Solid particles of silicone-functional copolymer, process for the production thereof and cosmetic

Abstract

There is provided a solid particle consisting essentially of a silicone-functional copolymer polymerized from a monomer composition, the monomer composition consists essentially of (A) one or more unsaturated polymerizable monomers having at least one silicone functional group and one polymerizable group in the molecule and (B) one or more unsaturated polymerizable monomers that do not contain or contain one silicon atom and have one polymerizable group in the molecule, wherein the mass ratio of the monomers (A) and (B) in the monomer composition is in the range of 35: 65 to 70: 30, and the length of the solid primary particles in three directions is in the range of 0.1 [mu] m to 5,000 [mu] m. Also provided are a method for producing the solid particles, the use of the solid particles as a cosmetic ingredient, a cosmetic composition comprising the solid particles, and a method for preparing the same.

Description

Technical Field

[0001] The present invention relates to solid particles of a silicone-functional copolymer that have excellent solubility in a cosmetic liquid medium and can be used as a cosmetic ingredient. The present invention also relates to a method for manufacturing the same and a cosmetic composition containing the solid particles. Background Art

[0002] Attempts have been made to improve the water resistance and sebum resistance of cosmetic materials in order to (lastingly) improve the cosmetic retention of cosmetic materials, particularly makeup cosmetic materials. For the purpose of improving the water resistance of cosmetic materials and the like, it is conventionally known to use a polymer containing an organopolysiloxane in a cosmetic material (for example, see Patent Document 1). However, commercially available silicone acrylates can be obtained in the form of a solution or a dispersion. Therefore, when used in each downstream formulation together with various other additives, such a product form containing additives and / or solvents limits the carrier or reduces the degree of freedom of choice and the diversity of formulation design. For example, when a silicone acrylate has isododecane as a solvent, the resulting cosmetic formulation and / or commercial products such as lipsticks also contain isododecane. Lipsticks formulated with isododecane give an unpleasant feeling to users because isododecane acts as a plasticizer.

[0003] In addition, such carrier fluids have a low flash point, so careful transportation and handling are required.

[0004] Known methods for overcoming these drawbacks have been found in the prior art.

[0005] As an exemplary method, a commercially available silicone acrylate isododecane solution is evaporated and pulverized to be crushed by hand to prepare silicone acrylate particles. Such solids can be dispersed or dissolved in natural cosmetic oils (see Patent Document 2). However, achieving manual crushing requires arduous work, and the method for achieving such manual crushing of solid silicone acrylate cannot be applied to large-scale preparation. In addition, the pulverized silicone acrylate solids require high-shear mixing, a long time, and heating to be completely dissolved. Therefore, only solution-type products are available on the market. Attempts with a ball mill are known (see Patent Document 1). In the experiment, the silicone acrylate used had a low glass transition temperature and was therefore soft. As a result, aggregation and / or accumulation was caused by a share exotherm during grinding (Comparative Example 3). As a result, the obtained solid was not easily dissolved in cosmetic oils. In addition, the low silicone portion in the polymer resulted in low oil repellency that was not allowed for cosmetic applications. For those prior arts, no appropriate characteristics of using solid silicone acrylate were described. Users of solid silicone acrylate desire easily soluble solid silicone acrylate for large-scale preparation. Then, the inventors studied to provide appropriate physical properties of solid silicone acrylate that satisfy both large-scale preparation and easy solubility.

[0006] On the other hand, powdering treatment has also been carried out. First, a silicone acrylate emulsion is prepared. Then, powders are obtained by a spray dryer (see Patent Document 3). However, the acryloyl silicone used as a starting material has two or more (meth)acrylic acid groups in one monomer, which enables crosslinking. Crosslinked silicone acrylates have less aggregation because they are no longer thermoplastic polymers. Therefore, such polymers can be easily processed into fine powders even at high temperatures during drying. However, such powder polymers cannot be dissolved in any oil due to their thermosetting property.

[0007] [Prior Art Documents]

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication 2000-63225

[0009] Patent Document 2: US Unexamined Patent US20160374930

[0010] Patent Document 4: German Unexamined Patent DE102007058713 Summary of the Invention

[0011] Problems to be Solved by the Present Invention

[0012] In the field of silicone acrylate technology, readily soluble solid particles are not well-known. Only a few prior arts include elastic silicone acrylates containing crosslinking agents, but such elastic particles cannot be dissolved in cosmetic oils. Although an example was found in an existing patent (see Patent Document 3) where silicone acrylate powders composed of 20% silicone monomers were prepared via a ball milling mechanism, the inventors recognized that it was difficult to prepare particles from such materials due to their viscosity, and the particles needed to be heated at higher temperatures and subjected to high-shear mixing to completely dissolve in isododecane. Therefore, there is a need for a manufacturable molecular design and more easily soluble solid silicone acrylates.

[0013] In addition, currently provided silicone acrylates are mainly provided in the form of dispersions with an active level of 30% to 50%. Cosmetic manufacturers cannot freely choose their preferred carrier / solvent or carrier-solvent blend because pure silicone acrylates may be used in formulations. In most cases, these silicone acrylate copolymers can be obtained in the form of dispersions delivered from volatile silicone fluids or hydrocarbons. In the case of volatile hydrocarbons such as isododecane, the final dispersion is classified as a dangerous good (flammable), resulting in significantly higher transportation and storage costs. According to the prior art, the only way to obtain pure solvent-free silicone acrylates is to evaporate the carrier / solvent present in the dispersion, thereby forming a massive solid that is difficult to redisperse in the selected solvent requiring high heat and high shear.

[0014] For these reasons, there is a great need for silicone acrylate powders that are easy to disperse to increase the flexibility of carrier selection and the possibility of preparing new dosage forms; loose powders and pressed powders that are difficult to prepare using silicone acrylate dispersions.

[0015] Accordingly, an object of the present invention is to provide solid particles of a silicone-functional copolymer that are soluble in cosmetic solvents.

[0016] In addition, other objects of the present invention are to provide a method for manufacturing and uses of the solid particles, as well as a cosmetic composition containing the solid particles and a method for preparing the cosmetic composition.

[0017] Means for Solving the Problems

[0018] As a result of extensive research, the present inventors have found that solvent-soluble solid particles of a silicone-functional copolymer can be formed by polymerizing a specific monomer composition and following a specific solid method. The present invention is the product of this discovery.

[0019] One aspect of the present invention is a solid particle consisting essentially of a silicone-functional copolymer, the silicone-functional copolymer being polymerized from a monomer composition consisting essentially of (A) one or more unsaturated polymerizable monomers having at least one silicone functional group and one polymerizable group in the molecule and (B) one or more unsaturated polymerizable monomers having no silicon atom or having one silicon atom and one polymerizable group in the molecule, wherein the mass ratio of the monomers (A) and (B) in the monomer composition is in the range of 35:65 to 70:30, and the long dimension of the solid primary particles in three directions is in the range of 0.1 μm to 5,000 μm.

[0020] In some embodiments, the glass transition point (Tg) of the solid particles calculated by the FOX formula is preferably in the range of 35°C to 120°C.

[0021] In some embodiments, the unsaturated polymerizable monomer (A) is preferably at least one monomer selected from the group consisting of monomers represented by any one of the following formulas (A-1) to (A-7):

[0022] Formula (A-1):

[0023]

[0024] {In this formula, Y is a free-radically polymerizable organic group, R 1 is an alkyl or aryl group having 1 to 10 carbon atoms, and X 1 is a silylalkyl group represented by the following formula, where i = 1.

[0025]

[0026] (In this formula, R 1 is the same as above, R 2 is an alkylene group having 2 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, X i+1 is a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above-mentioned silylalkyl group, i is an integer from 1 to 10 representing the order of the above-mentioned silylalkyl group, and a i is an integer from 0 to 3.)}

[0027] Formula (A-2):

[0028]

[0029] (In this formula, Y and R 1 are the same as above, m is 0, 1 or 2, and n is a number from 0 to 200 representing the average degree of polymerization.)

[0030] Formula (A-3):

[0031]

[0032] Formula (A-4):

[0033]

[0034] Formula (A-5):

[0035]

[0036] where n = 0 to 120

[0037] Formula (A-6):

[0038]

[0039] Formula (A-7):

[0040]

[0041] In some embodiments, the shape of the solid particles is preferably selected from spherical particles, non-spherical particles, powders, pellets, beads, short fibers, short tubes, and comminuted powders.

[0042] In some embodiments, the shape of the solid primary particles is preferably spherical particles having a diameter in the range of 0.1 μm to 5,000 μm. If the particles are aggregated, agglomerated or flocculated, the diameter is in the range of 1 μm to 5,000 μm.

[0043] A second aspect of the present invention is a method for manufacturing the solid particles described in the first aspect, the manufacturing method comprising the following steps:

[0044] Step (I): A step of preparing a solution or dispersion of a silicone-functional copolymer from a monomer composition by a polymerization reaction, the monomer composition consisting essentially of (A) an unsaturated polymerizable monomer having at least one silicone functional group and one polymerizable group in the molecule and (B) an unsaturated polymerizable monomer having no silicon atom or having one silicon atom and one polymerizable group in the molecule, wherein the mass ratio of the monomers (A) and (B) in the monomer composition is in the range of 35:65 to 70:30; and

[0045] Step (II): A step of removing the carrier fluid of water or solvent from the solution or dispersion of the silicone-functional copolymer prepared in the above step (I).

[0046] In some embodiments, the method for manufacturing the above solid particles further comprises the following steps:

[0047] Step (III): After the above step (II), a step of forming the solid particles consisting essentially of the silicone-functional copolymer using at least one device selected from an extruder, a granulator, a mill, a crusher, a pulverizer, a grinder, an ingotizer and a drum flaker.

[0048] In some embodiments, the method for manufacturing the above solid particles further comprises the following steps:

[0049] Step (IV): A step of classifying the coarse solid particles consisting essentially of the silicone-functional copolymer using at least one device selected from a screen filter, a sieve, a perforated plate, a cyclone separator and a dynamic air classifier.

[0050] In some embodiments, the step (II) is a step of a spray drying method to obtain spherical particles of the silicone-functional copolymer by spraying the solution or dispersion to remove the carrier fluid of water or solvent from the solution or dispersion of the silicone-functional copolymer.

[0051] In some embodiments, the step (I) is a step of preparing a solution or dispersion of a silicone-functional copolymer by a liquid-phase polymerization reaction selected from at least one of solution polymerization, miniemulsion polymerization and emulsion polymerization.

[0052] A third aspect of the present invention is the use of the solid particles described in the first aspect as a cosmetic ingredient, particularly as a cosmetic ingredient having a film-forming function on human skin and / or hair.

[0053] A fourth aspect of the present invention is a cosmetic composition comprising the solid particles described in the first aspect.

[0054] A fifth aspect of the present invention is a method for preparing the cosmetic composition of the fourth aspect, the preparation method comprising the step of preparing a solution or dispersion of the solid particles described in the first aspect into at least one cosmetic liquid medium.

[0055] In some embodiments, the cosmetic liquid medium is at least one selected from alcohols, esters, silicone fluids, hydrocarbon oils, fatty acid ester oils, liquid UV protectants, bio-based liquids, biodegradable liquids, cosmetically acceptable solvents, and mixtures thereof.

[0056] Effects of the Present Invention

[0057] The present invention can provide solid particles of a silicone-functional copolymer that are soluble in cosmetic solvents, and also provides a method for manufacturing and uses of the solid particles, as well as a cosmetic composition comprising the solid particles and a method for preparing the cosmetic composition.

[0058] In particular, the solid particles of the present invention are solids of silicone-grafted polyacrylate, wherein 1) the weight % of the silicone monomer is in the range of 35 mass % - 70 mass %, 2) the long dimension of the primary particles is less than 5,000 μm in three directions, and 3) the calculated glass transition temperature is in the range of 35 °C - 120 °C, and it enables the silicone acrylate to be readily soluble in various oils and can be actually manufactured. Therefore, the solid particles have excellent solubility and easy handling properties as a cosmetic ingredient when formulated into a cosmetic composition. Detailed Description

[0059] Solvent-Soluble Solid Particles

[0060] In this specification, “(meth)acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth)acrylate”, “(meth)acryloxy” and “(meth)acrylamide” mean acrylate and methacrylate, acryloxy and methacryloxy, and acrylamide and methacrylamide, respectively. In the present invention, “cosmetic” and “cosmetic product” are used interchangeably. In the present invention, unless otherwise specified, the singular articles “a / an” and “the” include plural references. In the present invention, the terms “comprise”, “comprising”, “contain”, “containing”, “include”, “including” and their variants are open claim languages, i.e., additional elements are allowed.

[0061] In the present invention, there are provided solvent-soluble solid particles consisting essentially of a silicone-functional copolymer. Here, the term “silicone-functional” means a silane, silyl, siloxane or organocarbosiloxane functional group bonded to a polymerizable group (-Y or acrylic end group) in the monomer or the obtained copolymer. The term “consisting essentially of” and its variants are closed claim languages, i.e., exclusive additional elements. For example, “solvent-soluble solid particles consisting essentially of a silicone-functional copolymer” means that the solvent-soluble solid particles of the present invention do not contain materials that substantially affect the basic and novel properties of the present invention except for the silicone-functional copolymer.

[0062] Specifically, the solid particles of the present invention are solids of silicone-grafted polyacrylate, wherein the long dimension of the solid particles (primary particles) in three directions is less than 5,000 μm. If the long dimension of the solid particles is greater than 5,000 μm, its solubility becomes poor and it becomes insoluble in various cosmetic solvents. Preferably, the solid particles of the present invention have a small size and a large surface area, and the average value of the long dimension in its three directions is in the range of 1 μm to 4,000 μm, preferably 10 μm to 4,000 μm, more preferably 100 μm to 3,000 μm, and most preferably 200 μm to 2,000 μm.

[0063] In some preferred embodiments, the calculated glass transition temperature (Tg, calculated by the FOX formula, described in detail below) of the solid particles is in the range of 35 °C - 120 °C. If the Tg of the solid particles exceeds the range of 35 °C - 120 °C, its solubility may become poor and it may become insoluble in various cosmetic solvents. Preferably, the Tg of the solid particles is in the range of 40 °C - 100 °C, more preferably 40 °C - 80 °C.

[0064] To form the solid particles of the present invention, a silicone-functional copolymer is used. The silicone-functional copolymer is polymerized from a monomer composition that consists essentially of (A) an unsaturated polymerizable monomer having at least one silicone functional group and one polymerizable group in the molecule and (B) an unsaturated polymerizable monomer that contains no silicon atoms or contains one silicon atom and has one polymerizable group in the molecule. Here, the term "consisting essentially of" means that the monomer composition for forming the silicone-functional copolymer of the present invention does not contain materials that substantially affect the basic and novel properties of the present invention other than the monomers (A) and (B).

