oxidant and reductant can be used.

[0216] 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(tert-butylperoxy)hexane, di-tert-butyl peroxide, tert-butyl peroxide, and hydrogen peroxide.

[0217] Alternatively, perchlorates such as potassium perchlorate and sodium perchlorate can also be used.

[0218] Examples of azo initiators include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(methyl 2-methylpropionate), 2,2'-azobis(methyl isobutyrate), tert-butyl peroxide of 2-ethylhexanoate, and 2,2-azobis(2-aminodipropane) dihydrochloride.

[0219] Examples of photoinitiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, methyl benzoylformate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide.

[0220] In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can also be used.

[0221] Examples of redox initiators include initiators that combine ferrous sulfate / sodium pyrophosphate / glucose / hydrogen peroxide and initiators that combine ferrous sulfate / disodium ethylenediaminetetraacetate / sodium formaldehyde sulfoxylate / hydrogen peroxide.

[0222] In addition, this redox initiator can also be used in combination with an azo initiator and a photoinitiator.

[0223] From the viewpoint of stability of the emulsified (suspension) composition during (free radical) polymerization and ease of handling, peroxide, azo initiators and photoinitiators used in heating or light irradiation methods are preferred as polymerization initiators.

[0224] The amount of polymerization initiator added is preferably in the range of 0.01 to 5.0 parts by mass relative to 100 parts by mass of component (A).

[0225] If the amount of polymerization initiator added is less than the lower limit mentioned above, poor curing (crosslinking) may occur. If the amount of polymerization initiator added is greater than the upper limit mentioned above, odors or leaching may occur due to the mixing (contamination) of reaction residues, etc., so it is not preferred.

[0226] Other additives

[0227] In the method for manufacturing elastomeric spherical particles, in the preparation step i) of the emulsified (suspended) composition, in addition to the above-mentioned components (A), (B), (C) and (D), various additives may also be added as needed.

[0228] Examples of additives include thickeners, pH adjusters, preservatives, antioxidants, and polymerization inhibitors. Each of these can be used alone or in combination of two or more, in appropriate amounts without impairing the effects of the present invention.

[0229] There is no particular limitation on the order in which the components are added and mixed in step i). For example, components (A) and (D) can be mixed beforehand, and then components (B) and (C) can be added to the mixture of components (A) and (D) to prepare an emulsion (suspension) composition; or components (A), (B) and (C) can be used to prepare an emulsion (suspension) composition, and then component (D) can be added.

[0230] Alternatively, after preparing an emulsified (suspension) composition from components (A), (B), (C), and (D), component (B) may be further added to dilute it to the desired concentration before submission to step ii).

[0231] In addition, when the polyester-polyether copolymer of component (A) with unsaturated groups that can be free radical polymerized has temperature dependence such as cloud point (the solubility of component (A) decreases rapidly and phase separation occurs when heated, with a certain temperature as the boundary), the preparation of the emulsified (suspended) composition in step i) can be carried out under temperature conditions corresponding to the temperature characteristics of component (A), for example, stirring, emulsification, and suspension can be carried out under heating conditions.

[0232] The temperature conditions for heating can be, for example, below 100°C, preferably in the range of 30 to 90°C, and more preferably in the range of 40 to 70°C. If the continuous phase is aqueous, and the heating temperature exceeds the above-mentioned upper limit, water may evaporate or violently boil, which is therefore undesirable.

[0233] When preparing the emulsified (suspension) composition in step i), conventionally known emulsifying dispersers can be used. Examples of common emulsifying dispersers include, for example, high-speed rotary shear mixers such as HOMO MIXER, high-speed centrifugal radial mixers such as HOMO DISPER, combined emulsifying mixers that combine a homogenizer and a homogenizer, mixing-emulsifying mixers (vacuum emulsifying homogenizers (Agi-Homo Mixer)) that combine a homogenizer or a homogenizer and an anchor mixer, high-pressure jet emulsifying dispersers such as homogenizers, colloid mills, ultrasonic emulsifiers, and paddle mixers.

[0234] Process (ii)

[0235] Step (ii) is a process in which component (A) in the emulsion (suspension) composition prepared in step (i) is reacted and solidified (crosslinked) by (free radical) polymerization to obtain a dispersion of elastomeric spherical particles.

[0236] In step ii), the conditions of the polymerization reaction can be appropriately determined according to the type of polymerization initiator (D).

[0237] For example, when using peroxide or azo initiators, a heating method involving reaction at 30–80°C for 10–24 hours can be cited; when using redox initiators, a redox method involving reaction at 30–70°C for 2–24 hours can be cited. When using photoinitiators, a photoirradiation method involving reaction under light irradiation can be cited; regarding the light source and wavelength range used for light or UV irradiation, conventionally known light sources and wavelength ranges can be used.

[0238] Process iii)

[0239] Step iii) is a process of obtaining elastomeric spherical particles by washing and drying the dispersion of elastomeric spherical particles obtained in step ii) to remove component (B) as the continuous phase.

[0240] In step iii), if the continuous phase (dispersion medium) of component (B) is an aqueous phase, specific methods for step iii) include, for example, concentrating the dispersion by methods such as heating and dehydration, (pressurized) filtration, centrifugation, and decantation, followed by washing with pure water as needed. Finally, methods include heating and drying under normal or reduced pressure; spraying the dispersion into a heated gas stream for heating and drying (spray drying); using a flowing heat medium for heating and drying; or freeze-drying by reducing pressure after solidifying the dispersion to remove the dispersion medium. This yields spherical elastomer particles.

[0241] It should be noted that when agglomerating the elastomeric spherical particles obtained by washing and drying to remove the dispersion medium, crushing can also be carried out using a mortar, ball mill, or jet mill.

[0242] In step iii), when the continuous phase (dispersion medium) of component (B) is an oil phase, the specific method for step iii) involves adding a hydrophobic organic solvent to the dispersion of elastomeric spherical particles, stirring for a certain period, and then pressure filtering to clean, remove, and replace the solvent in component (B). By repeating this cleaning operation multiple times, component (B) can be thoroughly removed and the solvent replaced. Examples of hydrophobic organic solvents used include toluene and hexane.

[0243] Finally, by implementing methods such as heating and drying under normal or reduced pressure; spraying the dispersion in a heated airflow and then heating and drying (spray drying); using a flowing heat medium for heating and drying; or freeze drying by reducing pressure and removing the dispersion medium after the dispersion has solidified, spherical elastomer particles can be obtained.

[0244] II. Elastomer composite particles and methods for manufacturing elastomeric composite particles

[0245] The elastomeric composite particles incorporated in cosmetics according to the present invention are elastomeric spherical particles having polyorganosilsesquioxane or silica on the surface of the elastomeric spherical particles which are crosslinked particles of copolymers having polyester and polyether structures. Preferably, the elastomeric composite particles have polyorganosilsesquioxane or silica with spherical microparticles attached and coated on the surface of the elastomeric spherical particles.

[0246] The shape of the elastomer composite particles is preferably spherical.

[0247] The shape of the elastomeric composite particles, like the aforementioned elastomeric spherical particles, can be confirmed using an optical microscope or an electron microscope.

[0248] In this 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.

[0249] When the volume average particle size is greater than 100 μm, the particle fluidity decreases and the cohesion increases, which results in insufficient smoothness and light diffusivity as particles. On the other hand, when the volume average particle size is less than 1.0 μm, the looseness and smoothness of the particles may decrease, resulting in a rough feeling and reduced light diffusivity.

[0250] The volume average particle size of the elastomer composite particles, as described above, can be measured by resistance method or laser diffraction / scattering method.

[0251] [Polyorganosilsesquioxane]

[0252] In this invention, the polyorganosilsesquioxane present on the surface of the elastomeric spherical particles is R 7 SiO 3 / 2 The unit represented is a resinous solid that is cross-linked into a three-dimensional network.

[0253] R in the above formula 7 It is a monovalent hydrocarbon group with 1 to 20 carbon atoms, either unsubstituted or substituted. As R 7 Examples of such groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; alkenyl groups such as vinyl and allyl; aromatic 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 formed by replacing some or all of the hydrogen atoms bonded to the carbon atoms of these groups with halogen atoms (fluorine, chlorine, bromine, iodine), and / or substituents such as amino, acryloyloxy, methacryloyloxy, epoxy, glycidyloxy, hydrogen sulfide, and carboxyl.

[0254] According to the method described later, in order to allow the polyorganosilsesquioxane to adhere to the surface of the elastomer spherical particles, the above-mentioned R is preferred. 7 More than 50 mol% of which are methyl, vinyl or phenyl, preferably R 7 More than 80 mol% of the substance is methyl, vinyl, or phenyl, with the above-mentioned R being more preferred. 7 More than 90 mol% of it is methyl, vinyl or phenyl.

[0255] Without compromising the non-cohesive, dispersible, or other properties of the obtained elastomer composite particles, and within the limits of usability or soft touch such as a loose, silky feel, polyorganosilsesquioxanes, except for R... 7 SiO 3 / 2 In addition to the unit, it can also contain R 7 2SiO 2 / 2 Unit, R 7 3SiO 1 / 2 unit and SiO 4 / 2 At least one of the units.

[0256] In such polyorganosilsesquioxanes, R 7 SiO 3 / 2 The content of the unit is preferably 70-100 mol% of all siloxane units, more preferably 80-100 mol%.

[0257] silicon dioxide

[0258] In this invention, the silicon dioxide on the surface of the elastomeric spherical particles is made of R 8 SiO 4 / 2 The units represented are cross-linked into a three-dimensional network of inorganic solids.

[0259] R in the above formula 8 It is a monovalent hydrocarbon group with 1 to 6 carbon atoms, either unsubstituted or substituted. As R 8 Examples of such compounds include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0260] Silica is obtained through the hydrolysis and condensation reaction of tetraalkoxysilane and is mainly composed of SiO2 units.

[0261] In addition, silicon dioxide is not only composed of SiO2 units; it may also contain alkoxy groups derived from tetraalkoxysilanes used as raw materials, and silanol groups that have not undergone condensation reactions.

[0262] In this invention, the polyorganosilsesquioxane or silicon dioxide is preferably spherical in shape.

[0263] The particle sizes of the polyorganosilsesquioxane and silica are preferably 10-500 nm, more preferably 20-200 nm.

[0264] When the particle size of the polyorganosilsesquioxane and silica is less than 10 nm, the light scattering property of the resulting elastomer composite particles may be reduced. Conversely, when the particle size of the polyorganosilsesquioxane and silica is greater than 500 nm, the resulting elastomer composite particles may lack a soft tactile feel and exhibit reduced light scattering property.

[0265] Polyorganosilsesquioxane or silica can be attached to a portion of the surface of the elastomeric spherical particles, or it can be attached in a manner that covers the entire surface of the particles, i.e., it can also cover the entire surface of the particles, but it is preferred that the particles be covered substantially without gaps on the entire surface of the elastomeric spherical particles.

[0266] It should be noted that by observing the particle surface of the obtained elastomer composite particles using an electron microscope, the particle size, shape, and adhesion density of the polyorganosilsesquioxane and silica on the surface of the spherical elastomer particles can be confirmed. The particle size of the polyorganosilsesquioxane and silica refers to the value calculated by averaging the particle size of any 50 particles measured from electron microscope images of the particle surface of the separately obtained elastomer composite particles.

[0267] In the elastomeric composite particles, the amount of polyorganosilsesquioxane or silica attached to the surface of the elastomeric spherical particles is preferably 0.2 to 200 parts by mass, and more preferably 0.5 to 50 parts by mass, relative to 100 parts by mass of the elastomeric spherical particles.

[0268] When the amount of polyorganosilsesquioxane or silica is less than the lower limit mentioned above, the cohesiveness is high and the dispersibility is poor, which may lead to reduced light scattering or a lack of a soft feel. In addition, when the amount of polyorganosilsesquioxane or silica exceeds the upper limit mentioned above, the soft touch of the elastomer composite particles may be lacking.

[0269] [Manufacturing method of elastomer composite particles]

[0270] Elastomer composite particles can be manufactured, for example, by a method having the following steps (iv).

[0271] iv)

[0272] The process of adding component (I) to a liquid phase containing components (E), (F), (G), and (H) to cause component (I) to undergo hydrolysis and polymerization.

[0273] (E) Elastomeric spherical particles

[0274] (F) Alkaline substances

[0275] (G) Selected from one or more cationic surfactants and cationic water-soluble polymers.

[0276] (H) water

[0277] (I) Trialkoxysilane or tetraalkoxysilane.

[0278] Engineering (iv)

[0279] In step iv), component (I) is added to a liquid phase containing components (E), (F), (G) and (H) to cause component (I) to undergo hydrolysis and polymerization.

[0280] The components used in process iv) are as follows.

[0281] (E) The elastomer spherical particles of component (E) are used in the elastomer spherical particles obtained in the processes described above (i) to (ii) or (i) to (iii).

[0282] Alternatively, if component (B) used in step i) is an aqueous component, step iii) can be omitted, and the aqueous dispersion of the elastomeric spherical particles obtained solely through steps i) and ii) can be provided to step iv as a mixture of components (E) and (H).

[0283] The amount of (E) elastomer spherical particles is preferably in the range of 1.0 to 150 parts by mass, more preferably in the range of 3.0 to 70 parts by mass, relative to 100 parts by mass of water in the liquid phase containing (E) to (H) components. Since the production efficiency of the target elastomer composite particles may decrease if the amount of (E) component is less than the lower limit mentioned above, and if the amount of (E) component is higher than the upper limit mentioned above, it is difficult to coat the polyorganosilsesquioxane and silica onto the surface of the elastomer spherical particles, potentially leading to particle aggregation or fusion, which is therefore undesirable.

[0284] (F) The basic substance is a substance that acts as a catalyst in the hydrolysis or condensation reaction of trialkoxysilanes or tetraalkoxysilanes. One basic substance may be used alone, or two or more may be used in appropriate combination.

[0285] There are no particular limitations on the alkaline substances used; for example, 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. It should be noted that these alkaline substances can be used alone or in appropriate combinations.

[0286] Ammonia is the most preferred alkaline substance, considering its ease of removal from the obtained elastomeric composite particle powder by evaporation. Commercially available ammonia solutions of various concentrations can be used as ammonia.

[0287] (F) The amount of alkaline substance added is preferably such that the pH value of the liquid phase containing components (E) to (H) at 25°C is 9.0 to 13.0, more preferably such that the pH value is in the range of 10.0 to 12.0. If an amount is added to make the pH value 9.0 to 13.0, the hydrolysis and condensation reaction of the trialkoxysilane or tetraalkoxysilane can be fully carried out, and the polyorganosilsesquioxane or silica can be fully coated on the surface of the elastomer spherical particles.

[0288] (G) Cationic surfactants and cationic water-soluble polymers promote the condensation reaction of hydrolyzed trialkoxysilanes or tetrakoxysilanes, and produce resins or silica. Additionally, they facilitate the adsorption of the resulting resins or silica onto the surface of elastomeric spherical particles.

[0289] Cationic surfactants and cationic water-soluble polymers can be used alone or in appropriate combinations of two or more.

[0290] As a cationic surfactant, the same substances as those exemplified as the cationic surfactants that are components (C) can be cited.

[0291] Examples of cationic water-soluble polymers include, for example, polymers of dimethyl diallyl ammonium chloride (DMDAAC), polymers of vinyl imidazoline, polymers of methyl vinyl imidazoline chloride, polymers of ethyl trimethyl ammonium chloride acrylate, polymers of ethyl trimethyl ammonium chloride methacrylate, polymers of acryloylaminopropyl trimethyl ammonium chloride, polymers of methacrylaminopropyl trimethyl ammonium chloride, polymers of epichlorohydrin (ECH) / dimethylamine, polymers of ethyleneimine, quaternary compounds of ethyleneimine polymers, polymers of allylamine hydrochloride, polylysine, cationic starch, cationic cellulose, chitosan, and copolymers thereof with monomers having nonionic and anionic groups, and their derivatives.

[0292] As component (G), alkyltrimethylammonium salts of cationic surfactants are preferred, with dodecyltrimethylammonium salts and hexadecyltrimethylammonium salts being more preferred.

[0293] Relative to 100 parts by mass of water in the liquid phase containing components (E) to (H), the amount of cationic surfactant and cationic water-soluble polymer compound added is preferably in the range of 0.01 to 2.0 parts by mass, more preferably in the range of 0.1 to 1.0 parts by mass. If the amount of component (G) added is less than the lower limit mentioned above, polyorganosilsesquioxanes or silica that are not coated on the surface of the elastomeric spherical particles may be generated. If the amount added is greater than the upper limit mentioned above, polyorganosilsesquioxanes or silica that are not coated on the surface of the elastomeric spherical particles may also be generated.