[0065] [Unsaturated Polymerizable Monomer (A)]

[0066] The unsaturated polymerizable monomer (A) is an unsaturated polymerizable monomer having at least one silicone functional group and one polymerizable group in the molecule, and is mainly used for the purpose of introducing a polysiloxane structure into the copolymer. In the present invention, considering the water / oil repellent properties and film-forming properties of the silicone-functional copolymer, the unsaturated polymerizable monomer (A) is preferably selected from the group consisting of: a carbosiloxane-dendrimer functional group derived from monomer (A-1), a macromonomer functional group derived from monomer (A-2), and other linear / branched / dendritic siloxane / carbosiloxane functional groups derived from monomers (A-3) to (A-7).

[0067] A preferred embodiment of the monomer (A) used in the present invention is the monomer (A1) represented by the following general formula (A-1).

[0068] Formula (A-1):

[0069]

[0070] In the general formula (A-1), Y is a free-radically polymerizable unsaturated organic group. Specific examples include organic groups containing a (meth)acryloyloxy group, organic groups containing a (meth)acrylamide group, organic groups containing a styryl group, or alkenyl groups having 2 to 10 carbon atoms, represented by the following general formulas.

[0071]

[0072] (In these formulas, R 4 and R 6 are hydrogen atoms or methyl groups, R 5 and R 8 are alkylene groups having 1 to 10 carbon atoms, R 7is an alkyl group having 1 to 10 carbon atoms, b is an integer of 0 to 4, and c is 0 or 1.) Examples of these free-radically polymerizable organic groups include acryloxymethyl group, 3-acryloxypropyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4-(2-propenyl)phenyl group, 3-(2-propenyl)phenyl group, 2-(4-vinylphenyl)ethyl group, 2-(3-vinylphenyl)ethyl group, vinyl group, allyl group, methallyl group, and 5-hexenyl group. R 1 is an alkyl group or an aryl group having 1 to 10 carbon atoms. The alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, or a cyclohexyl group. The aryl group may be a phenyl group or a naphthyl group. Among them, a methyl group or a phenyl group is preferred, and a methyl group is particularly preferred. X 1 is a silylalkyl group represented by the following formula, where i = 1.

[0073]

[0074] In this formula, R 2 is an alkylene group having 2 to 10 carbon atoms. Examples include straight-chain alkylene groups such as ethylene group, propylene group, butylene group, and hexylene group; and branched alkylene groups such as methylmethylene group, methylethylene group, 1-methylpentylene group, and 1,4-dimethylbutylene group. Among them, an ethylene group, a methylethylene group, a hexylene group, a 1-methylpentylene group, or a 1,4-dimethylbutylene group is preferred. R 3 is an alkyl group having 1 to 10 carbon atoms. Examples include methyl group, ethyl group, propyl group, butyl group, and isopropyl group. R 1 is the same as above. Xi+1 is a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group. a i is an integer of 0 to 3, preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. i is an integer of 1 to 10 and represents the number of stages of the above silylalkyl group, that is, the number of repeating silylalkyl groups. Therefore, when the number of stages is 1, the carbosiloxane dendrimer in this component is represented by the following general formula.

[0075]

[0076] (In this formula, Y, R 1 、R 2 and R 3 are the same as above, R 12is a hydrogen atom or 1 The same, and a 1 With the above a i The difference is that each molecule has a 1 The average total number is 0 to 7. ) When the order is 2, the carbosiloxane dendron in the component is represented by the following general formula.

[0077]

[0078] (In this formula, Y, R 1 , R 2 , R 3 and R 12 Same as above, and a 1 and a 2 With the above a i The only difference is that each molecule has a 1 and a 2 The average total number is 0 to 25. ) When the order number is 3, the carbosiloxane dendron in the component is represented by the following general formula.

[0079]

[0080] (In this formula, Y, R 1 , R 2 , R 3 and R 12 Same as above, and a 1 、a 2 and a 3 With the above a i The difference is that each molecule has a 1 、a 2 and a 3 The average total is 0 to 79. )

[0081] Examples of the carbosiloxane dendron containing a radically polymerizable organic group in the component include carbosiloxane dendrons represented by the following average composition formula.

[0082]

[0083]

[0084]

[0085] These carbosiloxane dendrons can be prepared using the method for preparing branched siloxane / silanylene copolymers described in JP H11-001530A (application number H09-171154). For example, the carbosiloxane dendrons can be prepared by treating a branched siloxane / silanylene copolymer having the general formula

[0086]

[0087] (wherein R 1 and Y are the same as above) is prepared by subjecting a silicon compound having a hydrogen atom bonded to a silicon atom and an organosilicon compound having an alkenyl group to a hydrosilylation reaction. Examples of these silicon compounds that can be used include 3-methacryloxypropyltris(dimethylsilyloxy)silane, 3-acryloxypropyltris(dimethylsilyloxy)silane, and 4-vinylphenyltris(dimethylsilyloxy)silane. Examples of these organosilicon compounds having an alkenyl group that can be used include vinyltris(trimethylsilyloxy)silane, vinyltris(dimethylphenylsilyloxy)silane, and 5-hexenyltris(trimethylsilyloxy)silane. The hydrosilylation reaction is preferably carried out in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

[0088] Another preferred embodiment of monomer (A) for use in the present invention is monomer (A2) represented by the following general formula (A-2).

[0089] Formula (A-2):

[0090]

[0091] (In this formula, Y and R 1 are the same as above, m is 0, 1, or 2, and n is a number from 0 to 200 representing the average degree of polymerization.)

[0092] Specific examples of the monomer represented by the general formula (A-2) include the following compounds.

[0093]

[0094] The following are examples of compounds in which m is 0 and n is 0 in the general formula (A-2). It can be used as one embodiment of monomer (A) in the present invention.

[0095]

[0096] Another preferred embodiment of monomer (A) for use in the present invention is monomer (A3) represented by the following general formula (A-3).

[0097] Formula (A-3):

[0098]

[0099] Another preferred embodiment of monomer (A) for use in the present invention is monomer (A4) represented by the following general formula (A-4).

[0100] Formula (A-4):

[0101]

[0102] Both monomers (A3) and (A4) are branched organosilicons having acrylate groups as polymerizable groups. Monomer (A3) has 16 silicon atoms. Monomer (A4) is structurally similar to monomer (A3), but has only 10 silicon atoms.

[0103] Another preferred embodiment of monomer (A) used in the present invention is monomer (A5) represented by the following general formula (A-5).

[0104] Formula (A-5):

[0105]

[0106] (In this formula, Me is methyl and Bu is butyl, and n = 0 to 120.)

[0107] Monomer (A5) is a linear organosilicon having an acrylate group as a polymerizable group.

[0108] Another preferred embodiment of monomer (A) used in the present invention is monomer (A6) represented by the following general formula (A-6).

[0109] Formula (A-6):

[0110]

[0111] Like monomers (A3) and (A4), monomer (A6) is also a branched organosilicon having an acrylate group as a polymerizable group, but it has only 4 silicon atoms.

[0112] Another preferred embodiment of monomer (A) used in the present invention is monomer (A7) represented by the following general formula (A-7).

[0113] Formula (A-7):

[0114]

[0115] (In this formula, Me is methyl and Bu is butyl.)

[0116] Like monomer (A6), monomer (A7) is also a branched organosilicon having an acrylate group as a polymerizable group, but it has only 3 silicon atoms.

[0117] The content of monomer (A) is 35% or more, preferably 40% or more, and more preferably 45% or more based on the weight of the monomer composition. When at least this amount of monomer (A) is used by weight, the water repellency and oil repellency of the resulting copolymer are higher, and the water resistance and sebum resistance of the cosmetic using the copolymer are improved. In addition, the content of monomer (A) is 70% or less, preferably 60% or less, and more preferably 55% or less based on the weight of the monomer composition.

[0118] [Unsaturated Polymerizable Monomer (B)]

[0119] The unsaturated polymerizable monomer (B) is an unsaturated polymerizable monomer that does not contain a silicon atom or contains one silicon atom and has one polymerizable group in the molecule. However, the type and properties of this monomer are not critical. The unsaturated polymerizable monomer (B) can be exemplified by an acidic group or its salt in the molecule, and it is selected from the group consisting of: (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, angelic acid, tigulinic acid, 2-carboxyethyl acrylate oligomer, styrenesulfonic acid, mono[(2-hydroxyethyl) methacrylate] phosphate, mono[(2-hydroxyethyl) acrylate] phosphate, ((2-hydroxyethyl) methacrylate) diphosphate, di[(2-hydroxyethyl) acrylate] phosphate, and their salts; lower (meth)acrylic acid alkyl esters or (meth)acrylic acid alkenyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate; higher (meth)acrylic acid esters, such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate; lower fatty acid vinyl esters, such as vinyl acetate and vinyl propionate; higher fatty acid esters, such as vinyl butyrate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, vinyl isostearate, vinyl behenate; vinyl aromatic monomers, such as styrene, vinyltoluene, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, vinylpyrrolidone; vinyl monomers containing an amide group, such as (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, isobutoxymethoxy (meth)acrylamide, and N,N-dimethyl (meth)acrylamide; vinyl monomers containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; fluorinated vinyl monomers, such as 3,3,3-trifluoropropyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, and perfluorooctylethyl (meth)acrylate; epoxy-functional vinyl monomers, such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate; vinyl monomers containing an ether bond, such as tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether;Vinyl monomers containing one silicon atom, such as (meth)acryloyloxypropyltrimethoxysilane, (meth)acryloyloxypropyltriethoxysilane, (meth)acryloyloxyoctyltrimethoxysilane, (meth)acryloyloxyoctyltriethoxysilane, (meth)acryloyloxymethyltrimethoxysilane, (meth)acryloyloxymethyltriethoxysilane, trimethoxysilylstyrene and triethoxysilylstyrene; styrene; butadiene; acrylonitrile; vinyl chloride; vinylidene chloride; (meth)acrylonitrile; dibutyl fumarate; maleic anhydride; (meth)acrylic acid glycidyl ether; quaternary ammonium salts derived from (meth)acrylic acid, such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, methacrylates of alcohols having a tertiary amine group, such as diethylaminoethyl methacrylate, and quaternary ammonium salts thereof.;

[0120] In addition, organosilicon compounds having a vinyl-based free-radically polymerizable unsaturated group and a hydrolyzable group can also be used. In this case, the film strength becomes hard and the water repellency durability is improved, which is preferable. Here, examples of the free-radically polymerizable group include an organic group containing a (meth)acryloyloxy group, an organic group containing a (meth)acrylamide group, and an organic group containing a styryl group represented by the following general formula, or an alkenyl group having 2 to 10 carbon atoms, and a vinyloxy group and an allyloxy group.

[0121] Similarly, unsaturated monomers having at least one acidic group or its salt in the molecule can also be used. An unsaturated monomer having at least one acidic group or its salt in the molecule is a compound having a free-radically polymerizable vinyl group and at least one acidic group or its salt in the molecule. Examples of the acidic group include carboxylic acid, sulfonic acid and phosphonic acid. Examples of its salt include alkali metal salts, alkaline earth metal salts, basic amino acid salts, ammonium salts, alkylammonium salts, alkylamine salts and alkanolamine salts, and specific examples include sodium salt, potassium salt, magnesium salt, calcium salt, L-arginine salt, L-histidine salt, L-lysine salt, ammonium salt, triethanolamine salt, aminomethylpropanediol salt and their complex salts. Compounds having these acidic groups change the hydrophilic-hydrophobic properties of the compound by releasing protons (H+) in an aqueous solution at their respective specific pH values or bonding with cation components in the liquid to form salts. Compounds having salts of acidic groups similarly undergo dissociation of the salt at a specific pH and exhibit a change in the hydrophilic-hydrophobic properties of the compound. Therefore, by appropriately adding compounds having these acidic groups or their salts to cosmetic materials, an effect of being easily washed off during cleaning can be achieved while exhibiting good cosmetic retention.

[0122] Similarly, for the purpose of improving the water repellency and the like of the copolymer containing a carbosiloxane dendrimer structure in the present invention, an unsaturated monomer containing a fluorinated organic group such as a perfluoroalkyl group or the like can also be used. An example is a vinyl-based monomer having a fluorinated organic group such as a perfluoroalkyl group or the like, such as an acrylic monomer, a methacrylic monomer, or the like.

[0123] [Organosilicon Functional Copolymer]

[0124] The copolymer containing a polysiloxane structure in the present invention is obtained by copolymerizing the above component (A) and component (B), and the mass ratio during copolymerization is preferably in the range of (A):(B) = 35:65 to 70:30, more preferably 40:60 to 65:35, and even more preferably 40:60 to 60:40. Specifically, based on the total mass of component (A) and component (B), the mass% of the above component (A) is at least 35 mass%, and preferably at least 40 mass%, and component (A) is particularly preferably 40 mass% to 60 mass% of the total monomer units.

[0125] The organosilicon-functional copolymer of the present invention is obtained by carrying out a copolymerization reaction of monomer (A) and monomer (B). Such an organosilicon-functional copolymer is a non-crosslinked copolymer. Therefore, different from the crosslinked copolymers in the prior art that generally exhibit poor solubility due to their thermosetting properties, the non-crosslinked organosilicon-functional copolymer of the present invention can be more easily dissolved in various oils suitable for cosmetics.

[0126] The method for copolymerizing the copolymer used to form the solid particles of the present invention can be a radical polymerization method, an anionic polymerization method, a cationic polymerization method, a group transfer method, an organometal-mediated radical polymerization, or an atom transfer radical addition method, but the radical polymerization method is preferred. The radical polymerization can be carried out by at least one liquid-phase polymerization reaction selected from solution polymerization, suspension polymerization, miniemulsion polymerization, and emulsion polymerization, but solution polymerization or miniemulsion polymerization is preferably used as the radical polymerization method, and solution polymerization is further preferably used as the radical polymerization method.

[0127] In miniemulsion polymerization, first, a monomer composition substantially composed of monomer (A) and monomer (B) is emulsified with an emulsifier, and they are reacted in a lipid in the presence of a radical initiator at a temperature of 20 °C to 95 °C for 0.5 hour to 20 hours. Examples of emulsifiers that can be used in the miniemulsion reaction include amphoteric surfactants, semi-polar surfactants, and reactive surfactants, such as sodium lauryl sulfate, lauryl alcohol polyether-1 phosphate, polyglycerol monostearate (polyglycerol-10 stearate, reaction product of polyglycerol having 10 glycerol repeating units and stearic acid), polyglycerol monolaurate (polyglycerol-10 laurate, reaction product of polyglycerol having 10 glycerol repeating units and lauric acid), etc.; and high molecular weight emulsifiers, such as ethylene oxide 20 mol adduct of polyoxyethylene (C16) ether, ethylene oxide 20 mol adduct of polyoxyethylene (C18) ether, etc. As the radical initiator that can be used in the miniemulsion reaction, there is no particular limitation as long as the radical polymerization initiator is a radical polymerization initiator commonly used in the emulsion polymerization of vinyl polymers. Examples thereof include water-soluble peroxides, including inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; and organic peroxides, such as tert-butyl peroxymaleic acid, succinic peroxide, and tert-butyl hydroperoxide. When using an oil-soluble radical initiator, the oil-soluble radical initiator can be mixed before emulsification and fed as a mixture containing monomer (A) or / and monomer (B), or the initiator can be pre-emulsified and fed. For the miniemulsion polymerization, its details have also been disclosed in US20190053999, which is incorporated herein by reference.

[0128] In solution polymerization, a monomer composition substantially composed of monomer (A) and monomer (B) is reacted in a solvent in the presence of a radical initiator at a temperature of 50 °C to 150 °C for 3 hours to 20 hours. Examples of solvents that can be used in the polymerization reaction include aliphatic hydrocarbons, such as hexane, octane, decane, and cyclohexane; aromatic hydrocarbons, such as benzene, toluene, and xylene; ethers, such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; esters, such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; alcohols, such as methanol, ethanol, isopropanol, and butanol; and organosiloxane oligomers, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane.

[0129] Any free radical initiator commonly used in free radical polymerization methods can be used. Specific examples include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, tert-amyl peroxyneopentanoate, tert-butyl peroxyneopentanoate, tert-hexyl peroxyneopentanoate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di(3,5,5-trimethylhexanoyl) peroxide, and diisopropyl peroxydicarbonate. These free radical initiators can be used alone or as a mixture of two or more. The preferred amount depends on the target molecular weight of the copolymer. Based on 100 parts by weight of the monomer composition, the amount of the free radical initiator used is preferably in the range of 0.005 parts by weight to 10 parts by weight.

[0130] To control the molecular weight of the copolymer, a chain transfer agent can also be added during polymerization. Specific examples of the chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butanethiol, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, polydimethylsiloxane having a mercaptopropyl group, and mercaptopropionic acid; and halides such as dichloromethane, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane; and secondary alcohols such as isopropyl alcohol and glycerol; and sulfurous acid (salt) such as sodium sulfite; and sulfurous acid (salt); sodium bisulfite; sodium dithionite; potassium metabisulfite; hydrogen peroxide, etc. Sulfurous acid (salt) such as sodium bisulfite; dithionous acid (salt) such as sodium dithionite; metabisulfurous acid (salt) such as potassium metabisulfite; and hydrogen peroxide.

[0131] After polymerization, purification can be carried out by reducing the pressure under heating to remove the remaining unreacted vinyl monomers, by hydrogenating the product in the presence of a hydrogenation catalyst and in the presence or absence of a solvent to deodorize the product, and / or by contacting the product with nitrogen under reduced pressure to remove light substances. The purified product is particularly preferred when used in topical preparations that require low odor and compatibility with other cosmetic components. There are no particular limitations on the solvent, reaction conditions, and reduced pressure conditions used in the hydrogenation reaction stripping process. Any solvent, reaction conditions, and reduced pressure conditions commonly used for purifying organopolysiloxane copolymers can be selected.

[0132] Then, the polymerization reaction product produced by this process is brought into contact with a nickel or palladium catalyst. By bringing the reaction product into contact with a palladium catalyst, the vinyl groups in the unreacted monomers remaining in the polymerization reaction product are saturated, and its irritation and odor can be reduced before adding the product to cosmetics. Examples of palladium catalysts include, but are not limited to, palladium compounds such as tetrakis(triphenylphosphine)palladium(0) and bis(triphenylphosphine)palladium(II) dichloride, as well as palladium on carbon, palladium hydroxide on carbon, and platinum oxide. Palladium on carbon is the preferred catalyst. Palladium is a noble metal, and when the palladium on carbon catalyst is used as a heterogeneous catalyst, such special problems do not occur. Therefore, it is preferably used as the catalyst in the present invention.

[0133] The temperature at which the hydrogenation reaction product is brought into contact with the nickel catalyst or palladium catalyst is from 50°C to 200°C, and preferably from 70°C to 130°C. The pressure (absolute pressure) is from 1 kg / cm 2 to 1,000 kg / cm 2 and preferably from 2 kg / cm 2 to 100 kg / cm 2 . The contact time is from 1 hour to 15 hours, and preferably from 3 hours to 10 hours. The reaction can be carried out in a solvent, and the solvent can be used directly during polymerization, or solvent replacement can be carried out. The solvent can be one of the solvents mentioned above regarding the polymerization reaction.

[0134] Stripping, reprecipitation, and filtration can also be carried out during this process. Stripping, reprecipitation, filtration, pulverization, and / or classification can be carried out after the hydrogenation reaction and after stripping and filtration.

[0135] The presence or absence of unreacted monomers in the resulting copolymer can be confirmed by 1 the presence of the peak integral value of the olefinic unsaturated group (5.5 ppm to 6.5 ppm) in 1H-NMR. The end of the reaction can be confirmed by the disappearance or reduction of the peak derived from the olefinic unsaturated group. More specifically, the ratio (residual unsaturation ratio) of the peak integral value of the olefinic unsaturated group to the product of the integral value of the methyl group of the unsaturated monomer having a polysiloxane structure (0 ppm to 0.3 ppm) and the weight percentage of the unsaturated monomer having a polysiloxane structure when added to the system can be used for comparison. The residual unsaturation ratio of the copolymer is 0.1 or less, and preferably 0.02 or less.

[0136] [Solid Particles]

[0137] After the polymerization and subsequent drying process, the obtained organosilicon-functional copolymer forms solid particles whose primary particles have a long dimension of 0.1 μm to 5,000 μm. Here, the method of such granulation is not limited, and any preparation method known in the art can be used.

[0138] The method for preparing the solid particles includes, for example, a method of pulverizing the above organosilicon-functional copolymer using a pulverizer, or a method of directly micronizing in the presence of a solvent. The pulverizer can be, for example but not limited to, a roll mill, a ball mill, a jet mill, a turbo mill, or a planetary mill. Examples of the method of directly micronizing the organosilicon-functional copolymer in the presence of a solvent include spraying through a spray dryer, or micronizing using a biaxial kneader or a belt dryer.

[0139] Specifically, by using a spray dryer or the like, the solid particles have a regular spherical shape and an average primary particle size of 0.1 μm to 5,000 μm. In addition, the solid particles obtained by the spray dryer can be aggregated into particles having an average secondary particle size of 0.5 μm to 5,000 μm, or 1.0 μm to 5,000 μm, or more preferably 3.0 μm to 3,000 μm, or even more preferably 5.0 μm to 2,000 μm. The heating and drying temperature of the spray dryer needs to be appropriately set based on the heat resistance of the organosilicon-functional copolymer solid particles and the like. It should be noted that in order to prevent secondary aggregation of the obtained solid particles, it is preferable to control the temperature of the organosilicon-functional copolymer solid particles below its glass transition temperature. The organosilicon-functional copolymer solid particles thus obtained can be recovered by a cyclone separator, a bag filter, or the like.

[0140] The solvent can be used for the above granulation to the extent that it is harmless to the desired properties of the solid particles of the present invention. Examples of the solvent include but are not limited to aliphatic hydrocarbons such as n-hexane, cyclohexane, n-octane, n-decane, n-dodecane, methylcyclohexane, and n-heptane; aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and dipropyl ether; silicones such as hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane; esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol, isopropanol, and butanol.

[0141] The obtained solid particles can have various shapes as long as they can exhibit desired excellent solubility and easy handling properties as cosmetic ingredients when formulated into a cosmetic composition. In some embodiments, the shape of the solid particles is preferably selected from granules, powders, pellets, beads, short fibers, chopped rovings, and pulverized powders.

[0142] Manufacturing Method of Solvent-Soluble Solid Particles

[0143] In the present invention, there is also provided a method for manufacturing the above solvent-soluble solid particles. The manufacturing method includes the following steps:

[0144] Step (I): A step of preparing a solution or dispersion of an organosilicon-functional copolymer from a monomer composition by a polymerization reaction, the monomer composition consisting essentially of (A) an unsaturated polymerizable monomer having at least one organosilicon functional group and one polymerizable group in the molecule and (B) an unsaturated polymerizable monomer having no silicon atom or having one silicon atom and one polymerizable group in the molecule, wherein the mass ratio of the monomers (A) and (B) in the monomer composition is in the range of 35:65 to 70:30; and

[0145] Step (II): A step of removing the carrier fluid of water or solvent from the solution or dispersion of the organosilicon-functional copolymer prepared in the above step (I).

[0146] Step (I) is a step of preparing an organosilicon-functional copolymer by a polymerization reaction. In some embodiments, the step (I) is a step of preparing a solution or dispersion of an organosilicon-functional copolymer by a liquid-phase polymerization reaction selected from at least one of solution polymerization, miniemulsion polymerization, and emulsion polymerization. Details of such polymerization reactions have been described in the [Organosilicon-functional copolymer] section.

[0147] Step (II) is a step for preparing solid particles from an organosilicon-functional copolymer. In some embodiments, the step (II) is a step of a spray drying method to obtain spherical particles of the organosilicon-functional copolymer by spraying the solution or dispersion to remove the carrier fluid of water or solvent from the solution or dispersion of the organosilicon-functional copolymer. Details of such spray drying methods have been described in the [Solid particles] section. Additionally, the step (II) can be a step of using a stripping process to remove the carrier fluid of water or solvent to obtain a solid organosilicon-functional copolymer. Specifically, the stripping process can be run in the barrel section of a single-screw or multi-screw extruder apparatus. Through the stripping process in the screw extruder apparatus under reduced pressure and high temperature, the solvent-removed organosilicon-functional copolymer is kneaded under high shear and ejected from the outlet of the screw extruder apparatus in a thermally molten state. The molten organosilicon-functional copolymer can be formed into a wire-like through-hole of a wire die equipped at the outlet of the screw extruder apparatus. Optionally, the wire-like organosilicon-functional copolymer is cooled using a water bath or other cooling device, and then subjected to a cutting / granulation process in the following step (III).

[0148] In some embodiments, the above method for manufacturing solid particles further includes the following steps:

[0149] Step (III): After said step (II), a step of forming solid particles substantially composed of a silicone-functional copolymer using at least one device selected from a granulator, a mill, a crusher, a grinder, and a drum flaker. As said extruder, granulator, mill, crusher, grinder, ingotizer, and drum flaker, any device known in the art can be used. In said step (III), in order to form the solid particles smoothly and granulate, the viscosity or melt viscosity of the silicone-functional copolymer at the processing temperature is preferably in the range of 0.05 Pas to 7,000 Pas. Specifically, the granulation method of the silicone-functional copolymer is one of the preferred methods for obtaining the shaped solid particles of the silicone-functional copolymer. That is, using a screw extruder instrument equipped with a strand die at its outlet, the linear silicone-functional copolymer is cut into small pelletized materials of solid particles by a granulator.

[0150] Step (III) is an optional step, but it is preferred to carry out step (III) to form solid particles substantially composed of a silicone-functional copolymer having a desired long dimension of 0.1 μm to 5,000 μm, or preferably 0.5 μm to 5,000 μm, or more preferably 1 μm to 5,000 μm.

[0151] Step (IV): A step of classifying the coarse solid particles substantially composed of a silicone-functional copolymer using at least one device selected from a screen filter, a sieve, a perforated plate, a cyclone separator, and a dynamic air classifier.

[0152] Step (IV) is also an optional step, but it is preferred to carry out step (III) or (IV) to form solid particles substantially composed of a silicone-functional copolymer having a desired long dimension of 0.1 μm to 10,000 μm, or preferably 0.1 μm to 5,000 μm, or more preferably 1 μm to 5,000 μm.

[0153] Uses of Solvent-Soluble Solid Particles

[0154] In the present invention, the use of the above solvent-soluble solid particles is also provided. Specifically, due to its high solubility in cosmetic solvents, the solvent-soluble solid particles of the present invention can be used as cosmetic ingredients, especially as cosmetic ingredients having a film-forming function on human skin and / or hair. In particular, different from the silicone acrylates currently provided mainly in the form of dispersions, the solvent-soluble solid particles of the present invention can be directly blended into cosmetics. Of course, it can also be used in the conventional form of a composition dissolved in a solvent or dispersed in a dispersion medium.

[0155] Cosmetic Composition and Its Preparation Method

[0156] [Cosmetic Composition]

[0157] In the present invention, there is also provided a cosmetic composition containing the above-mentioned solvent-soluble solid particles and a method for preparing the same. Specifically, the solvent-soluble solid particles of the present invention can be directly blended into the cosmetic composition, and from the viewpoints of processing and storage stability, they are very useful ingredients in cosmetics. Although potential cosmetic compositions are various and not limited thereto, the solvent-soluble solid particles of the present invention can be used to replace the copolymers having a silicone functional group derived from the above-mentioned Si-functional monomers represented by (A-1) to (A-7) in existing cosmetic preparations, wherein a carbosiloxane dendrimer structure is a preferred example of the silicone functional group.

[0158] For example, the solvent-soluble solid particles of the present invention can partially or completely replace the components of the silicone acrylate copolymer having a carbosiloxane dendrimer structure in the cosmetic preparations in the following patent publications (for example, conventional products such as FA 4001CM silicone acrylate, FA 4002ID silicone acrylate, FA 4003 silicone acrylate, FA 4004ID silicone acrylate, FAPEPS, etc.);

[0159] WO2012 / 143344, WO2014 / 154701, WO2014 / 154700, WO2015 / 092632, WO2015 / 097110, WO2015 / 097103, WO2017 / 050699, WO2017 / 050922, WO2010 / 026538, WO2014 / 087183, WO2011 / 051323, JP2007-320960, WO2016 / 030842;

[0160] JP2010-018612, JP2011-016734, JP2011-016732, JP2011-016733, JP2011-016734, JP 2011-126807, JP 2011-126808, JP2013-001672, JP 2014-034568, JP 2014-040388, JP 2014-227358, JP2015-098451, JP 2015-137252, JP 2016-008200, JP2016-088848, JP 2016-121095, JP 2016-160191, JP 2018-090495;

[0161] JP2000 - 072784, JP07 - 309714, JP2007 - 320960, JP2014 - 040512, WO2017 / 061090, JP2011 - 149017, JP2014 - 040512, JP2014 - 040511, WO / 2018 / 086139, WO / 2018 / 186138, PCT / JP18 / 022412, PCT / JP18 / 022413.

[0162] In this document, the applicant clearly and intentionally teaches and recommends to the readers of this patent application to replace the conventional copolymers having silicone functional groups derived from the Si - functional monomers represented by the above (A - 1) to (A - 7) in conventional and available cosmetic formulations with the solvent - soluble solid particles of the present invention.

[0163] Furthermore, the emulsion composition containing the solvent - soluble solid particles of the present invention can be used to partially or completely replace the silicone acrylate copolymer emulsions in the cosmetic formulations disclosed in WO2017 / 061090, WO / 2018 / 086139, WO / 2018 / 186138, PCT / JP18 / 022412, PCT / JP18 / 022413 and Research Publication IPCOM000243971D, IPCOM0002457480.