[0294] There are no special limitations on (H) water. For example, pure water, ion-exchanged water, pure water, etc. can be used. (B) component is an aqueous phase component. If the aqueous dispersion of the elastomeric spherical particles obtained in step ii) is provided directly to step iv) without going through the above step iii), it also includes the water in the aqueous dispersion and water added as needed.

[0295] There is no particular limitation on (I) trialkoxysilane and tetraalkoxysilane, and any conventionally known substance may be used. However, from the viewpoint of reactivity, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane are preferred, and methyltrimethoxysilane and tetramethoxysilane are more preferred.

[0296] Tetraalkoxysilanes can be tetraalkoxysilanes obtained by hydrolyzing some or all of the alkoxy groups, or tetraalkoxysilanes obtained by condensing some of the alkoxy groups.

[0297] The amount of trialkoxysilane added is preferably 1.0 to 50 parts by mass relative to 100 parts by mass of (E) elastomer spherical particles, more preferably 2 to 25 parts by mass.

[0298] Furthermore, the amount of tetraalkoxysilane added is preferably 0.5 to 200 parts by mass of silica, more preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of the (E) elastomer spherical particles.

[0299] Hydrolysis reaction, condensation reaction

[0300] In a liquid phase containing components (E) to (H), add (I) trialkoxysilane or tetraalkoxysilane and allow it to undergo hydrolysis and condensation reactions.

[0301] Specifically, in an aqueous dispersion prepared by dispersing (E) spherical elastomer particles in (H) water, and then dissolving one or more of (F) an alkaline substance, (G) a cationic surfactant, and a cationic water-soluble polymer, (I) a trialkoxysilane or tetraalkoxysilane is added, followed by hydrolysis and condensation. Through hydrolysis and condensation, as a condensate of the trialkoxysilane or tetraalkoxysilane, a polyorganosilsesquioxane or silica adheres to the surface of the spherical elastomer particles, thereby coating the surface of the spherical elastomer particles with a polyorganosilsesquioxane or silica.

[0302] The addition of trialkoxysilanes and tetraoxosilanes is preferably carried out using a conventional agitator equipped with propeller blades, flat blades, or similar devices, under stirring. They can be added all at once, but it is preferable to add them over a period of time. The preferred addition time is in the range of 1 minute to 6 hours, more preferably in the range of 10 minutes to 3 hours.

[0303] Furthermore, the temperature of the liquid phase is preferably in the range of 0 to 60°C, and more preferably in the range of 0 to 40°C. If the temperature is within the above range, the polyorganosilsesquioxane or silica can be perfectly attached to and coated on the surface of the elastomeric spherical particles in the liquid phase.

[0304] After adding trialkoxysilane or tetrakoxysilane, continue stirring until these hydrolysis and polycondensation reactions are complete. To complete the hydrolysis and polycondensation reactions, the reactions can be carried out at room temperature or under heating conditions of about 40~100°C. In addition, an alkaline substance may be added as appropriate.

[0305] Dehydration process, powdering process

[0306] Following the hydrolysis and condensation reaction in step iv), water is optionally removed from the aqueous dispersion of the obtained elastomer composite particles. Water removal can be performed by heating the aqueous dispersion after the reaction under normal or reduced pressure.

[0307] Specifically, examples include methods such as heating and drying under normal or reduced pressure, spraying the dispersion into a heated airflow for heating and drying (spray drying), using a flowing heat medium for heating and drying, or freeze drying to remove the dispersion medium by reducing pressure after solidification of the dispersion, thereby obtaining elastomer composite particles.

[0308] It should be noted that, as a pretreatment step for this operation, the dispersion can also be concentrated by methods such as heating and dehydration, filtration and separation, centrifugation and decantation. If necessary, the aqueous dispersion can also be washed with water or alcohol.

[0309] In the case of powder agglomeration of elastomeric composite particles obtained by removing water from the aqueous dispersion after reaction, they can be crushed using pulverizers such as jet mills, ball mills, and hammer mills.

[0310] III. Method for manufacturing cosmetics using elastomeric spherical particles and elastomeric composite particles

[0311] The cosmetics of the present invention can be manufactured using at least one of (i) elastomeric spherical particles and (ii) elastomeric composite particles manufactured by the methods described herein.

[0312] More specifically, by using elastomeric spherical particles and / or elastomeric composite particles, and in addition, by using various cosmetic ingredients described later and mixing, emulsifying, etc., a desired cosmetic can be manufactured.

[0313] IV. Cosmetics containing elastomeric spherical particles and elastomeric composite particles

[0314] The cosmetic material of the present invention is characterized in that it contains at least one of (i) elastomeric spherical particles and (ii) elastomeric composite particles.

[0315] There are no particular limitations on the proportion of the above-mentioned elastomer composite particles; they can be selected appropriately according to the specific formulation.

[0316] This invention is applicable to various cosmetics, and is particularly preferred to skin care cosmetics, makeup cosmetics, antiperspirant cosmetics, sunscreen cosmetics and other cosmetics applied externally to the skin, as well as hair cosmetics and other cosmetics applied externally to hair, and nail cosmetics.

[0317] In the cosmetics of the present invention, the amount of elastomeric spherical particles and elastomeric composite particles of the present invention is not limited.

[0318] Examples of skincare and cosmetic ingredients include, for example, lotions, creams, cleansing milks, face masks, liquid oils, massage agents, beauty serums, beauty oils, cleansers, deodorants, hand creams, lipsticks, and concealers. For instance, in skincare and cosmetic ingredients, the total proportion of (i) elastomeric spherical particles and (ii) elastomeric composite particles in the total mass of the compounded ingredients is preferably 0.1 to 99% by mass, more preferably 1 to 70% by mass.

[0319] As a color cosmetic ingredient, for example, in primers, foundations, concealers, powders, blushes, eyeshadows, eyeshadows, mascaras, eyeliners, eyebrow pencils, lipsticks, etc. In the color cosmetic ingredient, the total proportion of (i) elastomeric spherical particles and (ii) elastomeric composite particles in the total mass of the compounded ingredients is, for example, preferably 0.1 to 100% by mass, more preferably 1 to 90% by mass.

[0320] Examples of antiperspirant cosmetics include roll-on, cream, solution, and stick types. In antiperspirant cosmetics, the total proportion of (i) elastomeric spherical particles and (ii) elastomeric composite particles in the total mass of the compounded components is preferably 0.1 to 80% by mass, more preferably 1 to 70% by mass.

[0321] Examples of sunscreen cosmetic ingredients include, for example, sunscreen oils, sunscreen lotions, and sunscreen creams. For example, in sunscreen cosmetic ingredients, the total amount of (i) elastomeric spherical particles and (ii) elastomeric composite particles in the total mass of the compounded ingredients is preferably 0.1 to 90% by mass, and more preferably 0.1 to 80% by mass.

[0322] Examples of hair cosmetics include shampoos, conditioners, hair treatments, and styling agents. In hair cosmetics, the total amount of (i) elastomeric spherical particles and (ii) elastomeric composite particles in the total mass of the compounded components is preferably 0.1 to 80% by mass, and more preferably 1 to 70% by mass.

[0323] The cosmetic material of the present invention can be in any form, such as powder, oily liquid, water-in-oil emulsion, oil-in-water emulsion, non-aqueous emulsion, W / O / W type, O / W / O type, or other composite emulsions. Furthermore, the physical form of the cosmetic material of the present invention can be various, including liquid, emulsion, cream, solid, paste, gel, powder, pressed powder, multilayer, mousse, spray, stick, and pencil forms.

[0324] The cosmetics of the present invention may contain various ingredients commonly used in cosmetics, without impairing the effects of the present invention. They may contain, for example, (1) oils, (2) aqueous components, (3) surfactants, (4) powders other than the aforementioned elastomeric spherical particles and elastomeric composite particles, (5) compositions consisting of cross-linked organopolysiloxanes and oils that are liquid at room temperature, (6) film-forming agents, (7) ultraviolet absorbing and scattering agents, and (8) other additives. They may be used individually or in appropriate combinations of two or more.

[0325] (1) Oil

[0326] Oils can be volatile or non-volatile, and can be solid, semi-solid, or liquid at room temperature (25°C). Examples include silicone oil, organosilicon wax, natural animal and vegetable oils, semi-synthetic oils, hydrocarbon oils, higher alcohols, fatty acids, ester oils, fluorinated oils, and ultraviolet absorbers.

[0327] silicone oil

[0328] Examples of silicone oils include, for instance, alkyl-modified organosilicones such as polydimethylsiloxane (INCI), trisiloxane (INCI), methyl polytrimethylsiloxane (INCI), ethyltrisiloxane (INCI), ethyl polymethylsiloxane (INCI), and hexyl polydimethylsiloxane (INCI); long-chain alkyl-modified organosilicones such as octyl polymethylsiloxane (INCI); linear or branched organopolysiloxanes ranging from low to high viscosity, such as phenyl polytrimethylsiloxane (INCI), diphenyl polydimethylsiloxane (INCI), diphenylsiloxyphenyl polytrimethylsiloxane (INCI), tetraphenyldimethyldisiloxane (INCI), and methylhydropolysiloxane; and cyclotetrasiloxane (INCI) and cyclopentasiloxane (INCI). Cyclic organopolysiloxanes such as hexacyclohexane (INCI); amino-modified organopolysiloxanes such as amodimethicone (INCI) and aminopropyl polydimethylsiloxane (INCI); pyrrolidone-modified organopolysiloxanes such as PCA polydimethylsiloxane (INCI); pyrrolidone carboxylic acid-modified organopolysiloxanes; high-polymerization degree viscous dimethylpolysiloxanes; viscous amino-modified organopolysiloxanes; viscous dimethylsiloxane-methylphenylsiloxane copolymers and other organosilicone rubbers; as well as low-viscosity organopolysiloxane solutions of organosilicone adhesives or organosilicone rubbers; amino acid-modified organosilicones; fluorine-modified organosilicones; organosilicone resins; and solvents of organosilicone resins, etc.

[0329] Examples of commercially available silicone oils include those manufactured by Shin-Etsu Chemical Co., Ltd.: KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, KF-96A-6cs, KF-4422, KF-4418, KF-54, KF-54HV, KF-56A, KF-995, etc.

[0330] Oily components in solid state

[0331] In this invention, when it is desired to solidify the cosmetic, it is preferable to use an oily component that is solid at 25°C.

[0332] As an oily component that is solid at 25°C, it is preferably an oily component with a melting point of 40°C or higher, more preferably 60-110°C. Examples include waxes, hydrocarbons, esters, higher alcohols, and higher fatty acids, as long as they are ingredients that can be incorporated into common cosmetics, without particular limitation. Specifically, examples include carnauba wax (INCI: Copernicia Cerifera (Carnauba) Wax), sugarcane wax, candelilla wax (INCI: Euphorbia Cerifera (Candelilla) Wax), refined candelilla wax, rice wax, wood wax, jojoba wax, kapok wax, rice bran wax, waxed myrica fruit wax, shea butter, cocoa butter, wood wax (INCI: Rhus Succedanea Fruit Wax), Montan wax, etc. Vegetable waxes such as waxes (e.g., castor oil with isostearate), beeswax, tallow, beef bone fat, lard (INCI: Lard), horse fat (INCI: Horsefat), mutton fat, lanolin (INCI: Lanolin), Chinese wax, purpuric resin wax, and cetearyl wax, semi-synthetic waxes such as lanolin esters, lanolin fatty acid esters, and beeswax esters, hydrogenated oils such as hydrogenated castor oil and hydrogenated coconut oil, hydrocarbon waxes such as solid paraffin wax, polyethylene wax, refined cereswax, crude cereswax, and microcrystalline wax, and wax esters such as synthetic beeswax. Dioctyldodecyl lauroyl glutamate, dioctyldodecyl lauroyl glutamate, dioctyldodecyl lauroyl glutamate and other amino acid stearyl esters, stearic acid, benzyl acid and other fatty acids, and acrylic-organic silicone waxes such as acrylic-organic silicone resins (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Japan: acrylic-organic silicone graft copolymers: KP-561P, KP-562P, etc.) or their derivatives, preferably selected from one or more of the above-mentioned oily components.

[0333] Natural animal and vegetable oils and semi-synthetic oils

[0334] Examples of natural and semi-synthetic oils include: avocado oil (INCI: Persea Gratissima (Avocado) Oil), flaxseed oil (INCI: Linum Usitatissimum (Linseed) Seed Oil), almond oil (INCI: Prunus Amygdalus Dulcis (SweetAlmond) Oil), perilla oil, olive oil (INCI: Olea Europaea (Olive) Fruit Oil), Torreya California (California Nutmeg) Oil, citronella oil (INCI: Cymbopogon Nardus (Citronella) Oil), Torreya Nucifera Seed Oil, and almond oil (INCI: Kyounin). Yu), wheat germ oil (INCI: Triticum Vulgare (Wheat) Germ Oil), sesame oil (INCI: Sesamum Indicum (Sesame) Seed Oil), wheat germ oil (INCI: Triticum Vulgare (Wheat) Germ Oil), rice germ oil (INCI: Oryza Sativa (Rice) Germ Oil), rice bran oil (INCI: Oryza Sativa (Rice) Bran Oil), camellia seed oil (INCI: Camellia Kissi Seed Oil), safflower seed oil (INCI: Carthamus Tinctorius (Safflower) Seed Oil), soybean oil (INCI: Glycine Soja (Soybean) Oil), tea seed oil (INCI: Camellia Sinensis Seed Oil) Camellia Japonica Seed Oil (INCI: Camellia Japonica Seed Oil), Evening Primrose Oil (INCI: Oenothera Biennis (Evening Primrose Oil))Primrose oil, rapeseed oil (labeled name), corn germ oil (labeled name (INCI: ZeaMays (Corn) Germ Oil)), wheat germ oil (labeled name (INCI: Triticum Vulgare (Wheat) Germ Oil)), etc.; peach kernel oil (labeled name), palm oil (labeled name (INCI: Elaeis Guineensis (Palm) Oil), palm kernel oil (labeled name (INCI: Elaeis Guineensis (Palm) Kernel Oil)), castor oil (labeled name (INCI: Ricinus Communis (Castor) Seed Oil), sunflower seed oil (labeled name (INCI: Helianthus Annuus (Sunflower) Seed Oil), grape seed oil (labeled name (INCI: Vitis Vinifera (Grape) Seed Oil)), jojoba seed oil (labeled name (INCI: Simmondsia Chinensis (Jojoba) Seed Oil)). Natural plant oils including: macadamia ternifolia seed oil, meadowfoam seed oil, cottonseed oil, coconut oil, peanut oil, shark liver oil, cod liver oil, fish liver oil, turtle oil, mink oil, and egg yolk oil; (INCI: Macadamia Ternifolia Seed Oil, Limnanthes Alba (Meadowfoam) Seed Oil, cottonseed oil, Gossypium Herbaceum (Cotton) Seed Oil, coconut oil, peanut oil, and more; shark liver oil, cod liver oil, fish liver oil, turtle oil, mink oil, and egg yolk oil) Natural animal oils such as natural animal oils, hydrogenated coconut oil (INCI: Hydrogenated Coconut Oil), liquid lanolin (INCI: Lanolin Oil), and other semi-synthetic oils.

[0335] hydrocarbon oil

[0336] Examples of hydrocarbon oils include linear or branched hydrocarbon oils, which can be volatile or non-volatile. Specifically, examples include olefin oligomers (INCI), (C13, 14) isoalkanes (INCI), isoalkanes such as isododecane (INCI), undecane (INCI), dodecane (INCI), isohexadecane (INCI), hydrogenated polyisobutene (INCI: Hydrogenated Polyisobutene), squalane (INCI), mineral oil (INCI), coconut alkanes (INCI), (C13-15) alkanes (INCI), and other alkanes.

[0337] higher alcohols

[0338] Examples of higher alcohols include lauryl alcohol (INCI), hexyldecyl alcohol (INCI), oleyl alcohol (INCI), isostearyl alcohol (INCI), octyldodecanol (INCI), decyltetradecyl alcohol (INCI), myristyl alcohol (INCI), cetyl alcohol (INCI), stearyl alcohol (INCI), betaine alcohol (INCI), and squalene alcohol (INCI), which are straight-chain saturated alcohols with 6 or more carbon atoms, as well as squalene (INCI). Other examples include cholesterol (INCI), sitosterol (INCI: Beta-Sitosterol), phytosterols (INCI), lanosterol (INCI), and other sterols.