[0164] By replacing the existing silicone acrylate copolymers having silicone functional groups derived from the Si - functional monomers represented by the above (A - 1) to (A - 7) in available and conventional cosmetic formulations with the solvent - soluble solid particles of the present invention, those skilled in the art can anticipate and design similar or improved cosmetic formulations or compositions.

[0165] There is no particular limitation on the amount blended into the cosmetics, but the solvent - soluble solid particles of the present invention can be blended into the cosmetic composition in the range of 0.1% by mass to 50% by mass, preferably 1% by mass to 10% by mass of the entire cosmetic composition. When the added amount is within this range, the properties of the solvent - soluble solid particles of the present invention, namely, film - forming properties and film washability, can be imparted to the cosmetic composition.

[0166] In addition to the solvent - soluble solid particles of the present invention, the cosmetic composition of the present invention may further contain any conventional cosmetic ingredients, such as (D) oils, (E) alcohols, (F) surfactants, (G) powders or colorants, (H) thickeners or gelling agents, (I) organically modified clay minerals, (J) silicone resins, (K) silicone gums, (L) silicone elastomers, (M) organically modified silicones, (N) UV - protecting components, (O) water - soluble polymers, and water.

[0167] (D) Oil

[0168] The oil can be any animal oil, vegetable oil or mineral oil commonly used in cosmetics. The oil can be solid, semi-solid or liquid and can be non-volatile, semi-volatile or volatile. The oil is used to impart lubricity to the skin and hair, and to make the skin soft and give a moist feeling. The oil can also be used to dilute the silicone-functional copolymer of the present invention to obtain a copolymer composition. The oil is preferably at least one type selected from (D1) silicone oil and (D2) organic oil that is liquid at a temperature of 5 °C to 100 °C. The type and viscosity of the oil depend on the type of cosmetics and the intended use. These oils are simultaneously blended into the composition with the cosmetic composition of the present invention.

[0169] (D1) Silicone Oil

[0170] Silicone-based oils are generally hydrophobic and their molecular structure can be cyclic, linear or branched. Here, the molecular structure can be cyclic, linear or branched. The viscosity of silicone-based oils at 25 °C is generally in the range of 0.65 mm 2 / s to 100,000 mm 2 / s, and preferably in the range of 0.65 mm 2 / s to 10,000 mm 2 / s. The silicone oil agent can be volatile, and this is preferred.

[0171] Examples of silicone-based oils include cyclic organopolysiloxanes, linear organopolysiloxanes and branched organopolysiloxanes. Among them, volatile cyclic organopolysiloxanes, linear organopolysiloxanes and branched organopolysiloxanes are preferred.

[0172] The silicone oil can be an organopolysiloxane represented by the following general formula (3), (4) or (5).

[0173]

[0174] (In this formula, R 9 is a hydrogen atom or a group selected from a hydroxyl group, a monovalent unsubstituted or fluorine- or amino-substituted alkyl group having 1 to 30 carbon atoms, an aryl group and an alkoxy group, and (CH 3 ) 3 SiO{(CH 3 ) 2 SiO} l Si(CH 3 ) 2 CH 2 CH 2-(where l is an integer from 0 to 1,000, a' is an integer from 0 to 3, b is an integer from 0 to 1,000, and c is an integer from 0 to 1,000, provided that 1 ≤ b + c ≤ 2,000.)

[0175]

[0176] (wherein R 9 is the same as above, d is an integer from 0 to 8, and e is an integer from 0 to 8, provided that 3 ≤ d + e ≤ 8.)

[0177] R 9 (4-f) Si(OSiCH 3 ) g (5)

[0178] (wherein R 9 is the same as above, f is an integer from 1 to 4, and g is an integer from 0 to 500.)

[0179] Examples of the monovalent unsubstituted or fluorine- or amino-substituted alkyl groups, aryl groups, and alkoxy groups having 1 to 30 carbon atoms include straight-chain or branched-chain alkyl groups having 1 to 30 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, and dodecyl group; cycloalkyl groups having 3 to 30 carbon atoms, such as cyclopentyl group and cyclohexyl group; aryl groups having 6 to 30 carbon atoms, such as phenyl group, tolyl group, xylyl group, and naphthyl group; alkoxy groups having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, and propoxy group; and groups in which at least a part of the hydrogen atoms bonded to the carbon atoms in any one of these groups is replaced by a fluorine atom or an amino group. An unsubstituted alkyl group or aryl group is preferred, an unsubstituted alkyl group or aryl group having 1 to 6 carbon atoms is more preferred, and a methyl group, an ethyl group, or a phenyl group is particularly preferred.

[0180] Examples of silicone oils having these structures include cyclic organopolysiloxanes. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,1 - ethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1 - diphenylhexamethylcyclotetrasiloxane, 1,3,5,7 - tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7 - tetramethylcyclotetrasiloxane, 1,3,5,7 - tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3 - trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7 - tetra(3 - methacryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(3 - acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(3 - carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(3 - vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(p - vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra[3-(p - vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(N - acryloyl - N - methyl - 3 - aminopropyl)tetramethylcyclotetrasiloxane, and 1,3,5,7 - tetra(N,N - bis(lauroyl)-3 - aminopropyl)tetramethylcyclotetrasiloxane.

[0181] Examples of linear organopolysiloxanes include dimethylpolysiloxanes capped at both ends of the molecular chain with trimethylsilyloxy groups (dimethylsilicones with low viscosities of 2 mPa·s or 6 mPa·s to dimethylsilicones with high viscosities of 1 million mPa·s), diethylpolysiloxanes capped at both ends of the molecular chain with triethylsilyloxy groups, organohydrogenpolysiloxanes, methylphenylpolysiloxanes capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethylsiloxane / methylphenylsiloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, diphenylpolysiloxanes capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethylsiloxane / diphenylsiloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethylsiloxane / methylphenylsiloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, diphenylpolysiloxanes capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethylsiloxane / diphenylsiloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, diphenylpolysiloxanes capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethylsiloxane / diphenylsiloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, trimethylpentaphenyltrisiloxane capped at both ends of the molecular chain with trimethylsilyloxy groups, phenyl(trimethylsilyloxy)siloxane, methylalkylpolysiloxanes, dimethylpolysiloxane / methylalkylsiloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethylsiloxane-methyl(3,3,3-trifluoropropyl)siloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, α,ω-dihydroxypolydimethylsiloxane, α,ω-diethoxypolydimethylsiloxane, 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane, 1,1,1,3,5,5,5-heptamethyl-3-dodecyltrisiloxane, 1,1,1,3,5,5,5-heptamethyl-3-hexadecyltrisiloxane, tris(trimethylsilyloxy)methylsilane, tris(trimethylsilyloxy)alkylsilane, tetrakis(trimethylsilyloxy)silane, tetramethyl-1,3-dihydroxydisiloxane, octamethyl-1,7-dihydroxytetrasiloxane, hexamethyl-1,5-diethoxytrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, higher alkoxy-modified silicones, and higher fatty acid-modified silicones.

[0182] Examples of branched organopolysiloxanes include methyltris(trimethylsilyloxy)silane, ethyltris(trimethylsilyloxy)silane, propyltris(trimethylsilyloxy)silane, tetrakis(trimethylsilyloxy)silane, and phenyltris(trimethylsilyloxy)silane.

[0183] When the cosmetic or composition of the present invention containing at least one of these silicone-based oils is used as an ingredient in a cosmetic composition, the aging stability can be improved and the smooth feeling characteristics of the silicone oil can be achieved. Among these silicone-based oils, decamethylcyclopentasiloxane (a linear organopolysiloxane with a low viscosity in the range of 2 mPa·s to 6 mPa·s), 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane (octanoyl polymethylsiloxane), and tris(trimethylsilyloxy)methylsilane (M3T) are particularly preferred.

[0184] (D2) Organic Oil

[0185] Examples of the organic oil include (D2-1) hydrocarbon oils, (D2-2) fatty acid ester oils, higher alcohols, higher fatty acids, fats and oils, and fluorinated oils, and (D2-3) light ester oils. There is no particular limitation in the present invention, but the organic oil is preferably liquid at a temperature of 5°C to 100°C. In addition, hydrocarbon oils and / or fatty acid ester oils are preferred. These organic oils can be used alone or in combination with other organic oils and / or silicone-based oils. When appropriate oils are combined, the stability of the composition and / or cosmetic over time is improved, and the desired feeling can be imparted to each cosmetic. By blending in the silicone-based oil, the smooth feeling characteristics of the silicone oil can be imparted, by blending in the highly volatile oil, a refreshing feeling can be imparted to the skin, and by using a combination of hydrocarbon oils and / or fatty acid ester oils and silicone-based oils, a smooth feeling and a moisturizing effect (moist feeling) can be imparted to the skin and hair.

[0186] Examples of the hydrocarbon oil (D2-1) include liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, petrolatum, n-alkane, isoparaffin, isododecane, isohexadecane, polyisobutene, hydrogenated polyisobutene, polybutene, ozokerite, pure ozokerite, microcrystalline wax, paraffin wax, polyethylene wax, polyethylene / polypropylene wax, squalane, squalene, pristane, and polyisoprene. Here, linear alkanes from plant sources can be used, and volatile linear alkanes understood to be C9-17, preferably C11-13 are used. In the cosmetic composition of the present invention, isododecane, undecane, and / or tridecane are particularly preferably used because they have excellent volatility, excellent compatibility and affinity (combinatorial stability) with other cosmetic ingredients, and impart a refreshing feeling to the skin.

[0187] Examples of fatty acid ester oils (D2-2) include hexyl decyl octanoate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, dimethyl hexyl decyl octanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, ditrimethylolpropane triethylhexanoate, (isostearic acid / sebacic acid) ditrimethylolpropane, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, diisostearyl malate, hydrogenated castor oil monostearate, N-alkyl diol monoisostearate, octyldodecyl isostearate, isopropyl isostearate, isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, octyldodecyl gum ester, ethyl oleate, octyldodecyl oleate, neopentyl glycol didecanoate, triethyl citrate, 2-ethylhexyl succinate, dioctyl succinate, isocetyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, diethyl sebacate, dioctyl sebacate, dibutyl octyl sebacate, cetyl palmitate, octyldodecyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid ester, 2-hexyldecyl myristate, ethyl laurate, N-lauroyl-L-glutamic acid 2-octyldodecyl ester, di(cholesterol / behenyl / octyldodecyl) N-lauroyl-L-glutamate, di(cholesterol / octyldodecyl) N-lauroyl-L-glutamate, di(phytosterol / behenyl / octyldodecyl) N-lauroyl-L-glutamate, di(phytosterol / octyldodecyl) N-lauroyl-L-glutamate, isopropyl N-lauroylsarcosinate, diisostearyl malate, neopentyl glycol dioctanoate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, isotridecyl isononanoate, diethyl pentanediol dineopentanoate, methyl pentanediol neopentanoate, octyldodecyl neodecanoate, 2-butyl-2-ethyldioctanoate-1,3 - propylene glycol, pentaerythrityl tetraoctanoate, pentaerythritol hydrogenated rosin, pentaerythritol triethylhexanoate, dipentaerythritol (hydroxystearate / stearate / abietate), polyglyceryl tetra isostearate, polyglyceryl - 10 nona isostearate, polyglyceryl deca (erucate / isostearate / ricinoleate) - 8, diglycerol (caprylate / caprate) oligomer, ethylene glycol distearate (glycol distearate) (ethylene glycol distearate), diisopropyl dimer dilinoleate, diisostearyl dimer dilinoleate, di (isostearyl / phytosterol) linoleate, di (phytosterol / behenyl alcohol) linoleate, di (phytosterol / isostearyl / cetyl / stearyl / behenyl alcohol) linoleate, dimer dilinoleate dimer dilinoleate, dihydroxylinoleyl diisostearate, dihydroxylinoleyl hydrogenated rosin concentrate, dimer dilinoleate hydrogenated castor oil, hydroxyalkyl dihydroxylinoleyl ether, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl trimyristate, glyceryl triisopalmitate, glyceryl trioctanoate, glyceryl trioleate, glyceryl diisostearate, glyceryl tri (caprylate / caprate), glyceryl tri (caprylate / caprate / myristate / stearate), hydrogenated rosin glyceride (hydrogenated ester gum), rosin glyceride (ester gum), glyceryl beiconate eicosanedioate, di - 2 - heptylundecanoate, diglycerol myristate isostearate, cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, cholesteryl 12 - hydroxystearate, cholesteryl macadamia nut oil fatty acid, phytosterol macadamia nut oil fatty acid, phytosterol isostearate, cholesteryl lanolin fatty acid, cholesteryl hard lanolin fatty acid, cholesteryl long - chain branched fatty acid, cholesteryl long - chain α - hydroxy fatty acid, octyldodecyl ricinoleate, octyldodecyl lanolin fatty acid, octyldodecyl erucate, hydrogenated castor oil isostearate, ethyl avocado oil fatty acid, and isopropyl lanolin fatty acid. Lanolin and lanolin derivatives can also be used as fatty acid ester oils.,

[0188] In addition to the above - mentioned fatty acid ester oils, oils such as fats and oils, higher alcohols, higher fatty acids, and fluorine - based oils can be used, or two or more of these fatty acid ester oils can be used in combination. For example, two or more of the oils listed below can be used in combination. The following are specific examples of additional oils that can be used in the present invention. One or more of these fats and oils, higher alcohols, higher fatty acids, and fluorine - based oils can be selected and used.,

[0189] In fats and oils, natural animal and plant fats and oils, as well as semi-synthetic fats and oils that can be used include avocado oil, linseed oil, almond oil, Chinese insect wax, eno oil, olive oil, cocoa butter, kapok oil, torreya grandis oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef suet, beef bone fat, hardened beef tallow, almond oil, cetyl wax, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, camellia oil, safflower oil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, olive squalane, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese tung oil, rice bran wax, germ oil, horse fat, peach kernel oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, methyl ricinoleate, sunflower oil, grape oil, myrica wax, jojoba oil, hydrogenated jojoba ester, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, Japanese wax, Japanese wax kernel oil, montan wax, coconut oil, hardened coconut oil, glyceryl tricaprylate, mutton tallow, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, anhydrous lanolin, lanolin acetate, isopropyl lanolate, POE lanolin alcohol ether, POE lanolin alcohol acetate, polyethylene glycol lanolate, POE hydrogenated lanolin alcohol ether, and egg yolk oil. Here, POE refers to polyoxyethylene.

[0190] Higher alcohols have 10 to 30 carbon atoms. Higher alcohols are saturated or unsaturated monohydric fatty alcohols. Some of the hydrocarbon groups in the hydrocarbon group can be straight-chain or branched-chain, but straight-chain groups are preferred. Examples of higher alcohols having 10 to 30 carbon atoms include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, hexadecanol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetearyl alcohol, 2-decyltetradecanol, cholesterol, sitosterol, phytosterol, lanosterol, lanolin alcohol, hydrogenated lanolin alcohol, POE cholesterol ether, monostearyl glycerol ether (batyl alcohol), and monooleyl glycerol ether (selacholeyl alcohol), etc. Preferably, in the present invention, higher alcohols having a melting point of 40°C to 80°C are used alone or a combination of higher alcohols having a melting point of 40°C to 70°C is used. These higher alcohols form aggregates called α-gels together with surfactants and have the functions of increasing the viscosity of the preparation and stabilizing the emulsion. Therefore, they can be particularly used as bases in cosmetic emulsions.

[0191] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0192] Examples of fluorine-based oils include perfluoropolyether, perfluorodecalin, and perfluorooctane.

[0193] Examples of the light ester oil (D2-3) include methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, sec-butyl formate, tert-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, sec-butyl butyrate, tert-butyl butyrate.

[0194] (E) Alcohol

[0195] The organosilicon functional copolymer of the present invention can be used after being dispersed or dissolved in an alcohol. Since the organosilicon functional copolymer of the present invention has excellent affinity with alcohols which are commonly used as components in cosmetics, alcohols can also be used in cosmetic formulations. One or more polyhydric alcohols and / or lower monohydric alcohols can be used. Examples of the lower alcohols include ethanol, isopropyl alcohol, n-propyl alcohol, tert-butyl alcohol, and sec-butyl alcohol. Ethanol is preferred. Examples of the polyhydric alcohols include dihydric alcohols such as 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, dibutylene glycol, pentylene glycol, hexylene glycol, and octylene glycol; trihydric alcohols such as glycerol, trimethylolpropane, and 1,2,6-hexanetriol; tetrahydric alcohols and higher alcohols such as pentaerythritol and xylitol; and sugar alcohols such as sorbitol, mannitol, maltitol, maltotriose, sucrose, erythritol, glucose, fructose, starch degradation products, maltose, xylitolose, and starch degradation sugar-reduced alcohols. Examples other than these lower polyhydric alcohols include polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerol, polyethylene glycol, triglycerol, tetraglycerol, and polyglycerol. Among them, ethanol, 1,3-propanediol, 1,3-butanediol, sorbitol, dipropylene glycol, glycerol, and polyethylene glycol are particularly preferred.

[0196] (F) Surfactant

[0197] The cosmetic composition containing the solvent-soluble solid particles of the present invention may contain (F) surfactant as an optional component. Depending on the intended use, the (F) surfactant may be one or more surfactants selected from the group consisting of: (F1) silicone-based surfactants, (F2) anionic surfactants, (F3) cationic surfactants, (F4) nonionic surfactants, (F5) amphoteric surfactants, and (F6) semi-polar surfactants. For each use, reactive surfactants having polymerizable unsaturated groups are also applicable.

[0198] (F1) Examples of silicone-based surfactants include polyglycerol-modified silicones, diglycerol-modified silicones, glycerol-modified silicones, sugar-modified silicones, fluorinated polyether-modified silicones, polyether-modified silicones, carboxylic acid-modified silicones, linear silicone / polyether block copolymers (such as polysilicone-13, etc.), long-chain alkyl / polyether co-modified silicones, polyglycerol-modified silicone elastomers, diglycerol-based knitted elastomers, glycerol-modified elastomers, and polyether-modified elastomers. If necessary, the above-mentioned silicones and elastomers with alkyl side chains, linear silicone side chains, or siloxane dendrimer side chains simultaneously set as hydrophilic groups can also be used. Commercially available products include SH 3771M, SH 3772M, SH 3773M, SH 3775M, BY 22-008M, BY 11-030, ES-5226DM formulation aid, ES-5227DM formulation aid, ES-5373 FORMULATION AID, ES-5612 FORMULATION AID, ES-5300 FORMULATION AID, ES-5600 SILICONE GLYCEROLEMULSIFIER, ES-5700 FORMULATION AID, and ES-5800 FORMULATION AID (all from Dow Toray).

[0199] (F2) Examples of anionic surfactants include saturated or unsaturated fatty acid salts (such as sodium laurate, sodium stearate, sodium oleate, and sodium linolenate), alkyl sulfates, alkylbenzenesulfonic acids (such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, and dodecylbenzenesulfonic acid) and their salts, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyethylene alkyl sulfates, alkyl sulfosuccinates, polyoxyalkylene alkyl sulfosuccinate salts, polyoxyalkylene alkyl phenyl ether sulfates, alkanesulfonates, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, alkyl sulfonates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyalkylene alkyl ether acetates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, acyl glutamates, α-acyl sulfonates, alkyl sulfonates, alkyl allyl sulfonates, α-olefin sulfonates, alkyl naphthalenesulfonates, alkanesulfonates, alkyl or alkenyl sulfates, alkylamide sulfates, alkyl or alkenyl phosphates, alkylamide phosphates, alkanoylalkyl taurates, N-acyl amino acid salts, sulfosuccinates, alkyl ether carboxylates, amide ether carboxylates, α-sulfo fatty acid ester salts, alanine derivatives, glycine derivatives, and arginine derivatives. The salts include alkali metal salts such as sodium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as triethanolamine salts; and ammonium salts.

[0200] (F3) Examples of cationic surfactants include alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium bromide, distearyldimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di(POE) oleylmethylammonium chloride (2EO), benzalkonium chloride, alkylbenzalkonium chloride, alkyldimethylbenzalkonium chloride, benzethonium chloride, stearyldimethylbenzylammonium chloride, lanolin-derived quaternary ammonium salts, diethylaminoethyl stearate amide, dimethylaminopropyl stearate amide, amide propyl dimethyl hydroxypropyl ammonium behenate chloride, stearoylcholine carbamoylmethylpyridinium chloride, cetylpyridinium chloride, tall oil alkylbenzyl hydroxyethyl imidazolinium chloride, and benzyl ammonium salts.

[0201] (F4) Examples of nonionic surfactants include polyglyceryl diisostearate or diglyceryl polyhydroxystearate, isostearyl glyceryl ether, polyoxyalkylene ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene fatty acid diester, polyoxyalkylene resin acid ester, polyoxyalkylene (hydrogenated) castor oil, polyoxyalkylene alkylphenol, polyoxyalkylene alkylphenyl ether, polyoxyalkylene phenyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene alkyl ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan alkyl ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene sorbitol fatty acid ester, polyoxyalkylene glyceryl fatty acid ester, polyglyceryl alkyl ether, polyglyceryl fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, alkyl glucoside, polyoxyalkylene fatty acid bisphenyl ether, polypropylene glycol, diethylene glycol, polyoxyethylene / polyoxypropylene block polymer, alkyl polyoxyethylene / polyoxypropylene block polymer ether, polyoxyethylene / polyoxypropylene block polymer, alkyl polyoxyethylene / polyoxypropylene block polymer ether, and fluorine-based surfactants.

[0202] (F5)Examples of amphoteric surfactants include imidazoline type, amide-based betaine type, alkyl betaine type, alkylamide-based betaine type, alkylsulfobetaine type, amidesulfobetaine type, hydroxysulfobetaine type, carbonyl betaine type, phosphate ester betaine type, amino carboxylic acid type, and amide-based amino acid type amphoteric surfactants. Specific examples include imidazoline type amphoteric surfactants such as sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline and disodium 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethoxylate; alkyl betaine type amphoteric surfactants such as lauryl dimethylaminoacetate betaine and myristyl betaine; amide-based betaine type amphoteric surfactants such as coconut oil fatty acid amide propyl dimethylaminoacetate betaine, palm kernel oil fatty acid amide propyl dimethylaminoacetate betaine, tallow fatty acid amide propyl dimethylaminoacetate betaine, hardened tallow fatty acid amide propyl dimethylaminoacetate betaine, lauric acid amide propyl dimethylaminoacetate betaine, myristic acid amide propyl dimethylaminoacetate betaine, amide propyl dimethylaminoacetate palmitate betaine, amide dimethyl dimethylaminoacetate acetate betaine, and amide oleate propyl dimethylaminoacetate betaine; alkylsulfobetaine type amphoteric surfactants such as coconut oil fatty acid dimethylsulfopropyl betaine; alkylhydroxysulfobetaine type amphoteric surfactants such as lauryl dimethylamino hydroxysulfobetaine; and amide-based amino acid type amphoteric surfactants such as sodium N-lauroyl-N'-hydroxyethyl-N'-carboxymethylethylenediamine, sodium N-oleoyl-N'-hydroxyethyl-N'-carboxymethylethylenediamine, sodium N-cocoyl-N'-hydroxyethyl-N'-carboxymethylethylenediamine, potassium N-lauroyl-N'-hydroxyethyl-N'-carboxymethylethylenediamine, potassium N-oleoyl-N'-hydroxyethyl-N'-carboxymethylethylenediamine, sodium N-lauroyl-N-hydroxyethyl-N'-carboxymethylethylenediamine, sodium N-oleoyl-N-hydroxyethyl-N'-carboxymethylethylenediamine, sodium N-cocoyl-N-hydroxyethyl-N'-carboxymethylethylenediamine, monosodium N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine, monosodium N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine, monosodium N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine, disodium N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine, disodium N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine, and disodium N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine.

[0203] (F6) Examples of semi-polar surfactants include alkylamine oxide type surfactants, alkylamine oxides, alkylamidopropylamine oxides, and alkylhydroxyamine oxides, etc. Alkyl dimethylamine oxides having 10 to 18 carbon atoms and alkoxyethyl dihydroxyethylamine oxides having 8 to 18 carbon atoms are preferred. Specific examples include dodecyldimethylamine oxide, dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryldimethylamine oxide, myristyldimethylamine oxide, stearyldimethylamine oxide, isostearyldimethylamine oxide, alkyl dimethylamine oxide of coconut fatty acid, octanamidopropyldimethylamine oxide, decanamidopropyldimethylamine oxide, lauramidopropyldimethylamine oxide, myristamidopropyldimethylamine oxide, palmitamidopropyldimethylamine, stearamidopropyldimethylamine oxide, isostearamidopropyldimethylamine oxide, oleamidopropyldimethylamine oxide, ricinoleamidopropyldimethylamine oxide, 12-hydroxystearamidopropyldimethylamine oxide, alkyl dimethylamine oxide of coconut fatty acid amide, alkyl dimethylamine oxide of palm kernel oil fatty acid amide, alkyl dimethylamine oxide of castor oil fatty acid amide, lauramidoethyldimethylamine oxide, myristamidoethyldimethylamine oxide, alkyl dimethylamine oxide of coconut fatty acid amide, lauramidoethyldiethyamine oxide, myristamidoethyldiethyamine oxide, alkyl diethyamine oxide of coconut fatty acid amide, lauramidoethyldihydroxyethylamine oxide, myristamidoethyldihydroxyethylamine oxide, and alkyl dihydroxyethylamine oxide of coconut fatty acid amide.

[0204] There is no particular limitation on the amount of the surfactant (F) in the cosmetic composition of the present invention. However, in order to stabilize the cosmetic composition, it can be blended into the cosmetic composition in the range of 0.05% by weight to 90% by weight, preferably 0.1% by weight to 50% by weight, and more preferably 0.5% by weight to 25% by weight.

[0205] (G) Powder or Colorant

[0206] The cosmetic composition of the present invention can be blended with powders or colorants, especially powders commonly used in cosmetic products (including powders used as colorants and pigments). Powders or colorants commonly used in cosmetics can be used regardless of shape (spherical, rod-shaped, needle-shaped, plate-shaped, flake-shaped, irregular, spindle-shaped, bowl-shaped, raspberry-shaped, etc.), particle size (mist, fine particles, pigment grade, etc.) or particle structure (porous, non-porous, secondary aggregates, etc.). When these powders and / or colorants are used as pigments, one or more are preferably selected from inorganic pigment powders, organic pigment powders and resin powders having an average particle diameter in the range of 1 nm to 20 μm.

[0207] Examples of powders and pigments include inorganic powders, organic powders, surfactant metal salt powders (metal soaps), colored pigments, pearlescent pigments, metal powder pigments and silicone elastomer powders. These compounds can also be used. These powders and colorants can also be used as UV protection components.

[0208] Specific examples include inorganic powders such as titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lepidolite, silicic acid, silicon anhydride, aluminum silicate, sodium silicate, sodium magnesium silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstates, hydroxyapatite, vermiculite, aluminum hydroxide (higilite), bentonite, montmorillonite, lithium montmorillonite, zeolite, ceramic powder, calcium hydrogen phosphate, alumina, aluminum hydroxide, and boron nitride; organic powders such as polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, nylon 12, nylon 6, silicone powder, silicone rubber powder, silicone elastomer spherical powder coated with polymethylsilsesquioxane, polymethylsilsesquioxane spherical powder, styrene / acrylic copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenolic resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, and lauroyl lysine; surfactant metal salt powders such as zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetyl phosphate, calcium cetyl phosphate, and sodium cetyl phosphate; colored pigments include inorganic red pigments such as iron oxide red, iron oxide, iron hydroxide, and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as iron oxide yellow and loess; inorganic black pigments such as iron oxide black and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; inorganic blue pigments such as navy blue and ultramarine blue; tar-based lake pigments such as Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, and Orange No. 207, and lake natural pigments such as carminic acid, laccaic acid, carthamin, bradylin, and crocin;Pearlescent pigments such as titanium oxide-coated mica, titan mica, iron oxide-treated titan mica, titanium oxide-coated mica, bismuth oxychloride, bismuth oxychloride coated with titanium oxide, talc coated with titanium oxide, fish scale guanine, and titanium oxide-coated colored mica; and metal powder pigments such as metal powders of aluminum, gold, silver, copper, platinum, and stainless steel.

[0209] Silicone elastomer powder is a powdery component of the following (L) silicone elastomer. These powders are crosslinked products of linear diorganopolysiloxanes mainly composed of diorganosilanoxy units (D units). These powders can be obtained by subjecting an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom in the side chain or at the terminal and a diorganopolysiloxane having an unsaturated hydrocarbon group such as an alkenyl group in the side chain or at the terminal to a crosslinking reaction in the presence of a hydrosilylation reaction catalyst. The silicone elastomer powder is softer and more elastic than silicone resin powder composed of T units and Q units. Because they have excellent oil-absorbing properties, they can absorb the oil on the skin and prevent the cosmetic from disintegrating.

[0210] The silicone elastomer powder can take various shapes such as spherical shape, flat shape, or irregular shape. The silicone elastomer powder can be in the form of an oil dispersion. The cosmetic composition of the present invention can use the silicone elastomer powder in particulate form, wherein the primary particle size and / or the average primary particle size measured by the laser diffraction / scattering method under observation using an electron microscope is in the range of 0.1 μm to 50 μm. The silicone elastomer powder having primary particles of spherical shape can be effectively blended. Measured using a Type A durometer according to JIS K6253 "Testing methods for the hardness of vulcanized rubbers and thermoplastic rubbers", the silicone elastomer constituting the silicone elastomer powder preferably has a hardness of 80 or less, and more preferably 65 or less.