[0339] Ester oil

[0340] Examples of ester oils include, for instance, diisobutyl adipate (INCI: DiisobutylAdipate), di(hexyldecyl) adipate (INCI: Diheptylundecyl) adipate, di(heptylundecyl) adipate, isostearyl isostearate, etc., monoisostearic acid n-alkyl glycol esters, isocetyl isostearate (INCI: Isocetyl Isostearate), trimethylolpropane triisostearate (INCI: Trimethylolpropane Triisostearate), ethylene glycol di(ethylhexanoate) (INCI: GlycolDiethylhexanoate), and cetyl ethylhexanoate (INCI: Cetyl... Octyl hexanoate, trimethylolpropane triethylhexanoate, pentaerythrityl tetraethylhexanoate, cetyl octanoate, octyl dodecyl stearate, oleyl alcohol oleate, octyl dodecyl oleate, and decyl oleate.Neopentyl hexanoate dioctanoate (INCI: Neopentyl Glycol Diethylhexanoate), Neopentyl hexanoate dicaprate (INCI: Neopentyl Glycol Dicaprate), Diisostearyl malate (INCI: Diisostearyl Malate), Triethyl citrate (INCI: Triethyl Citrate), Diethylhexyl succinate (INCI: Diethylhexyl Succinate), Amyl acetate (INCI: Amyl Acetate), Ethyl acetate (INCI: Etyl 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), isoamyl nonanoate (INCI: Isonononyl Isonononanoate), isotridecyl isonononanoate (INCI: Isotridecyl Isonononanoate), isopropyl palmitate (INCI: Isopropyl Palmitate), ethylhexyl palmitate (INCI: Ethylhexyl Isopalmitate), hexyl decyl palmitate (INCI: Isocetyl... Palmitate, Hexyldecyl Palmitate, and other palmitate esters; cholesterol hydroxystearate (INCI: CholesterylHydroxystearate); isopropyl myristate (INCI: Isopropyl Myristate); octyldodecyl myristate (INCI: Octyldodecyl Myristate); myristyl myristate (INCI: Myristyl Myristate), and other myristate esters.Ethylhexyl laurate (INCI: Ethylhexyl Laurate), Hexyl laurate (INCI: Hexyl Laurate)), Dioctyldodecyl Lauroyl Glutamate (INCI: Dioctyldodecyl Lauroyl Glutamate), Isopropyl Lauroyl Sarcosinate (INCI: Isopropyl Lauroyl Sarcosinate)), and Coco-Caprylate·Caprate (INCI: Coco-Caprylate·Caprate), etc.

[0341] In addition, among ester oils, examples of glyceryl ester oils include triglyceride (INCI), caprylic / capric triglyceride (INCI: Caprylic / Capric Triglyceride), cocoyl glyceride (INCI), caprylic / capric / succinic triglyceride (INCI: Caprylic / Capric / Succinic Triglyceride), and caprylic / capric triglyceride (INCI: Caprylic / Capric Glycerides).

[0342] Fluorinated oils

[0343] Examples of fluorinated oils include perfluoronaphthalene (INCI), perfluorononylpolydimethylsiloxane (INCI), and perfluoromethylcyclopentane (INCI).

[0344] UV absorber

[0345] Examples of UV absorbers include, for example, benzophenone-1 (INCI: Benzophenone-1), benzophenone-2 (INCI: Benzophenone-2), benzophenone-3 (INCI: Benzophenone-3), benzophenone-4 (INCI: Benzophenone-4), benzophenone-5 (INCI: Benzophenone-5), benzophenone-6 (INCI: Benzophenone-6), benzophenone-9 (INCI: Benzophenone-9), homosalate (INCI), octocrylene (INCI), tert-butylmethoxydibenzoylmethane (INCI: Butyl Methoxydibenzoylmethane), and ethylhexyl salicylate (INCI: Ethylhexyl... Salicylate), Diethylaminohydroxybenzoylhexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), Polysiloxane-15 (INCI), Ethylhexyldimethoxybenzylidene Dioxoimidazolidine Propionate (INCI: EthylhexylDimethoxybenzylidene Dioxoimidazolidine Propionate), Terephthalylidene Dicamphor Sulfonic Acid (INCI: Terephthalylidene Dicamphor Sulfonic Acid), Ethylhexyl Triazine (INCI), Isopentyl Trimethoxycinnamate Trisiloxane (INCI: Isopentyl Trimethoxycinnamate Trisiloxane), Ethylhexyl dimethylparaaminobenzoate (INCI: Ethylhexyl Dimethyl PABA), isopropyl methoxycinnamate (INCI: Isopropyl Methoxycinnamate), ethylhexyl methoxycinnamate,(INCI: Ethylhexyl Methoxycinnamate), bis-ethylhexyloxyphenol methoxyphenyl triazine (INCI), phenylbenzimidazole sulfonic acid (INCI: Phenylbenzimidazole Sulfonic Acid), methylene bisbenzotriazolyl tetramethyl butylphenol (INCI), glyceryl ethylhexanoate dimethoxycinnamate (INCI: Glyceryl Ethylhexanoate Dimethoxycinnamate), glyceryl para-aminobenzoate (INCI), diisopropyl methyl cinnamate (INCI: Diisopropyl Methyl Cinnamate), cinnoxalate (INCI), dimethoxybenzyl dioxoimidazolyl propionate ethylhexyl ester (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine) Propionate, etc. Alternatively, UVA absorbers (e.g., hexyl diethylaminohydroxybenzoyl benzoate) and UVB absorbers (e.g., ethylhexyl methoxycinnamate) can be used together, or they can be combined separately in any way.

[0346] (2) Aqueous components

[0347] If the water-based ingredient is one that can usually be incorporated into cosmetics, then there are no special restrictions on it. Specifically, examples include lower alcohols with a preferred number of carbon atoms of 2-5, such as water, ethanol (INCI: Alcohol), and isopropyl alcohol (INCI: Isopropyl Alcohol); sugar alcohols such as sorbitol (INCI), maltose (INCI), and xylitol (INCI). Additionally, examples include polyols such as BG (INCI: Butylene Glycol), PG (INCI: Propylene Glycol), DPG (INCI: Dipropylene Glycol), pentanediol (INCI), 1,10-decanediol (INCI), octanediol (INCI), 1,2-hexanediol (INCI), erythritol (INCI), glycerol (INCI), diglycerol (INCI), and polyethylene glycol; and glucose (INCI), glycerol glucoside (INCI), betaine (INCI), and sodium chondroitin sulfate (INCI: Sodium Chondroitin). Sulfate), PCA-Na (INCI: Sodium PCA), Methyl glucetol polyether-10 (INCI), Methyl glucetol polyether-20 (INCI), Hyaluronic acid, Egg yolk lecithin, Soy lecithin, Phosphatidylcholine, Phosphatidylethanolamine, Phosphatidylserine, Phosphatidylglycerol, Phosphatidylinositol, Sphingosine phospholipids and other moisturizers.

[0348] (3) Surfactants

[0349] Surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, but there are no particular limitations. Any surfactant commonly used in cosmetics can be used. Since a stable cosmetic can be obtained by selecting one or more non-crosslinked or crosslinked silicone surfactants, even among these surfactants, this is preferred. In any case, the amount of surfactant added is preferably 0.1% to 20% by mass of the total cosmetic. If the amount of surfactant added is 0.1% by mass or more of the total cosmetic, the dispersing and emulsifying functions can be fully exerted; if it is less than 20% by mass of the total cosmetic, there is no concern about a sticky feel in the cosmetic, which is also preferred.

[0350] There are no particular restrictions on the HLB value of the surfactant, but for the purpose of maintaining the water resistance of the cosmetic, the HLB value is preferably 2.0 to 14.5.

[0351] As a non-crosslinked organosilicon surfactant, it is a non-crosslinked organosilicon surfactant formed by replacing part of the methyl groups of the linear or branched organosilicon backbone with hydrophilic groups such as polyethylene glycol or polyglycerol. Specifically, it is preferably a linear or branched polyoxyethylene modified organopolysiloxane, a linear or branched polyoxyethylene polyoxypropylene modified organopolysiloxane, a linear or branched polyoxyethylene-alkyl co-modified organopolysiloxane, a linear or branched polyoxyethylene polyoxypropylene-alkyl co-modified organopolysiloxane, a linear or branched polyglycerol modified organopolysiloxane, a linear or branched polyglycerol-alkyl co-modified organopolysiloxane, or a linear or branched pyrrolidone modified organopolysiloxane.

[0352] Examples of non-crosslinked silicone surfactants include PEG-11 methyl ether polydimethylsiloxane (INCI), PEG / PPG-20 / 22 butyl ether polydimethylsiloxane (INCI), PEG-3 polydimethylsiloxane (INCI), PEG-10 polydimethylsiloxane (INCI), PEG-9 polydimethylsiloxyethyl polydimethylsiloxane (INCI), lauryl PEG-9 polydimethylsiloxyethyl polydimethylsiloxane (INCI), cetyl PEG / PPG-10 / 1 polydimethylsiloxane (INCI), polyglycerol-3 disiloxane polydimethylsiloxane (INCI), polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane (INCI), lauryl polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane (INCI), and bis-butyl polydimethylsiloxane polyglycerol-3 (INCI).

[0353] Examples of commercially available products include those manufactured by Shin-Etsu Chemical Co., Ltd. of Japan: 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, KF-6115, etc.

[0354] Examples of cross-linked silicone surfactants include: (polydimethylsiloxane / (PEG-10 / 15)) cross-linked polymer (INCI), (PEG-15 / lauryl polydimethylsiloxane) cross-linked polymer (INCI), (PEG-10 / lauryl polydimethylsiloxane) cross-linked polymer (INCI), (PEG-15 / lauryl polydimethylsiloxyethyl polydimethylsiloxane) cross-linked polymer (INCI), and other cross-linked polyglycerol modified silicones; (polydimethylsiloxane / polyglycerol-3) cross-linked polymer (INCI), (lauryl polydimethylsiloxane / polyglycerol-3) cross-linked polymer (INCI), (polyglycerol-3 / lauryl polydimethylsiloxyethyl polydimethylsiloxane) cross-linked polymer (INCI), and other cross-linked polyglycerol modified silicones.

[0355] Furthermore, when using a cross-linked silicone surfactant, in a composition consisting of the surfactant and an oil that is liquid at room temperature, preferably, the cross-linked silicone surfactant swells relative to the liquid oil, which contains more than its own weight in the liquid oil.

[0356] As the liquid oil, the following can be used as optional components: (1) liquid silicone oil, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil and fluorinated oil, etc. Examples include cyclopentasiloxane (INCI), polydimethylsiloxane (INCI), mineral oil (INCI), isododecane (INCI), isohexadecane (INCI), glyceryl tri(ethylhexanoate) ester (INCI), isotridecyl isononanoate (INCI: Isotridecyl Isonononanoate), squalane (INCI), etc.

[0357] Examples of commercially available cross-linked silicone surfactants that swell due to the presence of liquid oils include those manufactured by Shin-Etsu Chemical Co., Ltd. of Japan: 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, KSG-850Z, etc.

[0358] (4) Powders other than the above-mentioned elastomeric spherical particles and elastomeric composite particles

[0359] It can be used with powders other than the aforementioned elastomeric spherical particles and elastomeric composite particles. Examples of such powders include, for example, coloring pigments, inorganic powders, metallic powders, organic powders, and inorganic-organic composite powders. Details are as follows.

[0360] Coloring pigments

[0361] As coloring pigments, generally speaking, there are no particular restrictions on pigments used for the purpose of coloring cosmetics. Examples include red iron oxide (INCI: Iron Oxides), yellow iron oxide (INCI: Iron Oxides), white titanium dioxide (INCI: Titanium Dioxide), black iron oxide (INCI: Iron Oxides), ultramarine (INCI: Ultramarines), Prussian blue (INCI: Ferric Ferrocyanide, Ferric Ammonium Ferrocyanide), manganese violet (INCI: Manganese Violet), cobalt titanate (INCI: Cobalt Titanium Oxide), chromium hydroxide (INCI: Chromium Hydroxide Green), chromium oxide (INCI: Chromium Oxide Greens), and aluminum / cobalt oxide (INCI: Cobalt). Aluminum oxide), cobalt titanate (INCI: Cobalt Titanium Oxide), (titanium / titanium oxide) calcined products (INCI: Titanium / Titanium Dioxide), lithium / cobalt titanate (INCI: Lithium Cobalt Titanate), cobalt titanate (INCI: Cobalt Titanium Oxide), (iron oxide / titanium oxide) sintered products (INCI: Iron Oxides, Titanium Dioxide), iron oxide-doped titanium oxide (INCI: Iron Oxides, Titanium Dioxide), and other composites doped with dissimilar metals, titanium nitride (INCI: Titanium Nitride), ferrous hydroxide (INCI: Iron Hydroxide), γ-iron oxide and other inorganic brown pigments, loess and other inorganic yellow pigments, coloring pigments after laked tar-based pigments, coloring pigments after laked natural pigments, and other colored pigments, etc.

[0362] Furthermore, the shape of the pigment can be any of the following: spherical, roughly spherical, rod-shaped, spindle-shaped, petal-shaped, strip-shaped, irregular shape, etc. As long as it can impart color to cosmetics, its geometric shape is not restricted.

[0363] Inorganic powder

[0364] Examples of inorganic powders include, for instance, zirconium oxide (INCI: Zirconium Dioxide), zinc oxide (INCI: Zinc Oxide), cerium oxide (INCI: Cerium Oxide), magnesium oxide (INCI: Magnesium Oxide), barium sulfate (INCI: Barium Sulfate), calcium sulfate (INCI: Calcium Carbonate), magnesium sulfate (INCI: Magnesium Sulfate), calcium carbonate (INCI: Calcium Carbonate), magnesium carbonate (INCI: Magnesium Carbonate), talc (INCI), mica (INCI), kaolin (INCI), and synthetic fluorophlogopite (INCI: Synthetic Fluorphlogopite, synthetic phlogopite iron (INCI: Biotite), potassium silicate (INCI: Potassium Silicate), silicon dioxide (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 silicate (INCI: Aluminum Calcium Sodium Silicate), lithium / magnesium / sodium silicate (INCI: Lithium Magnesium Sodium Silicate), sodium / magnesium silicate (INCI: Sodium Magnesium Silicate), borosilicate (calcium / aluminum) (INCI: Calcium Aluminum Borosilicate), borosilicate (calcium / sodium) (INCI: Calcium Sodium Borosilicate), hydroxyapatite (INCI), bentonite (INCI), montmorillonite (INCI), lithium montmorillonite (INCI), zeolite (INCI), alumina (INCI), aluminum hydroxide (INCI: Aluminum Borosilicate).Particles composed of Hydroxide, Boron Nitride, and Glass.

[0365] In addition, examples of inorganic colored pearl pigments include, for instance, mica (INCI) coated with titanium dioxide (INCI), synthetic fluorophlogopite (INCI) coated with titanium dioxide (INCI), and pearl agents such as bismuth oxychloride (INCI) or bismuth oxychloride (INCI) coated with titanium dioxide (INCI), talc (INCI) coated with titanium dioxide (INCI), fish scale foil (INCI), colored mica (INCI) coated with titanium dioxide (INCI), etc. There are no particular limitations on whether they are untreated or have been treated with known surface treatments commonly used in cosmetics.

[0366] Metal powder

[0367] Examples of metal powders include microparticles composed of aluminum (INCI: Aluminum Powder), copper (INCI: Copper Powder), silver (INCI: Silver Powder), and gold (INCI: Gold).

[0368] organic powder

[0369] Examples of organic powders include those composed of organosilicon, polyamide, polyacrylate, polyester, polyethylene (INCI), polypropylene (INCI), polystyrene (INCI), styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, polyurethane, vinyl resin, urea-formaldehyde resin, melamine resin, benzo-melamine, polymethylbenzene melamine, tetrafluoroethylene, polymethyl methacrylate, cellulose (INCI), silk (INCI), nylon (identified name), phenolic resin, epoxy resin, polycarbonate, etc.