[0211] The silicone elastomer powder can be used in the cosmetic composition of the present invention in the form of an aqueous dispersion. Commercially available products of these aqueous dispersions include BY29-129 and PF-2001PIF emulsions from Dow Corning Toray.

[0212] The silicone elastomer powder can be surface-treated with a silicone resin or silica. Examples of the surface treatment are described in JP H02-243612A, JP H08-12545 A, JP H08-12546 A, JP H08-12524A, JP H09-241511A, JP H010-36219 A, JP H011-193331A, JP 2000-281523A, JP 2020-105330A, WO2019 / 124418, WO2020 / 137913, and WO2022 / 138346. Another example of the silicone elastomer powder is the crosslinked silicone powder listed in the "Cosmetic Classification and Blending Component Standards". Commercially available silicone elastomer powders include, for example, Tolefill E-5065, Tolefill E-508, 9701 cosmetic powder, and 9702 powder from DowCorning Toray.

[0213] It is preferable to perform a water-repellent treatment on some or all of the powders or colorants. This enables them to be stably blended in the oil phase. The powders or colorants can be blended and surface-treated with a general oil, a silicone compound other than the organopolysiloxane copolymer of the present invention, a fluorine compound, or a surfactant.

[0214] Examples of other waterproof treatments include treating the powders or colorants with various waterproof surface treatment agents. Examples include silicone treatments such as methylhydrogenpolysiloxane treatment, amino silicone treatment, silanol treatment, polyglycerol-functional silicone treatment, diglycerol-functional silicone treatment, silicone resin treatment, silicone rubber treatment, acrylic silicone treatment, and fluorinated silicone treatment; metal soap treatments such as zinc stearate treatment; silane treatments such as silane coupling agent treatment and alkylsilane treatment; fluorine compound treatments such as perfluoroalkylsilane, perfluoroalkyl phosphate salt, or perfluoropolyether treatment; amino acid treatments such as N-lauroyl-L-lysine treatment; oil treatments such as squalane treatment; and acrylic treatments such as acrylic alkyl ester treatment. These treatments can be used alone or in combination.

[0215] The powder or colorant is preferably treated with another powder dispersant or surface treatment agent. The dispersion or surface treatment can be carried out using the novel powder treatment agents or treatment methods proposed by the present inventors in WO 2009 / 022621 A, JP 2011-148784 A, JP 2011-149017 A, JP2011-246704 A, JP 2011-246705 A, JP 2011-246706 A, WO 2009 / 022621 A, WO 2011 / 049246 A, WO 2011 / 049248 A and Japanese Patent Application 2011-286973. It is also possible to use one of these novel powder treatment agents or treatment methods to slurrize the powder or colorant. Since these novel treatment agents improve properties such as improving the unique feel and dispersion stability, their combined use with the novel cosmetic materials of the present invention is expected to further improve the functionality, feel and storage stability of the cosmetics.

[0216] In addition, some or all of the powder or colorant can be hydrophilically treated. This enables the powder or colorant to be blended relative to the aqueous phase.

[0217] In addition, some or all of the powder or colorant can be hydrophobically and hydrophilically treated. This can impart emulsifying properties to the powder itself. An example of a commercially available product is MZY-500SHE from Teica.

[0218] If necessary, one or more (G) powders or colorants can be used in the cosmetic composition of the present invention. There is no particular limitation on the amount, but they can be blended in the range of 0.1% by mass to 99.5% by mass, and preferably 1% by mass to 99% by mass, relative to the entire cosmetic composition. In the case of solid powder cosmetics, the blending amount is preferably in the range of 80% by mass to 99% by mass relative to the entire cosmetic composition.

[0219] (H) Gelling Agent or Thickening Agent

[0220] The gelling agent is preferably oil-soluble. Specific examples include metal soaps such as aluminum stearate, magnesium stearate and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-din-butylamine; dextrin fatty acid esters such as dextrin palmitate, dextrin stearate and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; and benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol. These gelling agents can be used alone or in combination of two or more as needed.

[0221] (I) Organically Modified Clay Mineral

[0222] Examples of the organically modified clay minerals include dimethylbenzyldodecylammonium montmorillonite clay, dimethyldioctadecylammonium montmorillonite clay, dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, and magnesium aluminum silicate treated with distearyldimethylammonium chloride. Commercially available products include Benton 27 (hectorite treated with benzyldimethylstearylammonium chloride from NationalRed) and Benton 38 (hectorite treated with distearyldimethylammonium chloride from NationalRed).

[0223] (J) Silicone Resin

[0224] Silicone resins are organopolysiloxanes having a highly branched, network, or cage-like structure and are liquids or solids at room temperature. Any silicone resin commonly used in cosmetics can be used as long as it does not impair the object of the present invention. Solid silicone resins include MQ resins, MDQ resins, MTQ resins, MDTQ resins, TD resins, TQ resins, and TDQ, which combine monoorganosiloxane units (M units) (where the organic group is only a methyl group, or a methyl group and a vinyl group or a phenyl group), diorganosiloxane units (D units) (where the organic group is only a methyl group, or a methyl group and a vinyl group or a phenyl group), triorganosiloxane units (T units) (where the organic group is a methyl group, a vinyl group, or a phenyl group), and siloxane units (Q units). Examples include trimethylsiloxysilicic acid, polyalkylsiloxysilicic acid, trimethylsiloxysilicic acid containing dimethylsiloxane units, and alkyl(perfluoroalkyl)siloxysilicic acid. These silicone resins are oil-soluble, and preferably those silicone resins that can be dissolved in D4 and D5. The silicone resin forms a uniform film when applied to the skin and hair to prevent drying and low temperature. The silicone resin having these branched units adheres firmly to the skin and hair and imparts luster and translucency to the skin and hair.

[0225] (K) Silicone Gum

[0226] In the present invention, having 1,000,000 mm 2Organic polysiloxanes with an ultra-high viscosity of / s or greater are called silicone rubbers, but can be used as silicone oils. Silicone rubbers are linear diorganopolysiloxanes with a very high degree of polymerization and are also called raw silicone rubbers or organopolysiloxane rubbers. The difference between silicone rubbers and oily silicones is that due to their high degree of polymerization, they have a measurable degree of plasticity. Examples of raw silicone rubbers include substituted or unsubstituted organopolysiloxanes having dialkylsilyloxy units (D units), dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, and methylfluoroalkylpolysiloxane, or those raw silicone rubbers having a fine crosslinked structure of these polysiloxanes. A typical example is a compound represented by the general formula R 10 (CH 3 ) 2 SiO{(CH 3 ) 2 SiO} s {(CH 3 )R 11 SiO} t Si(CH 3 ) 2 R 10 (In this formula, R 11 is a group selected from a vinyl group, a phenyl group, an alkyl group having 6 to 20 carbon atoms, an aminoalkyl group having 3 to 15 carbon atoms, a perfluoroalkyl group having 3 to 15 carbon atoms, and an alkyl group containing a quaternary ammonium base having 3 to 15 carbon atoms, and the terminal R 10 is a group selected from an alkyl group having 1 to 8 carbon atoms, a phenyl group, a vinyl group, an aminoalkyl group having 3 to 15 carbon atoms, a hydroxyl group, and an alkoxy group having 1 to 8 carbon atoms, s = 2,000 to 6,000, t = 0 to 1,000, and s + t = 2,000 to 6,000.) Among them, dimethylpolysiloxane raw rubber with a degree of polymerization of 3,000 to 20,000 is preferred. These silicone rubbers can be added directly or in the form of a liquid rubber dispersion (oil dispersion of silicone rubber) dispersed in an oily silicone to the cosmetic composition of the present invention.

[0227] Examples of raw silicone rubbers include substituted or unsubstituted organopolysiloxanes having dialkylsilyloxy units (D units), dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, and methylfluoroalkylpolysiloxane, or those raw silicone rubbers having a fine crosslinked structure of these polysiloxanes. A typical example is a compound represented by the general formula R 10 (CH 3 ) 2 SiO{(CH 3 ) 2 SiO} s {(CH 3 )R12 SiO} t Si(CH 3 ) 2 R 10 The compound represented by. (In this formula, R 12 is a group selected from a vinyl group, a phenyl group, an alkyl group having 6 to 20 carbon atoms, an aminoalkyl group having 3 to 15 carbon atoms, a perfluoroalkyl group having 3 to 15 carbon atoms, and an alkyl group containing a quaternary ammonium base having 3 to 15 carbon atoms, and the terminal R 10 is a group selected from an alkyl group having 1 to 8 carbon atoms, a phenyl group, a vinyl group, an aminoalkyl group having 3 to 15 carbon atoms, a hydroxyl group, and an alkoxy group having 1 to 8 carbon atoms, s = 2,000 to 6,000, t = 0 to 1,000, and s + t = 2,000 to 6,000.) Preferably, an amino-modified methyl polysiloxane raw rubber having, for example, a 3-aminopropyl group or an N-(2-aminoethyl)-3-aminopropyl group at the side chain or terminal of the molecule. In the present invention, these silicone rubbers can be used alone or in combination of two or more as needed.

[0228] Since the silicone rubbers have a very high degree of polymerization, they form a durable protective film with excellent air permeability on the skin and hair. This enables the skin and hair to be given luster and a natural sheen, and texture and firmness are imparted to the skin and hair during and after use.

[0229] The amount of the silicone rubber added can range from 0.05% by weight (mass) to 30% by weight (mass) relative to the entire cosmetic composition, preferably in the range of 1% by weight (mass) to 15% by weight (mass). If the silicone rubber is used in the form of an emulsified composition prepared in advance using an emulsification step such as emulsion polymerization, it can be more easily and stably blended into the cosmetic composition of the present invention. If the amount of the silicone rubber is below the lower limit, it may not be sufficient to impart luster to the skin and hair.

[0230] (L) Silicone Elastomer

[0231] The silicone elastomer can be blended with the cosmetic composition in any form according to the intended purpose. In addition to the silicone elastomer powder described above in the (G) Powder or Colorant section, silicone elastomers in the form of crosslinkable organopolysiloxanes are preferably blended. The silicone elastomer powder can also be used in the cosmetic composition of the present invention in the form of an aqueous dispersion. Commercially available aqueous dispersions include, for example, BY 29-129 and PF-2001PIF emulsions from Dow Corning Toray. From the viewpoint of further improving the feel of the cosmetic composition of the present invention during use, blending in the form of an aqueous dispersion (i.e., a suspension) in these silicone elastomer powders is extremely useful.

[0232] An unemulsifiable crosslinkable organopolysiloxane is preferably used which has a structure in which the organopolysiloxane chains are three-dimensionally crosslinked in the reaction with the crosslinkable component and does not have hydrophilic components such as polyoxyalkylene units. These crosslinkable organopolysiloxanes can be used without limitation, regardless of the manufacturing method (such as dilution) and physical form (such as its properties). Particularly preferred examples include the a,w-diene crosslinked silicone elastomers described in U.S. Patent 5,654,362 (which can be commercially obtained from Dow Corning in the United States in the form of DC 9040 silicone elastomer blend, DC 9041 silicone elastomer blend, DC 9045 silicone elastomer blend, and DC 9046 silicone elastomer blend). Crosslinkable organopolysiloxanes having fluidity at room temperature can also be used. One example is 3901 LIQUID SATIN BLEND (Dow Chemical in the United States).

[0233] (M) Organically Modified Silicone

[0234] These organomodified silicones are preferably lipophilic. Specific examples include amino-modified silicones, amino polyether-modified silicones, epoxy-modified silicones, carboxyl-modified silicones, amino acid-modified silicones, methanol-modified silicones, acrylic acid-modified silicones, phenol-modified silicones, amide group alkyl-modified silicones, amino diol-modified silicones, and alkoxy-modified silicones. In addition to the polysiloxane bond as the main chain, these organomodified silicones can have an alkylene chain, an amino alkylene chain, or a polyether chain to the extent that the compound does not have hydrophilicity. The organomodifying groups can be in the side chain and / or at the end of the polysiloxane chain. When the cosmetic composition of the present invention is a hair care product, amino-modified silicones, methanol-modified silicones, amino polyether-modified silicones, or amino diol-modified silicones can be used. One example is an amino-modified silicone having a 3-aminopropyl group or an N-(2-aminoethyl)-3-aminopropyl group.

[0235] The following is a description of higher alkyl-modified silicones, alkyl-modified silicone resins, and polyamide-modified silicone resins, which are preferred examples of organically modified silicones. Higher alkyl-modified silicones are waxy at room temperature and are useful components as raw materials in cosmetics. Therefore, they can be advantageously used in the cosmetics of the present invention. Examples of higher alkyl-modified silicone waxes include methyl long-chain alkyl polysiloxanes capped at both ends of the molecular chain with trimethylsilyloxy groups, dimethyl polysiloxane / methyl long-chain alkyl siloxane copolymers capped at both ends of the molecular chain with trimethylsilyloxy groups, and long-chain alkyl-modified dimethyl polysiloxanes capped at both ends of the molecular chain. Commercially available products include AMS-C30 cosmetic grade wax and 2503 cosmetic grade wax (from Dow Chemical, USA).

[0236] In the cosmetic composition of the present invention, from the viewpoints of more durable makeup and higher temperature stability, the higher alkyl-modified silicone wax preferably has a melting point of 60 °C or higher.

[0237] Alkyl-modified silicone resins impart sebum resistance, moisturizing properties, and a delicate texture to cosmetics. Those silicones that are preferably waxy at room temperature are preferred. Preferred examples are the silsesquioxane resin waxes described in JP 2007-532754 A. A commercially available product is SW-8005C30 RESIN WAX (from Dow Chemical, USA).

[0238] Examples of polyamide-modified silicones include, for example, silicone-based polyamide compounds described in U.S. Patent 5,981,680 (JP 2000-038450A) and JP 2001-512164 A. Commercially available products include 2-8178 gelling agent and 2-8179 gelling agent (from Dow Chemical, USA). These polyamide-modified silicones are also used as thickeners / gelling agents for oily raw materials, especially silicone oils.

[0239] (N) UV Protection Component

[0240] The UV protection components include organic UV protection components and inorganic UV protection components. When the cosmetic composition of the present invention is a sunscreen cosmetic, it is preferable to use at least one type of organic or inorganic UV protection component, and it is particularly preferable to use organic UV protection components. The solvent-soluble solid particles of the present invention are generally compatible with poorly soluble organic ultraviolet protection components such as diethylhexyl butamido triazone (Ubinal A), bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene), and cinnamic acid-based UV absorbers, and these components can improve the blending stability of the solvent-soluble solid particles of the present invention.

[0241] The inorganic ultraviolet protection components include inorganic pigment powders and metal powder pigments blended in the form of ultraviolet dispersants. Examples include metal oxides such as titanium oxide, zinc oxide, cerium oxide, lower titanium oxide, and iron-doped titanium oxide; metal hydroxides such as iron hydroxide; metal flakes such as plate-like iron oxide and aluminum flakes; and ceramics such as silicon carbide. Among them, at least one selected from particulate, plate-like, needle-like, or fibrous fine particles of metal oxides and metal hydroxides with an average particle size in the range of 1 nm to 100 nm is preferred. These powders can be subjected to one or more surface treatments commonly used in the art. Examples include fluorine compound treatment (preferably perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, and fluorinated silicone resin treatment), silicone treatment (preferably methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, and gaseous tetramethyltetrahydrocyclotetrasiloxane treatment), silicone resin treatment (preferably trimethylsilyloxy silicate treatment), side chain treatment (a method of adding an alkyl chain, etc. after gaseous silicone treatment), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (preferably alkylsilane or alkylsilazane treatment), oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment (preferably with stearic acid or myristate), acrylic resin treatment, and metal oxide treatment. In another example, after coating the surface of the fine particles with a metal oxide such as silica or alumina, the surface of the fine titanium oxide particles is treated with an alkylsilane. The amount of the surface treatment is preferably in the range of 0.1% by mass to 50% by mass relative to the total mass of the powder.

[0242] Organic UV protection components are lipophilic UV protection components. Examples include benzoic acid-based UV absorbers such as p-aminobenzoic acid (PABA), PABA monoglyceride, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, and hexyl diethylamino hydroxybenzoyl benzoate; anthranilic acid-based UV absorbers such as homomenthyl N-acetylanthranilate; salicylic acid-based UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropylphenyl salicylate; cinnamic acid-based UV absorbers such as octyl cinnamate, ethyl 4-isopropylcinnamate, methyl 2,5-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, methyl 2,4-diisopropylcinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate, mono-2-ethylhexanoyl-di-p-methoxycinnamoyl glycerol, and 3-methyl-4-[methylbis(trimethylsilyloxy)silyl]butyl 3,4,5-trimethoxycinnamate; benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl 4'-phenyl-benzophenone-2-carboxylate, 4-hydroxy-3-carboxybenzophenone, and 4-hydroxy-3-carboxybenzophenone; and other UV absorbers such as 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, urocanic acid, ethyl urocanate, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, dibenzylideneazine, dianisoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, and 5-(3,3-dimethyl-2-norbornene)-3-pent-2-one.

[0243] These organic UV protection components can also be incorporated into hydrophobic polymer powders. The polymer powders can be hollow, have an average primary particle size in the range of 0.1 μm to 50 μm, and have a broad or narrow particle size distribution. The polymers used herein can be acrylic resins, methacrylic resins, styrene resins, polyurethane resins, polyethylene, polypropylene, polyethylene terephthalate, silicone resins, nylon, acrylamide resins, or silylated polypeptide resins. Polymer powders containing 0.1% to 30% by mass of the organic UV protection components are preferred, and polymer powders containing the UV-A absorber 4-tert-butyl-4'-methoxybenzoylmethane are particularly preferred.

[0244] These organic UV protection components can also be dispersed in water. An example of such a commercially available product is Tinosorb A2B (from BASF).

[0245] In the cosmetic compositions of the present invention, at least one type of UV protection component selected from the group consisting of fine particle titanium oxide, fine particle zinc oxide, 2-ethylhexyl p-methoxycinnamate, 4-tert-butyl-4'-methoxybenzoylmethane, hexyl diethylamino hydroxybenzoyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and benzophenone UV absorbers can be used. These UV protection components are widely used and easily available, and have a high UV protection effect. A combination of organic and inorganic UV protection components is preferred, and a combination of a UV protection component corresponding to UV-A and a UV protection component corresponding to UV-B is particularly preferred.

[0246] (O) Water-Soluble Polymer

[0247] The cosmetic composition of the present invention may also be an aqueous emulsion containing a large amount of water-soluble components, and preferably the incorporated (O) water-soluble polymer depends on the formulation. One or more water-soluble polymers may be used. Examples of water-soluble polymers include plant polymers such as gum arabic, tragacanth, galactan, guar gum, long bean gum, karaya gum, carrageenan, pectin, agar, rowanberry (rowan), algin (brown algae extract), starch (rice, corn, potato, wheat), and glycyrrhizic acid; microbial polymers such as xanthan gum, dextran, succinoglucan, and pullulan; and animal polymers such as collagen, casein, albumin, and gelatin. Examples of semi-synthetic water-soluble polymers include starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; cellulose polymers such as methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose (CMC), crystalline cellulose, and cellulose powder; and alginic acid-based polymers such as sodium alginate and propylene glycol alginate. Examples of synthetic water-soluble polymers include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether polymer, polyvinylpyrrolidone, and carboxyvinyl polymer (CARBOPOL 940 and 941 from BF Goodrich); polyoxyethylene polymers such as polyethylene glycol 20,000, polyethylene glycol 6,000, and polyethylene glycol 4,000; copolymers such as polyoxyethylene polyoxypropylene copolymer and PEG / PPG methyl ether; acrylic polymers such as sodium polyacrylate, ethyl polyacrylate, and polyacrylamide; polyethyleneimine; and cationic polymers. Other cationic water-soluble polymers that can be particularly used in hair care products include quaternary nitrogen-modified polysaccharides (cationic-modified cellulose, cationic-modified hydroxyethyl cellulose, cationic-modified guar gum, cationic-modified locust bean gum, cationic-modified starch, etc.), dimethyldiallylammonium chloride derivatives (such as dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylene piperidinium chloride, etc.), and vinylpyrrolidone derivatives (such as vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer salt, vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.).

[0248] Other components commonly used in the art can be added to the cosmetic composition of the present invention within the range that does not impair the effects of the present invention. Examples include organic resins, humectants, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH regulators, chelating agents, cooling agents, anti-inflammatory agents, skin beautifying components (whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, and inclusion compounds. Specific examples are listed in paragraphs 0100 to 0113 of JP 2011-149017 A, but the present invention is not limited to these examples.

[0249] The cosmetic composition of the present invention can be blended with natural plant extract components, seaweed extract components, and herbal components according to the intended use. Two or more of these components can also be used. Specific examples are listed in paragraph 0115 of JP 2011-149017A, but the present invention is not limited to these examples.

[0250] The cosmetic composition of the present invention can be blended with solvents other than pure water or mineral water, such as light isoparaffin, ether, LPG, N-methylpyrrolidone, or next-generation fluorocarbons, according to the intended use.

[0251] In addition to the copolymer of the present invention, the cosmetic composition of the present invention may further contain at least one type selected from the group consisting of acrylic silicone dendrimer copolymers and alkyl-modified silicone resin waxes. These substances are film-forming components similar to the copolymer of the present invention, but different from the copolymer of the present invention, they do not improve washability. Therefore, they should be used within the range that does not impair the technical effects of the present invention.

[0252] Preferred examples of acrylic silicone dendrimer copolymers are vinyl polymers having a carbosiloxane dendrimer structure in the side chain, as described in Japanese Patent 4,009,382 (JP 2000-063225A). Examples of commercially available products include FA 4001CM silicone acrylate and FA 4002ID silicone acrylate from Dow Corning Toray.

[0253] Preferred examples of alkyl-modified silicone resin waxes are silsesquioxane resin waxes as described in JP 2007-532754 A.

[0254] The cosmetic composition of the present invention can take the form of a liquid, emulsion, cream, solid, paste, gel, powder, multi-layer emulsion, mousse, or spray.

[0255] [Preparation Method of Cosmetic Composition]

[0256] The cosmetic composition of the present invention can be prepared by a method including the step of preparing a solution or dispersion of the above solid particles into at least one cosmetic liquid medium.

[0257] As the cosmetic liquid medium, any cosmetic liquid medium commonly used in cosmetics can be used alone or in combination with other cosmetic liquid media, as long as it does not impair the purpose of the present invention. Preferably, the cosmetic liquid medium is at least one selected from alcohols, esters, silicone fluids, hydrocarbon oils, fatty acid ester oils, liquid UV protectants, and mixtures thereof.

[0258] As an exemplary alcohol, any alcohol disclosed in the section of “(E) Alcohols” can be used, as long as it does not impair the purpose of the present invention.

[0259] As an exemplary ester, any conventional ester solvent such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate can be used, as long as it does not impair the purpose of the present invention.

[0260] As an exemplary silicone fluid, any silicone oil disclosed in the section of “(D1) Silicone Oils” can be used, as long as it does not impair the purpose of the present invention.

[0261] As an exemplary hydrocarbon oil, any hydrocarbon oil exemplified above as the hydrocarbon oil (D2-1) can be used, as long as it does not impair the purpose of the present invention.

[0262] As an exemplary fatty acid ester oil, any fatty acid ester oil exemplified above as the fatty acid ester oil (D2-2) can be used, as long as it does not impair the purpose of the present invention.

[0263] As an exemplary liquid UV protectant, any reagent disclosed in the section of “(N) UV Protection Components” can be used, as long as it does not impair the purpose of the present invention.

[0264] More preferably, when the above solid particles are applied / formulated into the cosmetic composition, a liquid UV protectant or a mixture of cosmetic liquid media containing a liquid UV protectant is expected to be used as the medium. As an exemplary liquid UV protectant, there is OMC: ethylhexyl methoxycinnamate ( MC 80, BASF).

[0265] In addition, since the solvent-soluble solid particles of the present invention have excellent solubility and easy handling properties as cosmetic ingredients, they can also be used in non-cosmetic products such as topical preparations, paints, coating agents, defoamers, and deodorants.

[0266] [Examples]

[0267] The following is a more detailed description of the present invention with reference to the exemplary embodiments. However, the present invention is not limited to these embodiments.

[0268] [Calculation of Glass Transition Point]

[0269] The glass transition point of the vinyl-based copolymer is calculated using the FOX formula. The FOX formula for the glass transition point (Tg) is as follows.

[0270] Tg is determined by the Fox formula (Source: Radical Polymerization Handbook, P 566 (1999))

[0271]

[0272] (Wn: monomer weight, Tgn: Tg of the homopolymer of monomer n, unit: K)

[0273] [Particle Size]

[0274] For the emulsion, the particle size is determined by Beckman Coulter DelsaNano C in the form of D(50).

[0275] For the solid size, the size is determined by the mesh size of the sieve (JIS Z 8801) or an optical microscope.

[0276] [Contact Angle (Water)]

[0277] The IPA solution of the vinyl-based copolymer is coated on a glass plate, and then the solvent is removed by drying at room temperature, and a coating film of the vinyl-based polymer is obtained. A 5 μL water droplet is placed on the surface of the coating film, and the contact angle with water is measured. A droplet shape analysis system (KRUSS DSA10 Mk-2) is used as the measuring device, and the average value with n = 5 or more is determined.

[0278] [Contact Angle (Artificial Sebum)]

[0279] The IPA solution of the vinyl-based copolymer is coated on a glass plate, and then the solvent is removed by drying at room temperature, and a coating film of the vinyl-based polymer is obtained. A 5 μL droplet of artificial sebum (a mixture of triolein:oleic acid:squalene = 3:1:1) is placed on the surface of the coating film, and the contact angle with respect to the artificial sebum is measured. A droplet shape analysis system (KRUSS DSA10 Mk-2) is used as the measuring device, and the average value with n = 5 or more is determined.

[0280] [Aggregation]

[0281] After loading 1 g of the sample into a 20 cc vial and sealing it, the vial was placed in an oven at 40 °C for 30 minutes. After that, the vial was placed on its side and the appearance of the vial was evaluated. An amount of adhesion to the inner wall of less than 10% was designated as "less", an adhesion amount of 10% - 25% was designated as "some", and an adhesion amount of 50% or more was designated as "much".

[0282] Since many curing processes are exothermic or heated, agglomeration is a problem and less agglomeration is required in this test.

[0283] [Solubility Test]

[0284] After loading 0.5 g of the sample and 2 g of oil into a 20 cc vial and sealing it, the vial was placed in an oven at 50 °C. This portion was mixed with a dental mixer for 10 seconds every 5 minutes. Then, the time for complete dissolution was recorded.

[0285] [Synthesis Example 1][Copolymer Intermediate 1 (CI-1)]

[0286] 16.3 kg of isopropyl alcohol (IPA) was placed into a 100 - liter four - necked flask equipped with a stirring device, a thermometer, and a reflux tube. The mixture was bubbled with nitrogen, then thoroughly degassed and heated to 70 °C. 7.6 kg (38 wt%) of methyl methacrylate (MMA), 2.4 kg (12 wt%) of n - butyl acrylate (BA), 10.0 kg (50 wt%) of a carbosiloxane dendrimer monomer represented by the following formula (A - 1):

[0287]

[0288] 440 g (2.2 wt%) of 2,2'-azobis - 2 - methylpropionitrile (V - 601, manufactured by Wako Pure Chemical Industries, Ltd.) and 10.7 kg of IPA were introduced and dissolved in a dropping funnel.

[0289] In a nitrogen atmosphere, the monomer mixture was added dropwise through the dropping funnel over 1 hour while maintaining at 70 °C. After the addition was complete, heating and stirring were carried out in a nitrogen atmosphere for 8 hours to obtain a reaction product with a non - volatile content of 40.6%.

[0290] [Synthesis Examples 2 to 7][CF-2 to 7]

[0291] The copolymer in the solvent was prepared in the same manner as in Example 1, except that the monomer raw materials / radical initiator / solvent and weight% in Example 1 were changed as shown in Tables 1 to 5 below. The abbreviations used in the table are as follows:

[0292] Component (A) :

[0293] A-2:

[0294]

[0295] A-3: MCR-M11 (Gelest Inc.)

[0296]

[0297] A-4:

[0298]

[0299] Component (B) :

[0300] BA: n-Butyl acrylate

[0301] MMA: Methyl methacrylate

[0302] [Synthesis Example 8][Copolymer Intermediate 8 (CI-8)]

[0303] [Monomer Emulsification]

[0304] In the first beaker, weigh 5.4 g (1.79 wt%) of ECOSURF EH-40 (75% 2-ethylhexanol EO-PO nonionic surfactant aqueous solution, Dow) and 181 g (60.35 parts by weight) of ion-exchanged water and stir to form an aqueous solution. In the second beaker, weigh 0.06 g (0.02 parts by weight) of 2-phenoxyethanol, 0.22 g (0.07 parts by weight) of 2,4-diphenyl-4-methyl-1-pentene, 46.3 g (15.42 parts by weight) of methyl methacrylate, 4.02 g (1.34 parts by weight) of butyl acrylate, and 50.3 g (16.76 parts by weight) of A-1 and homogenize them. After feeding the mixture in the second beaker into the first beaker and stirring for a few minutes, using a homogenizer, pass the contents through a pressure of 300 kg / cm2 to 400 kg / cm2 multiple times to obtain a milky white monomer emulsion. D50 is 144 nm, and it is stable without any phase separation.