[0370] In particular, examples of organosilicon include organosilicon resin particles; polymethylsilsesquioxane (INCI), organosilicon rubber powder, organosilicon rubber powder coated with organosilicon resin; (vinyl polydimethylsiloxane / polymethylsiloxane silsesquioxane) crosslinked polymer (INCI), (diphenyl polydimethylsiloxane / vinyl diphenyl polydimethylsiloxane / silsesquioxane) crosslinked polymer (INCI), polysiloxane-1 crosslinked polymer (INCI), polysiloxane-22 (INCI), etc.

[0371] Examples of commercially available powders composed of organosilicon include those manufactured by Shin-Etsu Chemical Co., Ltd. of Japan: 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, KM-440, etc.

[0372] In addition, examples such as metallic soaps can be cited. Specific examples include powders composed of zinc stearate (INCI: Zinc Stearate), aluminum stearate (INCI: Aluminum Stearate), calcium stearate (INCI: Calcium Stearate), magnesium stearate (INCI: Magnesium Stearate), zinc myristate (INCI: Zinc Myristate), magnesium myristate (INCI: Magnesium Myristate), sodium cetyl phosphate (Zinc / Sodium) (INCI: Sodium Zinc Cetyl Phosphate), and potassium cetyl phosphate (INCI: Potassium Cetyl Phosphate).

[0373] Furthermore, organic pigments can be cited as examples. Specific examples include Red No. 3, Red No. 104 (1) (identification name (INCI: Red 28, Red 28 Lake), Red No. 106, Red No. 201 (identification name (INCI: Red 6)), Red No. 202 (identification name (INCI: Red 7)), Red No. 204, Red No. 205, Red No. 220 (identification name (INCI: Red 34), Red No. 226 (identification name (INCI: Red 30), Red No. 227 (identification name: INCI: Red 33, Red 33 Lake), Red No. 228 (identification name (INCI: Red 36)), and Red No. 230 (1) (identification name (INCI: Red 22, Red 22 Lake)). Lake), Red 230 (2) (Identifier name), Red 401 (Identifier name), Red 505 (Identifier name), Yellow 4 (Identifier name (INCI: Yellow 5)), Yellow 5 (Identifier name: INCI: Yellow 6, Yellow 6 Lake), Yellow 202 (1) (Identifier name (INCI: Yellow 8)), Yellow 203 (Identifier name: INCI: Yellow 10, Yellow 10 Lake), Yellow 204 (Identifier name (INCI: Yellow 11)), Yellow 401, Blue 1 (Identifier name (INCI: Blue 1, Blue 1 Lake), Blue 2, Blue 201, Blue 205 (Identifier name (INCI: Blue 4)), Blue 404 (Identifier name), Green 3 (Identifier: INCI: Green 3, Green 3 Lake), Green 201 (Identifier name: INCI: Green 3 Lake) 5) Organic synthetic pigments such as Green 202 (INCI: Green 6) and Green 204 (INCI: Green 8), Green 205 (INCI: Orange 5), Orange 201 (INCI: Orange 5), Orange 203 (INCI: Pigment Orange 5), Orange 204 (INCI: Orange 4), Orange 205 (INCI: Orange 4, Orange 4 Lake), Orange 206 (INCI: Orange 10), and Orange 207 (INCI: Orange 11).Natural pigments include carmine (INCI), shellac acid (INCI: Laccaic Acid), safflower red (INCI: Carthamus Tinctorius (Safflower) Flower Extract), ginkgo biloba and lithospermum Root Extract (INCI: Lithospermum Officinale Root Extract), gardenia yellow (INCI: Gardenia Yellow), and gardenia blue (INCI: Hydrolyzed Gardenia Florida Extract).

[0374] Inorganic-organic composite powder

[0375] As an inorganic-organic composite powder, an example is a composite powder formed by coating an organic powder onto the surface of an inorganic powder using known methods.

[0376] Alternatively, the powders mentioned above can also be powders with particle surface treatment. From the viewpoint of the water resistance of cosmetics, the surface treatment agent is preferably a substance capable of imparting hydrophobicity. No particular limitation is placed on the surface treatment agent that imparts hydrophobicity; examples include, for instance, silicone treatment agents, waxes, paraffins, perfluoroalkyl and phosphate organic fluorine compounds, surfactants, amino acids such as N-acylglutamic acid, and metal soaps such as aluminum stearate and magnesium myristate.

[0377] More preferably, examples of organosilicon treatment agents include silanes or silanizing agents such as triethoxyoctylsilane (INCI), polydimethylsiloxane (INCI), polymethylsiloxane (INCI), hydrogen polydimethylsiloxane (INCI), triethoxysilylethyl polydimethylsiloxane (INCI), triethoxysilylethyl polydimethylsiloxane (INCI), triethoxysilylethyl polydimethylsiloxane (INCI), and copolymers of (acrylate / tridecyl acrylate / triethoxysilylpropyl methacrylate / polydimethylsiloxane methacrylate) (identified name (INCI: Acrylates / TridecylAcryl / TriethoxysilylpropylMethacryl / DimethiconeMethacrylCopolymer), etc.).

[0378] Specific examples of these organosilicon treatment agents include, for instance, those manufactured by Shin-Etsu Chemical Co., Ltd. of Japan: AES-3083, KF-99P, KF-9901, KF-9908, KF-9909, KP-574, KP-541, etc.

[0379] Furthermore, the aforementioned surface hydrophobic treatment agents can be used alone or in combination of two or more. Specific examples of coloring pigments that have undergone surface treatment include, for instance, the KTP-09 series manufactured by Shin-Etsu Chemical Co., Ltd. of Japan, particularly KTP-09W, KTP-09R, KTP-09Y, and KTP-09B.

[0380] (5) A composition consisting of a cross-linked organopolysiloxane and a liquid oiling agent at room temperature.

[0381] In a composition consisting of a cross-linked organopolysiloxane and a liquid oiling agent at room temperature, preferably, the cross-linked organopolysiloxane swells relative to the liquid oil by a weight greater than that of the liquid oil.

[0382] As the liquid oil, liquid silicone oil, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil, fluorinated oil, etc., can be used as optional components. Examples include, for example, cyclopentasiloxane (INCI), polydimethylsiloxane (INCI), mineral oil (INCI), isododecane (INCI), isohexadecane (INCI), glyceryl tri(ethylhexanoate) ester (INCI), isotridecyl isononanoate (INCI: Isotridecyl Isonononanoate), squalane (INCI), etc.

[0383] (5) The cross-linked silicone surfactants of the above (3) are different from those of the above (3). They are compounds that do not have polyether or polyglycerol structures in their molecular structure. For specific examples, such as (polydimethylsiloxane / vinyl polydimethylsiloxane) cross-linked polymer (INCI), (polydimethylsiloxane / phenylvinyl polydimethylsiloxane) cross-linked polymer (INCI), (vinyl polydimethylsiloxane / lauryl polydimethylsiloxane) cross-linked polymer (INCI), (lauryl polydimethylsiloxyethyl polydimethylsiloxane / bisvinyl polydimethylsiloxane) cross-linked polymer (INCI), etc.

[0384] Examples of compositions consisting of commercially available cross-linked organopolysiloxanes and liquid oils at room temperature include those manufactured by Shin-Etsu Chemical Co., Ltd. of Japan: 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, KSG-048Z, etc.

[0385] (6) Film-forming agent

[0386] The film-forming agent is formulated primarily to further maintain the lasting effect of the cosmetic. While there are no particular limitations, from the viewpoint of imparting water resistance, a silicone-based composition is preferred. Specifically, examples such as trimethylsiloxysilicate, acrylic-based silicone coating agents, silicone-modified norbornene, silicone-modified pullulan, and silicone-modified polyvinyl alcohol can be used.

[0387] Examples of film-forming agents for organosilicon compositions include, for example, trimethylsiloxysilicate (INCI), (acrylate / polydimethylsiloxane) copolymer (INCI), (norbornene / tri(trimethylsiloxy)silylnorbornene) copolymer (INCI), tri(trimethylsiloxy)silylpropylcarbamoylpullulan (INCI), etc.

[0388] The film-forming agent can also be dissolved in a liquid oil at room temperature before being incorporated into cosmetics. As the liquid oil, liquid silicone oil, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil, and fluorinated oil can be used from the optional components of (1) the oil.

[0389] Specific examples of commercially available silicone film-forming agents include those manufactured by Shin-Etsu Chemical Co., Ltd. of Japan: KF-7312 J, KP-545, KP-549, KP-543, NBN-30-ID, TSPL-30-ID, TSPL-30-D5, etc.

[0390] (7) Ultraviolet absorbers / scatterers

[0391] Examples of ultraviolet (UV) absorbers / scatterers include microparticles such as particulate titanium dioxide, particulate iron-containing titanium dioxide, particulate zinc oxide, particulate cerium oxide, and their complexes. Dispersions in which these UV-absorbing and scattering particles are pre-dispersed in the oil can also be used.

[0392] As the oiling agent, liquid silicone oil, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil, and fluorinated oil can be used as optional components of (1) the oiling agent.

[0393] As a specific example of a dispersion in which particles that absorb and scatter ultraviolet light are pre-dispersed in an oil, examples include the SPD series (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. of Japan, particularly SPD-T5, SPD-T5L, SPD-Z5, SPD-Z5L, SPD-T6, SPD-Z6, SPD-T7, and SPD-Z7L.

[0394] (8) Other additives

[0395] Other additives include, for example, oil-soluble gelling agents, preservatives / bactericides, antiperspirants, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin care ingredients (whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, and encapsulation compounds.

[0396] Oil-soluble gelling agents

[0397] Examples of oil-soluble gelling agents include, for instance, metal soaps such as aluminum stearate, magnesium stearate, and zinc tetradecanoate; amino acid derivatives such as lauroyl glutamate (INCI: Lauroyl Glutamic Acid) and α, γ-di-n-butylamine; dextrin palmitate (INCI: Dextrin Palmitate), dextrin isostearate (INCI: Dextrin Isostearate), dextrin myristate (INCI: Dextrin Myristate), stearoyl inulin (INCI: Stearoyl Inulin), and dextrin palmitate / ethylhexanoate (INCI: Dextrin Palmitate / ethylhexanoate). Dextrin fatty acid esters such as palmitate / ethylhexanoate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; oligofructose fatty acid esters such as oligofructose stearate and oligofructose 2-ethylhexanoate; benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol; organically modified clay minerals of distearate dimethylammonium lithium montmorillonite (INCI), silachlorium lithium montmorillonite (INCI), and lithium montmorillonite; silachlorium bentonite (INCI), etc.

[0398] Preservatives / bactericides

[0399] Examples of preservatives and bactericides include alkyl p-hydroxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropyl methylphenol, carbolic acid, p-chloro-m-cresol, hexachlorophenol, benzalkonium chloride, chlorhexidine chloride, triclocarban, iodopropynyl butylcarbamate, polylysine, photosensitizer, silver, and plant extracts.

[0400] antiperspirant

[0401] Examples of antiperspirants include, for example, aluminum hydroxy halides such as aluminum hydroxychloride, aluminum halides such as aluminum chloride, allantoin aluminum salts, tannic acid, persimmon tannin, sulfuric acid (aluminum / potassium), zinc oxide, zinc p-phenolsulfonate, pyroxene, tetrachloro(aluminum / zirconium) hydrate, trichlorohydroxyglycine (aluminum / zirconium), etc.

[0402] In particular, aluminum hydroxyhalides, aluminum halides, and their zirconium oxyhalides, as well as complexes or mixtures with zirconium hydroxyhalides (e.g., tetrachloro(aluminum / zirconium) hydrate, trichlorohydroxyglycine(aluminum / zirconium), etc., are preferred as components exhibiting high efficacy.

[0403] spices

[0404] As a fragrance, it includes both natural and synthetic fragrances. Natural fragrances include plant-based fragrances extracted from flowers, leaves, wood, fruit peels, etc., 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, acetals, etc.

[0405] Salts

[0406] Examples of salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. Inorganic salts include, for example, sodium, potassium, magnesium, calcium, aluminum, zirconium, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid. Organic acid salts include, for example, salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid. Amino acid and amino acid salts include, for example, salts of amines such as triethanolamine and salts of amino acids such as glutamic acid. Furthermore, salts of hyaluronic acid, chondroitin sulfate, aluminum zirconium glycine complexes, etc., can also be used, or, more specifically, acid-base neutralizing salts used in cosmetic formulations.

[0407] antioxidants

[0408] As antioxidants, there are no particular limitations. Examples include carotene, ascorbic acid and its salts, ascorbic acid stearate, vitamin E, vitamin E acetate, tocopherol, p-tert-butylphenol, butylated hydroxyanisole, butylated hydroxytoluene, phytic acid, ferulic acid, thiotaurine, taurine, sulfites, erythritol and its salts, chlorogenic acid, epicatechin, epigallocatechin (EGC), epigallocatechin gallate (EGCG), apigenin, kaempferol, myricetin, quercetin, etc. Antioxidants can be used alone or in combination with two or more.

[0409] pH adjuster

[0410] Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate.

[0411] Chelating agents

[0412] Examples of chelating agents include alanine, sodium ethionate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid.

[0413] Cooling agent

[0414] Examples of cooling agents include L-menthol, camphor, and menthyl lactate.

[0415] anti-inflammatory agents

[0416] Examples of anti-inflammatory agents include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid and glycyrrhetinic acid stearate, tranexamic acid, and chamomile.

[0417] Skin care ingredients

[0418] As skin-beautifying ingredients, examples include whitening agents such as arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extract; skin roughness improvers; blood circulation promoters such as vanillin nonanoate, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin, gingerone, cantharides tincture, ichthammol, caffeine, tannic acid, α-carboxyl alcohol, nicotinic acid tocopherol, inositol nicotinate, cyclomansyl ester, cinnarizine, tolazoline, acetylcholine, verapamil, sennae, and γ-oryzanol; skin astringents such as zinc oxide and tannic acid; and anti-seborrheic agents such as sulfur and dimethylthione.

[0419] Vitamins

[0420] Examples of vitamins include, for instance, vitamin A derivatives such as vitamin A oil, retinol, retinol acetate, and retinol palmitate; vitamin B2 derivatives such as riboflavin, riboflavin butyrate, and flavin adenine nucleotide; vitamin B6 derivatives such as pyridoxine hydrochloride, pyridoxine dioctanoate, and pyridoxine trimalpalmitate; vitamin B12 and its derivatives; vitamin B15 and its derivatives; and L-ascorbic acid, L-ascorbic acid dipalmitate, and L-ascorbic acid-2-sulfate. Sodium, dipotassium L-ascorbic acid phosphate diester and other vitamin C derivatives; ergocalcisterol, cholecalciferol and other vitamin D derivatives; α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol niacin, dl-α-tocopherol succinate and other vitamin E derivatives; niacin, benzyl nicotinic acid ester, nicotinamide and other niacin derivatives; vitamin H; vitamin P; pantothenic acid derivatives such as calcium pantothenate, D-panthenol, panthenol ethyl ether, acetylpanthenol ethyl ether and other pantothenic acid derivatives; biotin, etc.

[0421] amino acids

[0422] Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, asparagine, glutamic acid, cystine, methionine, and tryptophan.

[0423] Nucleic acid

[0424] Examples of nucleic acids include, for example, deoxyribonucleic acid (DNA).

[0425] hormone

[0426] Examples of hormones include estradiol and ethinylestradiol.

[0427] Envelope

[0428] Examples of inclusion compounds include cyclodextrins.

[0429] [Example]

[0430] The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited to the following examples.

[0431] It should be noted that, in the following examples, unless otherwise specified, "%" indicating concentration and content ratio refers to "mass %" and "parts" refers to "parts by mass". Additionally, the kinematic viscosity is the value measured at 25°C. Furthermore, in the following examples, the volume average particle size and aspect ratio of the elastomeric spherical particles and elastomeric composite particles represent values ​​measured using the methods described above.

[0432] The hardness of the cured rubber (elastomer) is the value measured according to the Japan Rubber Industry Association Standard Specification (SRIS).

[0433] The molecular weight of a copolymer having both polyester and polyether structures (a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule) is the weight-average molecular weight (M) of polystyrene as a standard substance, which will be determined by GPC under the following conditions. W . ).

[0434] [Measurement Conditions]

[0435] Elution solvent: Tetrahydrofuran (THF)

[0436] Flow rate: 0.60 mL / min

[0437] Detector: Differential Refractive Index Detector (RI)

[0438] Column: TSK Guardcolumn SuperH-H

[0439] TSKgel SuperHM-N

[0440] TSKgel SuperH2500 (all manufactured by Tosoh Corporation, Japan)

[0441] Column temperature: 40℃

[0442] Sample injection volume: 50 µL (0.5% by mass THF solution)

[0443] [Methods for determining / evaluating biodegradability]

[0444] Biodegradability was determined using activated sludge from a microbial (degradation) source, according to the OECD Guidelines for the Testing of Chemicals, No. 301F, July 17, 1992, “Ready Biodegradability: MANOMETRIC RESPIROMETRY TEST” standard, and evaluated based on the degree of biodegradability. The activated sludge used was from a municipal wastewater treatment plant, with a suspended solids concentration of 2400 mg / L. Sodium benzoate was used as a standard (control).

[0445] As a method for determining biodegradability, a BOD measuring instrument was used to measure the oxygen consumption (biochemical oxygen consumption (BOD)) in the closed system inside the incubator, and the biodegradability was calculated according to the following formula.

[0446] Biodegradability (%) = BOD - B / TOD × 100

[0447] BOD: Biochemical oxygen demand of the test suspension or control (measured value: mg)

[0448] B: Mean biochemical oxygen demand (measured value: mg) of plant-derived blank samples

[0449] TOD: The theoretical oxygen consumption required for the complete oxidation of the tested substance or sodium benzoate (calculated value: mg).

[0450] [Synthesis Example 1: Acrylic-modified poly-ε-caprolactone / polyether copolymer 1]

[0451] In a 2L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 500g of terminally carbide EO (ethylene oxide) / PO (propylene oxide) polyether (molecular weight: approximately 2000, OH group equivalent: 0.09~0.10mol / 100g), 183.6g of ε-caprolactone (molecular weight 114.1), and 350g of dehydrated toluene were added and heated to 90°C under nitrogen flow. After reaching the target temperature, 0.68g of tetrabutyl titanate (molecular weight 340.0) was added as a catalyst, and the mixture was aged at 120°C for 4~6 hours.

[0452] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 60.7 g of triethylamine (molecular weight 101.2), 100 g of dehydrated toluene, and 0.22 g of butylated hydroxytoluene (BHT) (molecular weight 220.4) as a polymerization inhibitor were added. After stirring for a certain period of time to ensure uniform dissolution, 49.7 g of acryloyl chloride (molecular weight 90.5) was added dropwise using a dropping funnel. After confirming the heating effect, the mixture was cured at 60°C for 4 hours.

[0453] After pressure filtration of the obtained crude product, washing with sodium chloride aqueous solution using a separatory funnel, centrifugation, etc., magnesium sulfate, silica gel, activated carbon, etc. were added, and impurities were adsorbed and removed by vibrating powder treatment. After removing the above powders by pressure filtration, 0.22g of butylated hydroxytoluene (BHT) was added, and the solvent was removed by distillation at 60~70℃ and below 50mmHg, thereby obtaining acrylic modified poly-ε-caprolactone / polyether copolymer 1 (hereinafter formula (11), weight average molecular weight: 2880).

[0454] [Chemical Formula 11]

[0455]

[0456] (l≈12~14, m≈22~26, r≈3~4)

[0457] [Synthesis Example 2: Acrylic Acid Modified Poly-ε-Caprolactone / Polyether Copolymer 2]

[0458] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (similar to that in Synthesis Example 1), 110.2g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.41g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0459] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 100g of dehydrated toluene, 0.96g of dioctyl dinecaproyltin oxide (molecular weight 687.7) and 0.12g of dibutylhydroxytoluene (BHT) as catalysts were added, and the mixture was stirred for a certain period of time. After it was uniformly dissolved, 44.4g of ethyl 2-isocyanate acrylate (molecular weight 141.1) was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was cured at 60°C for 4 hours.

[0460] After cooling the obtained crude product to below 40°C, 0.8 g of ethanol was added to react with unreacted (residual) isocyanate groups, and rapid cooling was performed. Then, magnesium sulfate, silica gel, activated carbon, etc. were added, and impurities were adsorbed and removed by vibrating powder treatment. After removing the above powders by pressure filtration, 0.12 g of butylated hydroxytoluene (BHT) was added, and the solvent was removed by distillation at 60~70°C and below 50 mmHg, thereby obtaining acrylic modified poly-ε-caprolactone / polyether copolymer 2 (hereinafter, formula (12), weight average molecular weight: 3120).

[0461] [Chemical Formula 12]

[0462]

[0463] (l≈12~14, m≈22~26, r≈3~4)

[0464] [Synthesis Example 3: Acrylic Acid Modified Poly-ε-Caprolactone / Polyether Copolymer 3]

[0465] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (molecular weight: approximately 2600, OH group equivalent: 0.09~0.10mol / 100g), 115.2g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.42g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4~6 hours.

[0466] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 70g of dehydrated toluene, 0.18g of tris(2,4-pentanedione)ferro(III) (also known as acetylacetone ferro(III) (molecular weight: 353.2) as a catalyst) and 0.13g of butylated hydroxytoluene (BHT) were added. After stirring for a certain period of time and allowing it to dissolve evenly, 46.4g of ethyl 2-isocyanate acrylate was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was aged at 60°C for 4 hours.

[0467] Similar to the method described in Synthesis Example 2 above, the crude product was subjected to post-processing and refining steps to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 3. The acrylic-modified poly-ε-caprolactone / polyether copolymer 3 has the structure of formula (12), in formula (12), l≈18~21, m≈34~38, r≈3~4, and weight-average molecular weight: 4870.

[0468] [Synthetic Example 4: Acrylic Acid Modified Poly-ε-Caprolactone / Polyether Copolymer 4]

[0469] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (similar to that used in Synthesis Example 3), 115.2g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.42g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0470] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 70g of dehydrated toluene, 2.77g of tetraacetylacetone zirconium (molecular weight: 487.7) as a catalyst, and 0.13g of butylated hydroxytoluene (BHT) were added. The mixture was stirred for a certain period of time until it was uniformly dissolved. Then, 46.4g of ethyl 2-isocyanate acrylate was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was cured at 60°C for 4 hours.

[0471] Similar to the method described in Synthesis Example 2 above, the crude product was subjected to post-processing and refining steps to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 4. The acrylic-modified poly-ε-caprolactone / polyether copolymer 4 has the structure of formula (12), in which l≈18~21, m≈34~38, r≈3~4, and weight-average molecular weight: 4990.

[0472] [Synthetic Example 5: Acrylic Acid Modified Poly-ε-Caprolactone / Polyether Copolymer 5]

[0473] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (molecular weight: approximately 3200, OH group equivalent: 0.062mol / 100g), 106.3g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.41g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0474] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 70g of dehydrated toluene, 1.01g of dioctyl dineodecanotin oxide as a catalyst, and 0.13g of dibutylhydroxytoluene (BHT) were added. The mixture was stirred for a certain period of time until it was uniformly dissolved. Then, 28.4g of ethyl 2-isocyanate acrylate was added dropwise using a dropping funnel, and the mixture was aged at 60°C for 4 hours.

[0475] Similar to the method described in Synthesis Example 2 above, the crude product was subjected to post-treatment and refining processes to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 5 (Formula (13), weight average molecular weight: 7940).

[0476] [Chemical Formula 13]

[0477]

[0478] (l≈24~26, m≈35~37, r≈4~5)

[0479] [Synthetic Example 6: Acrylic Acid Modified Poly-ε-Caprolactone / Polyether Copolymer 6]

[0480] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (molecular weight: approximately 1100, OH group equivalent: 0.182mol / 100g), 311.6g of ε-caprolactone, and 250g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.61g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0481] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 100g of dehydrated toluene, 2.77g of tetraacetylacetonate zirconium (IV) (molecular weight: 487.7) as a catalyst and 0.21g of butylated hydroxytoluene (BHT) were added. The mixture was stirred for a certain period of time until it was uniformly dissolved. Then, 80.84g of ethyl 2-isocyanate acrylate (molecular weight: 141.1) was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was cured at 60°C for 4 hours.

[0482] Similar to the method described in Synthesis Example 2 above, the crude product was subjected to post-treatment and refining processes to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 6 (Formula (14), weight average molecular weight: 2530).

[0483] [Chemical Formula 14]

[0484]

[0485] (l≈6~8, m≈11~13, r≈5~6)

[0486] [Synthesis Example 7: Acrylic-modified poly-ε-caprolactone / polyether copolymer 7]

[0487] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (molecular weight: approximately 7200, OH group equivalent: 0.028mol / 100g), 31.4g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.33g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0488] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 50g of dehydrated toluene, 1.37g of zirconium tetraacetylacetonate (IV) (molecular weight: 487.7) as a catalyst, and 0.11g of butylated hydroxytoluene (BHT) were added. The mixture was stirred for a certain period of time until it was uniformly dissolved. Then, 12.3g of ethyl 2-isocyanate acrylate (molecular weight: 141.1) was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was cured at 60°C for 4 hours.

[0489] Similar to the method described in Synthesis Example 2 above, the crude product was subjected to post-treatment and refining processes to obtain acrylic-modified poly-ε-caprolactone / polyether copolymer 7 (Formula (15), weight average molecular weight: 8250).

[0490] [Chemical Formula 15]

[0491]

[0492] (l≈24~32, m≈44~50, r≈3~4)

[0493] [Biodegradability Evaluation]

[0494] Based on the evaluation method, the biodegradability of acrylic-modified poly-ε-caprolactone poly / ether copolymer 1 was determined during a 60-day culture period at a culture temperature of 22±1℃. The results showed that the biodegradability of acrylic-modified poly-ε-caprolactone / ether copolymer 1 was 62% on average after 28 days and 73% on average after 60 days, meeting the criterion of 60% biodegradability after 28 days. Therefore, acrylic-modified poly-ε-caprolactone / ether copolymer 1 was judged as a "biodegradable substance".

[0495] Therefore, it can be inferred that the elastomeric spherical particles and elastomeric composite particles, which are crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymer 1, will not remain in the environment as particles after being used and will eventually be degraded if they flow directly into the ocean through land water systems.

[0496] The biodegradability of acrylic-modified poly-ε-caprolactone poly / ether copolymers 2-4 was determined over a 60-day incubation period at a culture temperature of 22±1℃. The results showed that the biodegradability of acrylic-modified poly-ε-caprolactone / ether copolymers 2-4 averaged 40% after 28 days and 65% after 60 days, meeting the criterion of 60% biodegradability after 60 days. Therefore, acrylic-modified poly-ε-caprolactone / ether copolymers 2-4 were judged to be "inherently biodegradable substances".

[0497] Therefore, it can be inferred that the elastomeric spherical particles and elastomeric composite particles, which are crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymers 2-4, and the elastomeric spherical particles and elastomeric composite particles, which have the same structure as the repeating units of acrylic-modified poly-ε-caprolactone / polyether copolymers 2-4 but have different numbers of repeating units, will not remain in the environment as particles after using these particles and will eventually be degraded if they flow directly into the ocean through land water systems.

[0498] [Preparation Example 1: Elastomer Spherical Particles 1]

[0499] 250g of a 2.6% aqueous solution of hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) was loaded into a 1L container of a vacuum emulsifier (AGI-HOMO MIXER). The mixture was stirred and mixed under heating conditions of 55~60°C while the homogenizer and anchor mixer were running.

[0500] Meanwhile, 100g of the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 described in Synthesis Example 4 above and 1.0g of 2,2'-azobis(2-methylpropionate) (molecular weight: 230.3) were placed into a graduated cup, mixed in advance using a dispersion mixer, and preheated to 60~65°C.

[0501] Next, the pre-mixed acrylic-modified poly-ε-caprolactone / polyether copolymer was added to a 1L vacuum emulsifier containing a preheated aqueous solution of hydroxypropyl methylcellulose. The mixture was stirred for more than 10 minutes at a temperature of 55-60°C and a speed of 4500 rpm in a homogenizer to suspend and emulsify it, thus obtaining an O / W type emulsified (suspension) composition.

[0502] Subsequently, the obtained emulsified (suspension) composition was stirred and matured for 8 hours at 200 rpm and 70°C using a paddle impeller. After adding 50 g of pure water, it was matured again at 80°C for 6 hours at the same speed to obtain a dispersion of elastomer spherical particles 1.

[0503] When the shape of the elastomeric spherical particles 1 in the obtained dispersion was observed using an optical microscope, they were confirmed to be spherical. The volume average particle size was measured using a resistive particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.), and the volume average particle size was found to be 5 µm.

[0504] Using a filter screen (#100), the obtained dispersion of elastomer spherical particles 1 was checked for the presence or absence of agglomerates. If agglomerates were found, they were removed, and then solid-liquid separation was performed by pressure filtration to remove the continuous phase of pure water. The above washing and separation operation was repeated three times with pure water to remove the water. It should be noted that if solid-liquid separation is not perfectly achieved in the pressure filtration process, centrifugation can also be used.

[0505] Finally, by allowing the concentrate of the elastomer spherical particles 1 obtained above to stand and dry for more than 8 hours, a white to light yellow powder of the target elastomer spherical particles 1 was obtained.

[0506] The obtained elastomer spherical particle 1 powder was observed using an electron microscope (S-4700 scanning microscope, manufactured by Hitachi High Technology Co., Ltd., Japan), and was confirmed to be spherical particles with a volume average particle size of approximately 5 μm. Furthermore, the aspect ratio of the obtained elastomer spherical particles 1 was 1.0.

[0507] In addition, the dispersion of elastomeric spherical particles 1 obtained by using lauryl alcohol polyoxyethylene ether as a surfactant was measured and evaluated in water by resistance method, and the results confirmed that the volume average particle size was 5 μm.

[0508] The hardness of the elastomer (rubber) constituting the elastomer spherical particles 1 was determined using the method described below.

[0509] 30g of the synthesized acrylic-modified poly-ε-caprolactone / polyether copolymer 4 and 0.24g of 2'-azobis-(2,4-dimethylpentanonitrile) (molecular weight: 248.4) were stirred and mixed, and then poured into an aluminum container to form a thickness of 10mm. After standing in an air-conditioning bath at 70℃ for 1-2 hours, a non-sticky, flat rubber was obtained. The hardness of the obtained flat rubber was measured to be 72 using an Asker C hardness tester and 55 using an Asker A hardness tester.

[0510] [Preparation Example 2: Elastomeric Spherical Particles 2]

[0511] Except that the 250g of 2.6% aqueous solution of hydroxypropyl methylcellulose in Preparation Example 1 was replaced with 173g of 3.8% aqueous solution of hydroxypropyl methylcellulose, elastomer spherical particles 2 were manufactured using the same method as in Preparation Example 1. As a result, elastomer spherical particles with a volume average particle size of 2μm were obtained.

[0512] [Preparation Example 3: Elastomer Spherical Particles 3]

[0513] Except that the hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) used in Preparation Example 1 was replaced with hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-50, manufactured by Shin-Etsu Chemical Co., Ltd., Japan), elastomeric spherical particles 3 were manufactured using the same method as in Preparation Example 1. As a result, elastomeric spherical particles with a volume average particle size of 11 μm were obtained.

[0514] [Preparation Example 4: Elastomer Spherical Particles 4]

[0515] Except that the 2.6% aqueous solution of 250g of hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) used in Preparation Example 1 was replaced with a 5.2% aqueous solution of 250g of xanthan gum, elastomeric spherical particles 4 were manufactured using the same method as in Preparation Example 1. As a result, elastomeric spherical particles with a volume average particle size of 20μm were obtained.

[0516] [Preparation Example 5: Elastomeric Spherical Particles 5]

[0517] Except that the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 of Preparation Example 1 was replaced with the acrylic-modified poly-ε-caprolactone / polyether copolymer 6, elastomeric spherical particles 5 were manufactured using the same method as in Preparation Example 1. As a result, elastomeric spherical particles with a volume average particle size of 5 μm were obtained.

[0518] In addition, the hardness of the elastomer (rubber) constituting the spherical particles 5 was measured using the same method as described above. As a result, a non-sticky (non-greasy) flat rubber was obtained, and the hardness measured by the Asker A hardness tester was 78.

[0519] [Preparation Example 6: Elastomeric Spherical Particles 6]

[0520] Except that the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 of Preparation Example 1 was replaced with the acrylic-modified poly-ε-caprolactone / polyether copolymer 7, elastomeric spherical particles 6 were manufactured using the same method as in Preparation Example 1. As a result, elastomeric spherical particles with a volume average particle size of 5 μm were obtained.

[0521] In addition, the hardness of the elastomer (rubber) constituting the spherical particles 6 was measured using the same method as described above. As a result, the hardness of the obtained non-sticky (non-adhesive) flat rubber was measured to be 22 using an Asker A hardness tester.

[0522] [Comparative Example 1: Cellulose Powder]

[0523] Cellulose powder CELLULOBEADS D-5 (average particle size of 5μm) manufactured by Daito Kasei Corporation of Japan was used.

[0524] [Comparative Example 2: Spherical Silica Particles]

[0525] Spherical silica SILICA MICRO BEAD P-1500 (average particle size of 5 μm) manufactured by JGC Catalysts and Chemicals Ltd. of Japan was used.

[0526] [Preparation / Manufacturing Example 1: Elastomer Composite Particle 1]

[0527] 100g of a dispersion of 20% solids elastomer spherical particles 1 obtained in Preparation Example 1, 184.9g of pure water, and 0.2g of a 30% dodecyltrimethylammonium chloride aqueous solution were placed into a 500ml glass flask equipped with a paddle impeller. After the aqueous dispersion was heated to 5-10°C, while maintaining the aqueous dispersion containing 0.75g of 5.0% ammonia at 5-10°C, 11.2g of tetramethoxysilane (an amount that, relative to 100 parts by mass of the elastomer spherical particles, reduces the amount of silica after hydrolysis and condensation reaction to 22.0 parts by mass) was added dropwise over 15-30 minutes, while maintaining the liquid temperature at 5-10°C and stirring for 1 hour.

[0528] Next, the mixture was heated to 55-60°C and stirred and matured for 1 hour while maintaining the temperature, thus completing the hydrolysis and condensation reaction of tetramethoxysilane.

[0529] Using a pressure filter, the dispersion of tetramethoxysilane in the dispersion of elastomer spherical particles 1, obtained by hydrolysis and condensation reaction, was dehydrated to approximately 30% moisture content. Next, the dehydrated material was transferred to a 1L glass flask equipped with an anchor stirrer, 500g of water was added, and the mixture was stirred for 30 minutes. Dehydration was then carried out by pressure filtration. The dehydrated material, after undergoing three repeated washing and dehydration processes, was dried in a hot air flow dryer at 105°C, and the dried material was crushed using a jet mill to obtain free-flowing particles.

[0530] When the obtained particles were observed using an electron microscope, it was confirmed that spherical silica adhered and coated the entire surface of the elastomeric spherical particles, thereby obtaining silica-coated elastomeric spherical particles (elastomeric composite particles 1). In addition, the aspect ratio of the silica-coated elastomeric spherical particles (elastomeric composite particles 1) obtained in Example 1 was 1.0.

[0531] The obtained silica-coated elastomer spherical particles (elastomer composite particles 1) were dispersed in water using a surfactant (lauryl alcohol polyoxyethylene ether). The particle size distribution was measured using a resistivity particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.). The particle size distribution was confirmed to be the same as that of the aqueous dispersion of the above-mentioned elastomer spherical particles 1, with a volume average particle size of about 5 µm.

[0532] [Preparation / Manufacturing Example 2: Elastomer Composite Particles 2]

[0533] Except that the elastomeric spherical particles 1 in Preparation / Manufacturing Example 1 were replaced with elastomeric spherical particles 2 (Preparation Example 2), elastomeric composite particles were manufactured using the same method as in Preparation / Manufacturing Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles 2) with a volume average particle size of approximately 2 µm were obtained.

[0534] [Preparation / Manufacturing Example 3: Elastomer Composite Particles 3]

[0535] Except that the elastomeric spherical particles 1 in Preparation / Manufacturing Example 1 were replaced with elastomeric spherical particles 3 (Preparation Example 3), elastomeric composite particles were manufactured using the same method as in Preparation / Manufacturing Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles 3) with a volume average particle size of approximately 11 µm were obtained.

[0536] [Preparation / Manufacturing Example 4: Elastomer Composite Particles 4]

[0537] Except that the elastomeric spherical particles 1 in Preparation / Manufacturing Example 1 were replaced with elastomeric spherical particles 4 (Preparation Example 4), elastomeric composite particles were manufactured using the same method as in Preparation / Manufacturing Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles 4) with a volume average particle size of approximately 20 µm were obtained.

[0538] [Preparation / Manufacturing Example 5: Elastomer Composite Particles 5]

[0539] Except that the elastomeric spherical particles 1 in Preparation / Manufacturing Example 1 were replaced with elastomeric spherical particles 5 (Preparation Example 5), elastomeric composite particles were manufactured using the same method as in Preparation / Manufacturing Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles 5) with a volume average particle size of approximately 5 µm were obtained.

[0540] [Preparation / Manufacturing Example 6: Elastomer Composite Particles 6]

[0541] Except that the elastomeric spherical particles 1 in Preparation / Manufacturing Example 1 were replaced with elastomeric spherical particles 6 (Preparation Example 6), elastomeric composite particles were manufactured using the same method as in Preparation / Manufacturing Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles 6) with a volume average particle size of approximately 5 µm were obtained.

[0542] [Preparation / Manufacturing Example 7: Elastomer Composite Particles 7]

[0543] 100g of a dispersion of 20% solids elastomer spherical particles 3 obtained in Preparation Example 3, 184.9g of pure water, and 0.2g of a 30% dodecyltrimethylammonium chloride aqueous solution were added to a 500ml glass flask equipped with a paddle impeller. After the aqueous dispersion was heated to 5-10°C, while maintaining the aqueous dispersion with 0.84g of 5.0% ammonia added at 5-10°C, 12.5g of methyltrimethoxysilane (an amount equal to 22.0 parts by mass relative to 100 parts by mass of the elastomer spherical particles after hydrolysis and condensation) was added dropwise over 15-20 minutes, maintaining the liquid temperature at 5-10°C during this period, and stirring was performed for 1 hour. Subsequent operations were performed using the same method as in Preparation and Manufacturing Example 1, resulting in flowable particles.

[0544] When the obtained particles were observed using an electron microscope, it was confirmed that they were attached and coated with spherical polyorganosilsesquioxane throughout the entire surface of the elastomer spherical particles, thus obtaining polyorganosilsesquioxane-coated elastomer spherical particles (elastomer composite particles 7). In addition, the aspect ratio of the obtained polyorganosilsesquioxane-coated elastomer spherical particles (elastomer composite particles 7) is 1.0.

[0545] The obtained polyorganosilsesquioxane-coated elastomer spherical particles (elastomer spherical particles 7) were dispersed in water using a surfactant (lauryl alcohol polyoxyethylene ether). The results of measuring the elastomer spherical particles 7 using a resistivity particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.) confirmed that the volume average particle size was approximately 11 µm.

[0546] [Preparation / Manufacturing Example 8: Elastomer Composite Particles 8]

[0547] Except that the amount of tetramethoxysilane added was adjusted from 11.2 g (an amount of 22.0 parts by mass of silica after hydrolysis and condensation reaction relative to 100 parts by mass of elastomer spherical particles) to 5.6 g (an amount of 11.0 parts by mass of silica after hydrolysis and condensation reaction relative to 100 parts by mass of elastomer spherical particles), elastomer composite particles were manufactured using the same method as in Preparation / Manufacturing Example 1. As a result, silica-coated elastomer spherical particles (elastomer composite particles 8) with a volume average particle size of approximately 5 µm were obtained.

[0548] [Preparation / Manufacturing Example 9: Elastomer Composite Particles 9]

[0549] Except that the elastomeric spherical particles 3 in Preparation / Manufacturing Example 7 were replaced with elastomeric spherical particles 4, and the amount of methyltrimethoxysilane added was adjusted from 12.5 g (an amount that makes the silane after hydrolysis and condensation reaction 22.0 parts by mass relative to 100 parts by mass of elastomeric spherical particles) to 0.51 g (an amount that makes the silane after hydrolysis and condensation reaction 0.9 parts by mass relative to 100 parts by mass of elastomeric spherical particles), elastomeric composite particles were manufactured using the same method as in Preparation / Manufacturing Example 7. As a result, polyorganosilsesquioxane-coated elastomeric spherical particles (elastomeric composite particles 9) with a volume average particle size of approximately 20 µm were obtained.

[0550] [Comparative Example 3: Silica-coated mica]

[0551] The silica-coated mica VELVETVEIL310 (a composite powder in which 10% of silica with an average particle size of 300 nm is coated with mica) manufactured by JGC Catalysts and Chemicals Ltd. was used.

[0552] The particle size of the spherical silica or polyorganosilsesquioxanes attached to or coated on the surface of the elastomeric spherical particles obtained in each example is as shown in the table below.

[0553] [Table 1-1]

[0554]

[0555] (1) Usability evaluation

[0556] The particles from Preparation Examples 1-6, Preparation / Manufacturing Examples 1-9, and Comparative Examples 1-3 were incorporated into cosmetics, and their usability was evaluated.

[0557] For the oil-in-water creams formulated in Formulation Examples 1-15 and Comparative Examples 1-3, the applicability during application (spreadability, even adhesion to the skin) and the applicability after application (transparency, softness, coverage of pores and wrinkles) were evaluated.

[0558] For the powder foundations formulated in Formulation Examples 16-30 and Comparative Examples 4-6, the following items were evaluated: formability and usability during application (powder pick-up, spreadability, and even adhesion to the skin) and usability after application (softness, coverage of pores and wrinkles).

[0559] The oil-in-water sunscreens formulated in Formulation Examples 31-45 and Comparative Examples 7-9 were evaluated for their usability during application (spreadability, even adhesion to the skin) and their usability after application (transparency, coverage of pores and wrinkles, degree of oil-free film).

[0560] Ten members of a professional panel evaluated each aspect of usability. The evaluation was conducted according to the criteria shown in Table 1, and the results were determined based on the average score from the ten panel members, following the judgment criteria outlined below.

[0561] The results for water-in-oil (liquid emulsion) creams are shown in Table 2 below, the results for powder foundations are shown in Table 3 below, and the results for water-in-oil sunscreens are shown in Table 4.

[0562] [Table 1]

[0563]

[0564] (2) Usability criteria

[0565] ◎: Average score of 4.0 or above

[0566] ○: Average score is 3.0 or higher but lower than 4.0.

[0567] △: Average score is 2.0 or higher but lower than 3.0.

[0568] ×: Average score is below 2.0.

[0569] [Table 2-1]

[0570]

[0571] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / (PEG-10 / 15)) crosslinked polymer.

[0572] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 90-96% cyclopentasiloxane and 4-10% (polydimethylsiloxane / vinyl polydimethylsiloxane) crosslinked polymer.

[0573] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-10 polydimethylsiloxane.

[0574] (Manufacturing method)

[0575] A: Mix components 1-6 until homogeneous.

[0576] B: Mix components 7-10 until homogeneous.

[0577] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0578] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain a water-in-oil cream.

[0579] [Table 2]

[0580]

[0581] The results in Table 2 above confirm that formulations 1-15 effectively achieved a transparent finish after application, as well as softness of the coating and smoothing of uneven skin texture. Among them, formulations 7-15 demonstrated particularly excellent spreadability and uniform adhesion to the skin during application.

[0582] On the other hand, the formulations in Comparative Examples 1-3 were less effective in achieving a transparent, refined finish after application, as well as in improving the softness of the coating and repairing skin imperfections.

[0583] [Table 3-1]

[0584]

[0585] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxyoctylsilane

[0586] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: KF-9909 Processing Coloring Inorganic Pigment, W: White; R: Red; Y: Yellow; B: Black.

[0587] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl PEG-9 polydimethylsiloxyethyl polydimethylsiloxane

[0588] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0589] (Manufacturing method)

[0590] A: Use a Henschel mixer to mix components 1-5 until homogeneous.

[0591] B: Mix components 6-10 until homogeneous.

[0592] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous using a Henschel mixer.

[0593] D: After sieving the mixture obtained in step C above, it is stamped onto a metal tray using a mold to obtain a powder foundation.

[0594] [Table 3]

[0595]

[0596] The results in Table 3 above confirm that formulations 16-30 effectively improved the softness of the applied film and the repair of skin unevenness. Among them, formulations 22-30 showed particularly excellent formability, spreadability during application, and uniform adhesion to the skin.

[0597] On the other hand, the formulations in Comparative Examples 4-6 showed poor results in terms of the softness of the applied film and the repair of skin unevenness after application.

[0598] [Table 4-1]

[0599]

[0600] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 75-85% cyclopentasiloxane and 15-25% (polydimethylsiloxane / (PEG-10 / 15)) crosslinked polymer.

[0601] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 80-90% diphenylsiloxyphenyl polytrimethylsiloxane and 10-20% (polydimethylsiloxane / phenyl vinyl polydimethylsiloxane) crosslinked polymer.

[0602] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Cetyl PEG / PPG-10 / 1 polydimethylsiloxane.

[0603] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0604] (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Dispersion of cyclopentasiloxane solvent containing 45% particulate titanium dioxide.

[0605] (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: A dispersion of cyclopentasiloxane solvent containing 60% particulate titanium dioxide.

[0606] (Manufacturing method)

[0607] A: Mix components 1-10 until homogeneous.

[0608] B: Mix components 13-17 until homogeneous.

[0609] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0610] D: Add components 11-12 to the mixture obtained in step C above, and mix until homogeneous.

[0611] E: After degassing the mixture obtained in step D above, it is filled into a container to obtain a water-in-oil sunscreen.

[0612] [Table 4]

[0613]

[0614] The results in Table 4 above confirm that formulations 31-45 effectively improved the skin's texture, smoothing and evenness, and eliminated the oily film after application, resulting in a transparent, refined finish. Formulations 37-45, in particular, demonstrated excellent spreadability and uniform adhesion to the skin.

[0615] On the other hand, the formulations 7-9 were less effective in achieving a transparent, refined finish on the applied film, repairing uneven skin texture, and eliminating the oily film feeling.

[0616] [Table 5]

[0617]

[0618] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polyglycerol-3 disiloxane polydimethylsiloxane.

[0619] (Manufacturing method)

[0620] A: Mix components 1-3 until homogeneous.

[0621] B: Mix 4 to 10 ingredients until homogeneous.

[0622] C: Add the mixture obtained in step A above to the mixture obtained in step B above, and mix until homogeneous.

[0623] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an aqueous gel.

[0624] The aqueous gel of the present invention obtained as described above has excellent moisturizing properties when applied, is non-sticky, spreads easily, has excellent adhesion, good makeup setting properties, and has a matte finish that suppresses shine.

[0625] [Table 6]

[0626]

[0627] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 80-90% polydimethylsiloxane and 10-20% (polydimethylsiloxane / vinyl polydimethylsiloxane) cross-linked polymer.

[0628] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 90-96% cyclopentasiloxane and 4-10% (polydimethylsiloxane / vinyl polydimethylsiloxane) crosslinked polymer.

[0629] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane.

[0630] (Manufacturing method)

[0631] A: Mix components 1-5 until homogeneous.

[0632] B: After degassing the mixture obtained in step A above, it is filled into a container to obtain an oily gel.

[0633] The oily gel of the present invention obtained as described above has excellent silky smoothness when applied, is non-sticky, spreads easily, has excellent adhesion, good makeup setting properties, and is a water-based gel with a matte finish that suppresses shine.

[0634] [Table 7]

[0635]

[0636] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 65-75% mineral oil and 25-35% (PEG-15 / lauryl polydimethylsiloxane) crosslinked polymer.

[0637] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: A mixture of 65-75% squalane and 25-35% (vinyl polydimethylsiloxane / lauryl polydimethylsiloxane) crosslinked polymers.

[0638] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Cetyl PEG / PPG-10 / 1 polydimethylsiloxane.

[0639] (Manufacturing method)

[0640] A: Mix components 1-5 until homogeneous.

[0641] B: Mix components 6-10 until homogeneous.

[0642] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0643] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain a water-in-oil cream.

[0644] The water-in-oil cream of the present invention obtained as described above has excellent silky smoothness when applied, is non-sticky, spreads easily, has excellent adhesion, good makeup setting properties, and has a natural, refined finish that suppresses the shine of oil.

[0645] [Table 8]

[0646]

[0647] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenyl polydimethylsiloxane

[0648] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG / PPG-20 / 22 butyl ether polydimethylsiloxane.

[0649] (Manufacturing method)

[0650] A: Mix components 1-5 until homogeneous.

[0651] B: Mix and dissolve components 6-7 and component 9.

[0652] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0653] D: Add component 8 to the mixture obtained in step C above and mix until homogeneous.

[0654] E: After degassing the mixture obtained in step D above, it is filled into a container to obtain a water-in-oil cream.

[0655] The water-in-oil cream obtained as described above is confirmed to be a water-in-oil cream with a fine texture, easy to spread, non-sticky and non-greasy, and excellent stability that does not change with temperature or time.

[0656] [Table 9]

[0657]

[0658] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 65-75% squalane and 25-35% (PEG-10 / lauryl polydimethylsiloxane) cross-linked polymer and (PEG-15 / lauryl polydimethylsiloxane) cross-linked polymer.

[0659] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0660] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (Vinyl polydimethylsiloxane / polymethylsiloxane silsesquioxane) crosslinked polymer.

[0661] (Manufacturing method)

[0662] A: Mix components 1-6.

[0663] B: Mix and dissolve components 7-10 and component 12.

[0664] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0665] D: Add component 11 to the mixture obtained in step C above and mix until homogeneous.

[0666] E: After degassing the mixture obtained in step D above, it is filled into a container to obtain a water-in-oil cream.

[0667] The water-in-oil cream of the present invention obtained as described above has been confirmed to have a fine texture, spread easily, be non-sticky and non-greasy, and exhibit excellent stability without changing due to temperature or time.

[0668] [Table 10]

[0669]

[0670] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-9 polydimethylsiloxyethyl polydimethylsiloxane

[0671] (Note 2) Scutellaria baicalensis extract: extracted with 50% BG water.

[0672] (Note 3) Extract of gentian: Extracted with 20% ethanol and water.

[0673] (Manufacturing method)

[0674] A: Mix components 1-8.

[0675] B: Mix components 9-14 and dissolve them.

[0676] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0677] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain a water-in-oil cream.

[0678] The water-in-oil cream obtained as described above has a fine texture, is not only non-sticky and easy to spread, but also has excellent adhesion and long-lasting makeup. Furthermore, the water-in-oil cream has been confirmed to be stable and unaffected by temperature changes or time.

[0679] [Table 11]

[0680]

[0681] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 65-75% triglyceride (ethylhexanoate) and 25-35% vinyl polydimethylsiloxane / lauryl polydimethylsiloxane cross-linked polymer.

[0682] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Methylcellulose

[0683] (Note 3) Manufactured by SEPPIC: SEPPICEL 305.

[0684] (Manufacturing method)

[0685] A: Mix components 1-3.

[0686] B: Mix components 4-10.

[0687] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0688] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oil-in-water cream.

[0689] The water-in-oil cream of the present invention obtained as described above has been confirmed to have a fine texture, spread easily, be non-sticky and non-greasy, and exhibit excellent stability without changing due to temperature or time.

[0690] [Table 12]

[0691]

[0692] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 75-85% diphenylsiloxyphenyl polytrimethylsiloxane and 15-25% polydimethylsiloxane / (PEG-10 / 15) cross-linked polymer.

[0693] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 80-90% diphenylsiloxyphenyl polytrimethylsiloxane and 10-20% (polydimethylsiloxane / phenyl vinyl polydimethylsiloxane) crosslinked polymer.

[0694] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Cetyl PEG / PPG-10 / 1 polydimethylsiloxane

[0695] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0696] (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Octyl polymethylsiloxane

[0697] (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Ethyl polytrimethylsiloxane.

[0698] (Manufacturing method)

[0699] A: Mix components 1-11 until homogeneous.

[0700] B: Mix components 12-15 until homogeneous.

[0701] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0702] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain a water-in-oil sunscreen emulsion.

[0703] As is known, the sunscreen lotion of the present invention obtained as described above has excellent silky smoothness when applied, presents a refined finish that suppresses shine, and has good makeup retention, which is excellent.

[0704] [Table 13]

[0705]

[0706] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 75-85% diphenylsiloxyphenyl polytrimethylsiloxane and 15-25% polydimethylsiloxane / (PEG-10 / 15) cross-linked polymer.

[0707] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0708] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 60% isododecane and 40% (acrylate / polydimethylsiloxane) copolymer.

[0709] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxyoctylsilane.

[0710] (Manufacturing method)

[0711] A: Add component 3 to part of component 2 and mix until homogeneous, then add component 10 and disperse using a bead mill.

[0712] B: Mix the remaining component 2 with components 1, 4-9 until homogeneous.

[0713] C: Mix and dissolve components 11-13 and component 15.

[0714] D: Add the mixture obtained in step C above to the mixture obtained in step B above, and mix until homogeneous.

[0715] E: Add the mixture obtained in step A above to the mixture obtained in step D above, and mix until homogeneous.

[0716] F: Add component 14 to the mixture obtained in step E above and mix until homogeneous.

[0717] G: After degassing the mixture obtained in step F above, it is filled into a container to obtain a water-in-oil sunscreen.

[0718] The oil-in-water sunscreen of the present invention, as described above, is non-sticky, spreads easily, has excellent adhesion, repairs skin texture, and has excellent makeup-holding properties. Furthermore, it has been confirmed to be highly stable even with temperature and time variations.

[0719] [Table 14]

[0720]

[0721] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl PEG-9 polydimethylsiloxyethyl polydimethylsiloxane

[0722] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0723] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate.

[0724] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (Vinyl polydimethylsiloxane / polymethylsiloxane silsesquioxane) crosslinked polymer.

[0725] (Manufacturing method)

[0726] A: Add component 2 to component 1 and mix until homogeneous, then add component 8-9 and disperse using a bead mill.

[0727] B: Mix components 3-7 until homogeneous.

[0728] C: Mix and dissolve components 10-12 and component 14.

[0729] D: Add the mixture obtained in step C above to the mixture obtained in step B above, and mix until homogeneous.

[0730] E: Add the mixture obtained in step A above to the mixture obtained in step D above, and mix until homogeneous.

[0731] F: Add component 13 to the mixture obtained in step E above and mix until homogeneous.

[0732] G: After degassing the mixture obtained in step F above, it is filled into a container to obtain a water-in-oil sunscreen emulsion.

[0733] The sunscreen lotion obtained as described above has a fine texture, spreads easily, and is non-sticky. Furthermore, it has been confirmed that due to its excellent staying power, it maintains its UV protection effect continuously and does not change with temperature variations or time, demonstrating excellent stability.

[0734] [Table 15]

[0735]

[0736] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / polyglycerol-3) cross-linked polymer.

[0737] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / vinyl polydimethylsiloxane) crosslinked polymer.

[0738] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0739] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 50% polydimethylsiloxane (2cs) + 50% trimethylsiloxysilicate.

[0740] (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0741] (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polymethylsiloxane.

[0742] (Manufacturing method)

[0743] A: Mix components 1-7.

[0744] B: Mix components 8-10 and process them using a roller mill.

[0745] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0746] D: Components 11-13 and Component 15 are mixed and dissolved.

[0747] E: Add the mixture obtained in step D above to the mixture obtained in step C above, and mix until homogeneous.

[0748] F: Add component 14 to the mixture obtained in step E above and mix until homogeneous.

[0749] G: After degassing the mixture obtained in step F above, it is filled into a container to obtain a water-in-oil foundation cream.

[0750] The foundation cream obtained as described above is an oil-in-water type foundation cream that has excellent silky smoothness and moisturizing properties when applied, is non-sticky and easy to spread, has excellent adhesion, good setting properties, and a natural, refined finish that inhibits shine.

[0751] [Table 16]

[0752]

[0753] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-9 polydimethylsiloxyethyl polydimethylsiloxane

[0754] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (acrylate / ethylhexyl acrylate / polydimethylsiloxane methacrylate) copolymer.

[0755] (Manufacturing method)

[0756] A: Mix components 1-5.

[0757] B: Mix components 6-8 and process them using a roller mill.

[0758] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0759] D: Mix and dissolve components 9-10 and component 12.

[0760] E: Add the mixture obtained in step D above to the mixture obtained in step C above, and mix until homogeneous.

[0761] F: Add component 11 to the mixture obtained in step E above and mix until homogeneous.

[0762] G: After degassing the mixture obtained in step F above, it is filled into a container to obtain a water-in-oil foundation cream.

[0763] The foundation cream obtained as described above was confirmed to have a fine texture, spread easily, be non-sticky and non-greasy, have good staying power, not change with temperature or time, and have excellent stability.

[0764] [Table 17]

[0765]

[0766] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0767] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate.

[0768] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane.

[0769] (Manufacturing method)

[0770] A: Mix components 1-7.

[0771] B: Mix components 8-10 and process them using a roller mill.

[0772] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0773] D: Mix and dissolve components 11-13.

[0774] E: Add the mixture obtained in step D above to the mixture obtained in step C above, and mix until homogeneous.

[0775] F: After degassing the mixture obtained in step E above, it is filled into a container to obtain a water-in-oil foundation.

[0776] The foundation obtained as described above has been confirmed to have low viscosity, fine texture, easy application, non-stickiness and non-greasyness, and has the effect of skin contour repair, good makeup retention, does not change with temperature changes or time, and has excellent stability.

[0777] [Table 18]

[0778]

[0779] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenyl polydimethylsiloxane

[0780] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-10 polydimethylsiloxane

[0781] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (methyl / phenyl) polysilsesquioxane

[0782] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane.

[0783] (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Hydrogen-modified dimethylsiloxane.

[0784] (Manufacturing method)

[0785] A: Mix components 1-7.

[0786] B: Mix components 8-11 and process them using a roller mill.

[0787] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0788] D: Mix components 12-14 and dissolve them.

[0789] E: Add the mixture obtained in step D above to the mixture obtained in step C above, and mix until homogeneous.

[0790] F: After degassing the mixture obtained in step E above, it is filled into a container to obtain a water-in-oil foundation.

[0791] The foundation obtained as described above is confirmed to be non-sticky, easy to spread, has excellent adhesion, and excellent staying power. Furthermore, it is known that the oil-in-water foundation does not change with temperature or time, exhibiting excellent stability.

[0792] [Table 19]

[0793]

[0794] (Manufacturing method)

[0795] A: Heat components 1-7 to 80°C and mix until homogeneous.

[0796] B: Heat components 8-10 to 80°C, add component 11, and mix until homogeneous.

[0797] C: Add the mixture obtained in the heated step B above to the mixture obtained in the heated step A above, and mix until homogeneous.

[0798] D: Mix components 12-13 and process them using a roller mill.

[0799] E: After cooling the mixture obtained in step C above to room temperature, add component 14-15 and mix until homogeneous.

[0800] F: Add the mixture obtained in step D above to the mixture obtained in step E above, and mix until homogeneous.

[0801] G: After degassing the mixture obtained in step F above, it is filled into a container to obtain an oil-in-water base cream.

[0802] The base cream obtained as described above is an oil-in-water type base cream that has excellent moisturizing properties, is non-sticky, spreads easily, has excellent adhesion, good makeup setting properties, and has a matte finish that suppresses shine.

[0803] [Table 20]

[0804]

[0805] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 75-85% isododecane and 15-25% (vinyl polydimethylsiloxane / lauryl polydimethylsiloxane) crosslinked polymer.

[0806] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0807] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: 30% tris(trimethylsiloxy)silylpropylcarbamoyl pullulan + 70% isododecane solution

[0808] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (acrylate / ethylhexyl acrylate / polydimethylsiloxane methacrylate) copolymer.

[0809] (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Hydrogen-modified polydimethylsiloxane

[0810] (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxyoctylsilane.

[0811] (Manufacturing method)

[0812] A: Mix ingredients 1-9 until homogeneous.

[0813] B: Mix components 10-14 until homogeneous, and process with a roller mill.

[0814] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0815] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oily foundation cream.

[0816] The foundation cream obtained as described above is a light and smooth foundation cream with good setting properties for the skin, presenting a moisturizing finish. In addition, it can produce a makeup film that inhibits shine and has a firming effect, and it has good staying power, making it an excellent oil-based foundation cream.

[0817] [Table 21]

[0818]

[0819] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 50% polydimethylsiloxane (2cs) + 50% trimethylsiloxysilicate.

[0820] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 75-85% polydimethylsiloxane and 15-25% (lauryl polydimethylsiloxyethyl polydimethylsiloxane / bisvinyl polydimethylsiloxane) crosslinking polymer.

[0821] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0822] (Note 4) KF-9909 Processing Coloring Inorganic Pigment manufactured by Shin-Etsu Chemical Co., Ltd., Japan. W: White; R: Red; Y: Yellow; B: Black.

[0823] (Manufacturing method)

[0824] A: Mix a portion of component 1 with components 2-9 until homogeneous.

[0825] B: Mix the remaining portion of component 1 into components 10-14 and process it using a roller mill.

[0826] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0827] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oily mousse foundation.

[0828] The mousse foundation obtained as described above is an oil-based mousse foundation with a souffle-like texture that is easy to apply, spreads smoothly, and has a non-greasy or powdery feel. Furthermore, it is confirmed to have good water resistance, water repellency, and sweat resistance, as well as good staying power, resistance to makeup fading, and excellent stability, unaffected by temperature changes or time.

[0829] [Table 22]

[0830]

[0831] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane

[0832] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polymethylsilsesquioxane

[0833] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane.

[0834] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Hydrogen-modified polydimethylsiloxane

[0835] (Note 5) KF-9909 Processing Coloring Inorganic Pigment manufactured by Shin-Etsu Chemical Co., Ltd., Japan. W: White; R: Red; Y: Yellow; B: Black.

[0836] (Manufacturing method)

[0837] A: Heat components 1-9 to dissolve them.

[0838] B: Mix components 12-15 until homogeneous, and process with a roller mill.

[0839] C: Add 10-11 of the mixture and ingredients obtained in step B above to the mixture obtained in the heated step A above, and mix until homogeneous.

[0840] D: By degassing the mixture obtained in step C above under a heated state, filling it into a container and cooling it to room temperature, an oily solid foundation is obtained.

[0841] The oil-based solid foundation obtained as described above is easy to spread, has good setting properties on the skin, presents a moisturizing finish, and also provides a makeup film that inhibits shine and has a firming effect. It is an excellent oil-based solid foundation.

[0842] [Table 23]

[0843]

[0844] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polysiloxane-1 cross-linked polymer

[0845] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxysilyl ethyl polydimethylsiloxane ethylhexyl polydimethylsiloxane

[0846] (Note 3) KF-9909 Processing Coloring Inorganic Pigment manufactured by Shin-Etsu Chemical Industry Co., Ltd., Japan, W: White, R: Red, Y: Yellow, B: Black

[0847] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Octyl polymethylsiloxane.

[0848] (Manufacturing method)

[0849] A: Use a Henschel mixer to mix components 1-7 until homogeneous.

[0850] B: Mix components 8-11 until homogeneous.

[0851] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous using a Henschel mixer.

[0852] D: After sieving the mixture obtained in step C above, it is stamped onto a metal tray using a mold to obtain a powder foundation.

[0853] As can be seen, the powder foundation of the present invention obtained as described above has excellent silkiness when applied, is non-sticky, spreads gently, has excellent adhesion, good makeup setting properties, presents a refined finish that suppresses shine, does not bleed, and has good staying power, which is very excellent.

[0854] [Table 24]

[0855]

[0856] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (Vinyl polydimethylsiloxane / polymethylsiloxane silsesquioxane) crosslinked polymer

[0857] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (Diphenyl polydimethylsiloxane / vinyl diphenyl polydimethylsiloxane / silsesquioxane) crosslinked polymer

[0858] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Hydrogen-modified dimethylsiloxane.

[0859] (Manufacturing method)

[0860] A: Use a Henschel mixer to mix components 1-9 until homogeneous.

[0861] B: Mix components 10-11 until homogeneous and dissolve them.

[0862] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous using a Henschel mixer.

[0863] D: After sieving the mixture obtained in step C above, it is filled into a container to obtain loose powder.

[0864] As can be seen, the loose powder obtained as described above has excellent silky smoothness when applied, presents a refined finish that suppresses shine, and has good staying power, making it very excellent.

[0865] [Table 25]

[0866]

[0867] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / vinyl polydimethylsiloxane) crosslinked polymer.

[0868] (Note 2) KF-9909 Processed Coloring Inorganic Pigment manufactured by Shin-Etsu Chemical Co., Ltd., Japan. W: White; R: Red; Y: Yellow; B: Black

[0869] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxysilyl ethyl polydimethylsiloxane.

[0870] (Manufacturing method)

[0871] A: Mix components 1-5, heat to 80℃ and mix until homogeneous.

[0872] B: Use a Henschel mixer to mix components 6-10 until homogeneous.

[0873] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix at 80°C until homogeneous.

[0874] D: An oily blush is obtained by degassing the mixture obtained in step C above under a heated state, filling it into a container, and cooling it to room temperature.

[0875] The blush obtained as described above is an oil-based blush with good sponge-like applicability, easy to spread, and without a greasy or powdery feel. In addition, it has been confirmed that it has good water resistance, water repellency, and sweat resistance, and also has good staying power, does not easily smudge, and does not change with temperature or time, exhibiting excellent stability.

[0876] [Table 26]

[0877]

[0878] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polysiloxane-22

[0879] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl PEG-9 polydimethylsiloxyethyl polydimethylsiloxane.

[0880] (Manufacturing method)

[0881] A: Use a Henschel mixer to mix components 1-9 until homogeneous.

[0882] B: Mix components 10-13 until homogeneous.

[0883] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous using a Henschel mixer.

[0884] D: After sieving the mixture obtained in step C above, it is stamped onto a metal tray using a mold to obtain loose powder blush.

[0885] As can be seen, the loose powder blush obtained as described above has excellent silkiness when applied, is not sticky, spreads easily, has excellent adhesion, good setting properties, and presents a refined finish that suppresses shine. It does not bleed and has good staying power, which is excellent.

[0886] [Table 27]

[0887]

[0888] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-9 polydimethylsiloxyethyl polydimethylsiloxane.

[0889] (Manufacturing method)

[0890] A: Mix components 1-4 until homogeneous.

[0891] B: Use a Henschel mixer to mix components 5-6 until homogeneous.

[0892] C: Mix components 7-9 and component 11 until homogeneous and dissolve.

[0893] D: Add the mixture obtained in step C above to the mixture obtained in step A above, and mix until homogeneous.

[0894] E: Add component 10 to the mixture obtained in step D above and mix until homogeneous.

[0895] F: After degassing the mixture obtained in step E above, it is filled into a container to obtain a water-in-oil eyeshadow cream.

[0896] The eyeshadow cream obtained as described above is an eyeshadow cream with a light, easy-to-apply, non-greasy and non-powdery feel. In addition, it can be confirmed that it has good water resistance, water repellency and sweat resistance, and also has good staying power, does not easily smudge, and does not change with temperature changes or time, and has excellent stability.

[0897] [Table 28]

[0898]

[0899] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / vinyl polydimethylsiloxane) crosslinked polymer.

[0900] (Manufacturing method)

[0901] A: Mix components 1-5, heat to 90℃ and mix until homogeneous.

[0902] B: Add components 6 to 11 to the mixture obtained in step A above, and mix at 90°C until homogeneous.

[0903] C: Oily eyeshadow is obtained by degassing the mixture obtained in step B above under a heated state, filling it into a container and cooling it to room temperature.

[0904] The eyeshadow obtained as described above has a gel-like texture, good applicability, spreads easily, and has a non-greasy or powdery feel. Furthermore, it is confirmed to have good water resistance, water repellency, and sweat resistance, is not prone to smudging, and exhibits excellent stability regardless of temperature changes or time.

[0905] [Table 29]

[0906]

[0907] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Hydrogen-modified polydimethylsiloxane

[0908] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (acrylate / stearyl acrylate / polydimethylsiloxane methacrylate) copolymer

[0909] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenylsiloxyphenyl polytrimethylsiloxane.

[0910] (Manufacturing method)

[0911] A: Use a Henschel mixer to mix components 1-10 until homogeneous.

[0912] B: Mix components 11-13 until homogeneous.

[0913] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous using a Henschel mixer.

[0914] D: After sieving the mixture obtained in step C above, it is stamped onto a metal tray using a mold to obtain eyeshadow powder.

[0915] As can be seen, the eyeshadow powder obtained as described above has excellent silkiness when applied, is not sticky, spreads easily, has excellent adhesion, good setting properties, and presents a refined finish that suppresses shine. It does not bleed and has good staying power, which is excellent.

[0916] [Table 30]

[0917]

[0918] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (acrylate / stearyl acrylate / polydimethylsiloxane methacrylate) copolymer

[0919] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Diphenyl polydimethylsiloxane

[0920] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxyoctylsilane.

[0921] (Manufacturing method)

[0922] A: Mix components 1-6 and a portion of component 7, heat to 90°C, and mix until homogeneous.

[0923] B: Mix components 8-9 and the remaining portion of component 7, and process them using a roller mill.

[0924] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix at 90°C until homogeneous.

[0925] D: Add component 10-11 to the mixture obtained in step C above, and mix at 90°C until homogeneous.

[0926] E: By degassing the mixture obtained in step D above while heating it, the mixture is then filled into a container to obtain a stick-shaped lipstick.

[0927] The stick lipstick obtained as described above is easy to spread, non-greasy and powdery, has good water resistance and water repellency, good staying power, and excellent stability.

[0928] [Table 31]

[0929]

[0930] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 65-75% triglyceride (ethylhexanoate) and 25-35% (vinyl polydimethylsiloxane / lauryl polydimethylsiloxane) cross-linked polymer.

[0931] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0932] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate.

[0933] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane.

[0934] (Manufacturing method)

[0935] A: Mix components 1-7, heat to 90℃, and mix until homogeneous.

[0936] B: Mix components 8-10 and process them using a roller mill.

[0937] C: Mix components 11-12 until homogeneous and dissolve them.

[0938] D: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix at 90°C until homogeneous.

[0939] E: Add the mixture obtained in step C above to the mixture obtained in step D above, and mix at 90°C until homogeneous.

[0940] F: After cooling the mixture obtained in step E above to room temperature and degassing it, it is filled into a container to obtain a water-in-oil cream lipstick.

[0941] The cream lipstick obtained by the present invention has excellent spreadability and silkiness when applied, is non-sticky, has excellent adhesion, good makeup setting, presents a beautiful decorative effect while suppressing unnatural shine, does not bleed, color shift, or fade, has good staying power, and does not cause dryness or chapped lips.

[0942] [Table 32]

[0943]

[0944] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 65-75% squalane and 25-35% (vinyl polydimethylsiloxane / lauryl polydimethylsiloxane) crosslinked polymer.

[0945] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 60% polydimethylsiloxane (2cs) + 40% (acrylate / polydimethylsiloxane) cross-linked polymer.

[0946] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-3 polydimethylsiloxane

[0947] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Polymethylsiloxane.

[0948] (Manufacturing method)

[0949] A: Mix components 1-6 until homogeneous.

[0950] B: Mix components 7-11 until homogeneous, and process with a roller mill.

[0951] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0952] D: Add component 12 to the mixture obtained in step C above and mix until homogeneous.

[0953] E: The mixture obtained in step E above is degassed and then filled into a container to obtain lip gloss.

[0954] The lip gloss obtained as described above has excellent spreadability and silkiness when applied, is non-sticky, has excellent adhesion, good setting power, and presents a beautiful and refined look while suppressing unnatural shine. It does not bleed, transfer, or fade, and has good staying power. Furthermore, it does not cause dryness or chapped lips.

[0955] [Table 33]

[0956]

[0957] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-9 polydimethylsiloxyethyl polydimethylsiloxane

[0958] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 70% isododecane and 30% (norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer.

[0959] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl polyglycerol-3-dimethylsiloxyethyl polydimethylsiloxane

[0960] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: KF-9909 Processing Coloring Inorganic Pigment, W: White; B: Black.

[0961] (Manufacturing method)

[0962] A: Heat and dissolve components 1-8.

[0963] B: Mix components 10-12 until homogeneous, and process with a roller mill.

[0964] C: Add the mixture and component 9 obtained in step B above to the mixture obtained in the heated step A above, and mix until homogeneous.

[0965] D: After degassing the mixture obtained in step C above and cooling it to room temperature, it is filled into a container to obtain an oily mascara.

[0966] It is known that the oil-based mascara obtained as described above has excellent silkiness when applied, is not sticky, spreads easily and has excellent adhesion, has good setting properties, presents a refined finish that suppresses shine, does not bleed and has good staying power, which is very good.

[0967] [Table 34]

[0968]

[0969] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-10 polydimethylsiloxane

[0970] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 50% cyclopentasiloxane and 50% trimethylsiloxysilicate.

[0971] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Hydrogen-modified dimethylsiloxane.

[0972] (Manufacturing method)

[0973] A: Mix ingredients 1-4, then add ingredients 5 and 6, and mix until homogeneous.

[0974] B: Mix components 7-9 until homogeneous and dissolve them.

[0975] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0976] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oil-in-water eyeliner.

[0977] The eyeliner described above is easy to apply and blend, has a cooling and refreshing feel, and is non-sticky. Furthermore, it has been confirmed that it does not change with temperature or time, exhibits excellent usability and stability, and demonstrates excellent water and sweat resistance, resulting in very good staying power.

[0978] [Table 35]

[0979]

[0980] Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-10 polydimethylsiloxane

[0981] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Lauryl PEG-9 polydimethylsiloxyethyl polydimethylsiloxane

[0982] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 70% cyclopentasiloxane and 30% (acrylate / polydimethylsiloxane) copolymer.

[0983] (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: KF-9909 Processing Coloring Inorganic Pigment, B: Black.

[0984] (Manufacturing method)

[0985] A: Mix ingredients 1-6, then add ingredients 7 and 8 and mix until homogeneous.

[0986] B: Mix components 9-11 until homogeneous and dissolve them.

[0987] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0988] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oil-in-water eyeliner.

[0989] The water-in-oil eyeliner obtained as described above is easy to apply, non-greasy and powdery, has good water resistance, water repellency and sweat resistance, and also has good staying power and is not easy to smudge. In addition, the water-in-oil eyeliner has also been confirmed to be unaffected by temperature changes and time, and has excellent stability.

[0990] [Table 36]

[0991]

[0992] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Triethoxyoctylsilane.

[0993] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 40% isododecane and 60% trimethylsiloxysilicate.

[0994] (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: PEG-10 polydimethylsiloxane.

[0995] (Manufacturing method)

[0996] A: Mix ingredients 1, 2, and 5-9, then add ingredients 3 and 4 and mix until homogeneous.

[0997] B: Mix components 10-13.

[0998] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[0999] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oil-in-water eyeliner.

[1000] The eyeliner described above has been confirmed to be easy to apply and blend, has a cooling and refreshing feel, is non-sticky, exhibits excellent water and sweat resistance, and has very good staying power. Furthermore, it does not change with temperature variations or over time.

[1001] [Table 37]

[1002]

[1003] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / (PEG-10 / 15)) crosslinked polymer.

[1004] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (Vinyl polydimethylsiloxane / polymethylsiloxane silsesquioxane) crosslinked polymer.

[1005] (Manufacturing method)

[1006] A: Mix components 1-5 until homogeneous.

[1007] B: Mix components 6-10 until homogeneous and dissolve them.

[1008] C: Add the mixture obtained in step B above to the mixture obtained in step A above, and mix until homogeneous.

[1009] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain a water-in-oil antiperspirant.

[1010] The antiperspirant obtained as described above is easy to spread and non-sticky and non-greasy, and it does not change due to temperature or time. It is an antiperspirant with excellent usability and stability.

[1011] [Table 38]

[1012]

[1013] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 70-80% polydimethylsiloxane and 20-30% (polydimethylsiloxane / (PEG-10 / 15)) crosslinked polymer.

[1014] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a mixture of 90-96% cyclopentasiloxane and 4-10% (polydimethylsiloxane / vinyl polydimethylsiloxane) crosslinked polymer.

[1015] (Manufacturing method)

[1016] A: Mix components 1-4 until homogeneous.

[1017] B: Add components 5-7 to the mixture obtained in step A above, and mix until homogeneous.

[1018] C: After degassing the mixture obtained in step B above, it is filled into a container to obtain a roll-on antiperspirant cosmetic.

[1019] The roll-on antiperspirant obtained as described above is easy to spread and non-sticky and non-greasy, and it does not change due to temperature or time. It is a roll-on antiperspirant with excellent usability and stability.

[1020] [Table 39]

[1021]

[1022] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Ethyl polytrimethylsiloxane

[1023] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: (90-96% cyclopentasiloxane + 4-10% (polydimethylsiloxane / vinyl polydimethylsiloxane) cross-linked polymer).

[1024] (Manufacturing method)

[1025] A: Heat components 1-6 and mix until homogeneous.

[1026] B: Add components 7-9 to the mixture obtained in step A above, and mix until homogeneous.

[1027] C: Add component 10 to the mixture obtained in step B above and mix until homogeneous.

[1028] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain an oily antiperspirant.

[1029] The antiperspirant obtained as described above is an oil-based antiperspirant that spreads very smoothly and silkily without excessive dryness or stickiness, and has excellent long-lasting deodorizing effect.

[1030] [Table 40]

[1031]

[1032] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: a solution of 60% methyl polytrimethylsiloxane and 40% (acrylate / polydimethylsiloxane) copolymer.

[1033] (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd., Japan: Methyl polytrimethylsiloxane.

[1034] (Manufacturing method)

[1035] A: Mix components 7-9, and add components 4-6 to the above mixture and mix until homogeneous.

[1036] B: Add components 1 to 3 to the mixture obtained in step A above, and mix until homogeneous.

[1037] C: Add component 10 to the mixture obtained in step B above and mix until homogeneous.

[1038] D: After degassing the mixture obtained in step C above, it is filled into a container to obtain nail polish.

[1039] The nail polish obtained as described above has been confirmed to be easy to spread, visually silky, water-resistant, oil-resistant, and has good staying power. Furthermore, it does not cause pressure on the nails, does not cause yellowing, and the makeup film does not change with temperature or time, exhibiting excellent stability. Industrial applicability

[1040] The elastomeric spherical particles and elastomeric composite particles (elastomeric spherical particles coated with polyorganosilsesquioxane or silica) in this invention are expected to be particularly useful for cosmetics and the like, based on their characteristic structural composition.

[1041] In addition, since the powder and particle skeleton contain degradable polyester structures (especially poly-ε-caprolactone) and polyether structures, it is expected to exhibit and impart high biodegradability.

[1042] Therefore, the cosmetic containing elastomeric spherical particles and / or elastomeric composite particles of the present invention can be expected to be used and utilized as a material that reduces environmental burden.

Claims

1. A cosmetic material containing particles of at least one of (i) and (ii) below, wherein, (i) Elastomer spherical particles, which are cross-linked particles of copolymers with polyester and polyether structures, with a volume average particle size of 1.0~100 μm; (ii) Elastomer composite particles having polyorganosilsesquioxane or silica on the surface of the (i) elastomeric spherical particles.

2. The cosmetic material according to claim 1, wherein, The copolymer is a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule.

3. The cosmetic material according to claim 2, wherein, The copolymer is a polyester-polyether copolymer represented by the following general formula (1) or general formula (2). [Chemical Formula 1] In general formula (1), R 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following formulas (3a), (3b), or (3c) represents an organic group containing a free radical polymerizable functional group, where k is a number that is 1 ≤ k ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and n is a number that is 1 ≤ n ≤ 100. In general formula (2), R 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the following formulas (4a) and (4b) represents an organic group containing a free radical polymerizable functional group, where p is a number that is 1 ≤ p ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and q is a number that is 1 ≤ q ≤ 100. [Chemical Formula 2] In general formulas (3a), (3b), (3c), (4a), and (4b), R 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be used independently to represent a hydrocarbon group consisting of 1 to 3 hydrogen atoms or carbon atoms.

4. The cosmetic material according to claim 2, wherein, The copolymer is a polyester-polyether copolymer represented by the following general formula (5). [Chemical Formula 3] In general formula (5), R 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Let each of the following independently represent an organic group containing a free radical polymerizable functional group, represented by general formula (3a), general formula (3b), or general formula (3c), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and r is a number 1 ≤ r ≤ 100. [Chemical Formula 4] In general formulas (3a), (3b), and (3c), R 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be used independently to represent a hydrocarbon group consisting of 1 to 3 hydrogen atoms or carbon atoms.

5. The cosmetic material according to claim 1, wherein, The elastomeric spherical particles are elastomeric spherical particles having a rubber hardness of 10 to 80 as measured by a type A hardness tester as specified in JIS K 6253.

6. The cosmetic material according to claim 1, wherein, The cosmetic material mentioned is a skincare cosmetic material.

7. The cosmetic material according to claim 1, wherein, The cosmetic material mentioned is a color cosmetic material.

8. The cosmetic material according to claim 1, wherein, The cosmetic material mentioned is a sunscreen cosmetic material.

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