[0305] [Free Radical Polymerization]

[0306] In a separable flask, the monomer emulsion obtained above was charged and heated to 45 °C while stirring the mixture. After the temperature reached 45 °C, an aqueous solution of 0.12 g (0.04 parts by weight) of 1% iron(II) sulfate heptahydrate and an aqueous solution of 0.15 g (0.05 parts by weight) of 0.1% sodium ethylenediaminetetraacetate tetrahydrate were added to the mixture in the flask. Thereafter, 6.03 g (2.01 parts by weight) of a 1.5% aqueous solution of tert-butyl hydroperoxide and 6.44 g (2.15 parts by weight) of a 1.5% aqueous solution of d-isoascorbic acid were gradually added dropwise separately and simultaneously to allow the reaction to proceed. After 2 hours, a silicone acrylate aqueous dispersion (CI-8) was obtained after filtration. The non-volatile content of 1 g at 150 °C after 1 hour was 98.4%. The Mw measured by THF-GPC was 116,000.

[0307] [Synthesis Example 9][Copolymer Intermediate 9 (CI-9)]

[0308] [Monomer Emulsification]

[0309] In the first flask, 2.12 g (0.705 parts by weight) of Phosten HLP-1 (90% aqueous solution of lauryl polyoxyethylene ether-1 phosphate, Nikko Chemicals), 1.2 g (0.4 parts by weight) of a 20% aqueous solution of sodium hydroxide, and 167.5 g (55.825 parts by weight) of ion-exchanged water were weighed and stirred to form an aqueous solution. In the second beaker, 2.70 g (0.9 parts by weight) of 2-phenoxyethanol, 29.7 g (9.9 parts by weight) of methyl methacrylate, 15.3 g (5.1 parts by weight) of butyl acrylate, and 45.0 g (15 parts by weight) of A-1 were weighed and homogenized. After feeding the mixture in the second beaker into the first beaker and stirring for a few minutes, the contents were passed through a pressure of 300 kg / cm2 to 400 kg / cm2 several times using a homogenizer to obtain a milky monomer emulsion.

[0310] [Free Radical Polymerization]

[0311] In a separable flask, the monomer emulsion obtained above was charged and heated to 80 °C while stirring the mixture. After the temperature reached 80 °C, 22.5 g (7.5 parts by weight) of a 3% aqueous potassium persulfate solution prepared with ion-exchanged water was gradually added dropwise simultaneously to allow the reaction to proceed. After reacting for 3 hours, 13.5 g (4.5 parts by weight) of a 5% VA-057 (2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate) aqueous solution prepared with ion-exchanged water was added. After 3 hours, 0.51 g (0.17 part by weight) of aminopropanediol was added. After filtration, a silicone acrylate aqueous dispersion (CI-9) was obtained. The D50 was 98 nm, and it was stable without any phase separation. The non-volatile content of 1 g at 150 °C after 1 hour was 30.8%.

[0312] [Synthesis Example 10][Copolymer Intermediate 10 (CI-10)]

[0313] [Monomer Emulsification]

[0314] In the first flask, 2.11 g (0.704 parts by weight) of Phosten HLP-1 (90% aqueous solution of lauryl polyoxyethylene ether-1 phosphate, Nikko Chemicals), 1.18 g (0.394 parts by weight) of a 20% aqueous sodium hydroxide solution, and 168.2 g (56.067 parts by weight) of ion-exchanged water were weighed and stirred to form an aqueous solution. In the second beaker, 1.80 g (0.6 parts by weight) of 2-phenoxyethanol, 29.7 g (9.9 parts by weight) of methyl methacrylate, 15.3 g (5.094 parts by weight) of butyl acrylate, and 44.9 g (14.983 parts by weight) of A-4 were weighed and homogenized. After feeding the mixture in the second beaker into the first beaker and stirring for a few minutes, the contents were passed through a pressure of 300 kg / cm2 to 400 kg / cm2 several times using a homogenizer to obtain a milky white monomer emulsion.

[0315] [Free Radical Polymerization]

[0316] In a separable flask, the monomer emulsion obtained above was charged and heated to 80 °C while stirring the mixture. After the temperature reached 80 °C, 22.5 g (7.5 parts by weight) of an aqueous solution of 3% potassium persulfate prepared with ion-exchanged water was gradually added dropwise simultaneously to allow the reaction to proceed. After reacting for 3 hours, 13.5 g (4.5 parts by weight) of an aqueous solution of 5% VA-057 (2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate) prepared with ion-exchanged water was added. After 3 hours, 0.54 g (0.18 part by weight) of aminopropanediol was added. After filtration, a silicone acrylate aqueous dispersion (CI-10) was obtained. The D50 was 129 nm, and it was stable without any phase separation.

[0317] Table 1. Copolymer Intermediates (CI Samples)

[0318]

[0319] V-601: 2,2'-azobis-2-methylpropionate (Fujifilm Wako Chemical Corporation)

[0320] AIBN: 2,2'-azobis(isobutyronitrile) (Fujifilm Wako Chemical Corporation)

[0321] t-BHP: Luperox TBH70X (70 wt% H 2 O solution, Sigma-Aldrich)

[0322] VA-057: 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (Fujifilm Wako Chemical Corporation)

[0323] Potassium persulfate: Potassium persulfate (Fujifilm Wako Chemical Corporation)

[0324] ECOSURF EH-40: 75% aqueous solution of 2-ethylhexanol EO-PO nonionic surfactant (Dow Chemical)

[0325] Phosten HLP-1: 90% aqueous solution of lauryl polyoxyethylene ether-1 phosphate (Nikko Chemicals)

[0326] EDTA·4H 2O: Sodium ethylenediaminetetraacetate tetrahydrate (Tokyo Chemical Industry Co., Ltd.)

[0327] IAA: d-Isoascorbic acid (Sigma-Aldrich)

[0328] KOH: Sodium hydroxide (Fujifilm Wako Chemical Corporation)

[0329] AMPD: 2-Amino-2-methyl-1,3-propanediol (Fujifilm Wako Chemical Corporation)

[0330] [Practical Example 1]

[0331] [Solid Copolymer 1] (Ground)

[0332] Charge 100 g of copolymer intermediate 1 (CI-1) into a single-necked flask. Place the flask on a rotary evaporator equipped with a vacuum pump. Remove IPA, residual monomers, and volatiles from CI-1 by vacuum stripping at 110 °C - 130 °C. Thereafter, 39 g of a solid polymer block is obtained. Grind the polymer block into beads using a crusher (Osaka Chemical Wonder, Crusher WC-3). 28 g of 250 μm - 500 μm beads are obtained after sieving.

[0333] [Practical Example 2]

[0334] [Solid Copolymer 2] (Pellets)

[0335] Before the test, adjust the polymer concentration of CI-1 to a 40 wt% concentration.

[0336] Construct the granulation process by connecting an extruder and a strand pelletizer. Set up a strand bath between the extruder and the strand pelletizer to cool the molten strand. Feed 20 kg of CI-1 (8 kg solid) into the extruder heated to 100 °C at a constant rate of 5 kg / h. After removing volatiles in the extruder, extrude the molten copolymer from the extruder using a strand die with holes having a diameter of 1.5 mm. The melt solidifies when passing through the strand bath where 25 °C water is applied. After applying the strand pelletizer, a pellet sample in the form of length is obtained.

[0337] [Practical Example 3]

[0338] [Solid Copolymer 3] (Spray-Dried)

[0339] Before the experiment, the polymer concentration of CI-1 was adjusted to a concentration of 32 wt%.

[0340] The spray dryer was constructed with an air flow feed rate = 3.5 Nm3 / min and an inlet temperature = 50 °C. 500 g of 32% CI-1 (160 g as solid) was loaded into the liquid component tank and fed into the two-fluid nozzle at a feed rate of 2.0 kg / h. The IPA feed rate was determined to keep the IPA vapor concentration below 20% LEL. The resulting outlet temperature was 28 °C - 31 °C. After that, 133 g of solid was obtained. Optical microscopy showed that the primary powder size was 20 μm - 30 μm.

[0341] [Comparative Example 1]

[0342] [Solid Copolymer CE1] (Large Pellets)

[0343] Before the experiment, the polymer concentration of CI-1 was adjusted to a concentration of 40 wt%.

[0344] The granulation process was constructed by connecting an extruder and a strand pelletizer. A strand bath was set between the extruder and the strand pelletizer to cool the molten strand. 20 kg of CI-1 (8 kg as solid) was constantly fed into the extruder heated to 100 °C at 5 kg / h. After removing volatiles in the extruder, the molten copolymer was extruded from the extruder using a strand die with holes of 5 mm in diameter. The melt solidified when passing through the strand bath where 25 °C water was applied. After applying the strand pelletizer, pellet samples in the form of length were obtained.

[0345] Before the experiment, the concentration of CI-1 was adjusted to a concentration of 40 wt% with IPA.

[0346] [Comparative Example 2]

[0347] [Solid Copolymer CE2] (Ground)

[0348] 100 g of CI-2 was loaded into a single-neck flask. The flask was placed on a rotary evaporator equipped with a vacuum pump. Ethyl acetate, residual monomers, and volatiles in CI-2 were removed by vacuum stripping at 110 °C - 130 °C. After that, 39 g of solid polymer block was obtained. The polymer block was ground into small beads using a crusher (Osaka Chemical Wonder, Crusher WC-3). 20 g of 250 μm - 500 μm beads were obtained after sieving.

[0349] [Comparative Example 3]

[0350] [Solid Copolymer CE3]

[0351] 100 g of CI-3 was charged into a single-necked flask. The flask was placed on a rotary evaporator equipped with a vacuum pump. Toluene, residual monomers, and volatiles in CI-3 were removed by vacuum stripping at 110 °C - 130 °C. Thereafter, 38.5 g of a solid polymer block was obtained. The polymer block was ground into small beads using a crusher (Osaka Chemical Wonder, Crusher WC-3). After sieving, 14.2 g of 250 μm - 500 μm beads were obtained. Some aggregated blocks remained on the sieve.

[0352] [Investigation 1]

[0353] [Size]

[0354] From the comparison among PE1, PE2, PE3, and CE1, larger sizes could not be dissolved in isododecane within 30 min or less. Since solubility affects productivity and energy consumption, a size less than 10 mm as the longest side is favorable.

[0355] [Si% and Tg]

[0356] From the comparison between PE1 and CE2, no Si% could not be dissolved in isododecane. In addition, the repellency performance was very low, indicating insufficient durability.

[0357] From the comparison between PE1 and CE3, a low Tg caused aggregation in the aggregation test. Since the curing process requires low aggregation, a higher Tg is needed.

[0358] Table 2. Solid Polymer Samples 1 (PE: Practical Example, CE: Comparative Example)

[0359]

[0360] [Practical Examples 4 - 7]

[0361] Samples were prepared in the same manner as in Example 1 or 3, except that the copolymer intermediate, weight %, and curing process of Example 1 were changed as shown in Table 3 below. Comparative Example 2 was the same as above.

[0362] [Consideration 2]

[0363] [Silicone Portion]

[0364] From the comparison among PE4 - PE7, various silicone structures enabled easy solubility in various oils suitable for cosmetics. At this time, polyacrylate without a silicone moiety was insoluble in those oils. Silicone contributed to compatibility with various oils.

[0365] Table 3. Solid Polymer Samples 2 (PE: Practical Example, CE: Comparative Example)

[0366]

[0367]

[0368] IPA: 2 - Propanol (Fujifilm Wako Chemical Corporation)

[0369] EA: Ethyl Acetate (Fujifilm Wako Chemical Corporation)

[0370] EtOH: Ethanol (Fujifilm Wako Chemical Corporation)

[0371] SH 245: Decamethylcyclopentasiloxane (DOWSIL TM SH 245Fluid, Dow Toray Co., Ltd.)

[0372] PDMS, 2cst: Polydimethylsiloxane (DOWSIL TM SH 200C Fluid 2cs, Dow Toray Co., Ltd.)

[0373] FZ - 3196: Octanoyl polymethylsiloxane (DOWSIL TM FZ - 3196Fluid, Dow Toray Co., Ltd.)

[0374] SH 556: Polyphenyltrimethylsiloxane (DOWSIL TM SH 556Fluid, Dow Toray Co., Ltd.)

[0375] IDD: Isododecane (PUROLAN IDD, LANXESS Distribution GmbH)

[0376] Cetiol ultimate: Undecane and Tridecane ( Ultimate, BASF Japan)

[0377] TKG: Glyceryl Tri - caprylate / Caprate (FineNeo - MCT, Nippon Fine Chemical)

[0378] OMC: Ethylhexyl Methoxycinnamate ( MC 80, BASF)

[0379] Butyl acetate: Butyl acetate (Fujifilm Wako Chemical Corporation)

[0380] [Practical Examples 8 - 9]

[0381] Samples were prepared in the same manner as in Example 1 or 3, except that the copolymer intermediate, weight %, and curing process in Example 1 were changed as shown in Table 3 below. Comparative Example 2 was the same as above.

[0382] [Investigation 3]

[0383] [Crosslinking]

[0384] Crosslinked copolymers obtained from two or more (meth)acryloyl-functional silicones cannot be prepared after solution polymerization due to gelling. Mini-emulsion polymerization (CI-10) was employed. From the comparison between PE8 - PE9 and CE4, the crosslinked structure cannot form a film after drying and cannot dissolve after isododecane, SH 556, and TKG.

[0385] Table 4. Solid Polymer Samples 3

[0386]

[0387] [Cosmetic Preparation Examples]

[0388] [Practical Example 10] Sunscreen Spray

[0389]

[0390] [Practical Example 11] Loose Powder Containing Active Substances

[0391]

[0392] [Practical Example 12] Sunscreen Powder

[0393]

[0394] [Practical Example 13] Glitter Powder, Heat Powder, Hair Thickening Powder

[0395]

[0396] [Practical Example 14] Antiperspirant and Deodorant Powder

[0397]

[0398] [Practical Example 15] Antiperspirant and Deodorant Powder

[0399]

[0400] [Practical Example 16] Antiperspirant and Deodorant Spray

[0401]

[0402] [Practical Example 17] Pressed Powder

[0403]

[0404] [Practical Example 18] Colored Ink

[0405]

[0406] A similar preparation can be used after a temporary hair coloring spray.

[0407] [Example 19 of Practice] Acne treatment gel

[0408]

[0409] [Practical Example 20] Anti-Aging Firming and Lifting Essence

[0410]

[0411] [Practical Example 21] Perfume Spray / Gel / Ointment / Stick

[0412]

[0413] [Practical Example 22] W / O Cream

[0414]

[0415] [Practical Example 23] O / W Cream

[0416]

Claims

1. A solid particle substantially composed of a silicone-functional copolymer, the silicone-functional copolymer being polymerized from a monomer composition substantially composed of (A) one or more unsaturated polymerizable monomers having at least one silicone functional group and one polymerizable group in the molecule and (B) one or more unsaturated polymerizable monomers having no silicon atom or having one silicon atom and one polymerizable group in the molecule, wherein the mass ratio of the monomers (A) and (B) in the monomer composition is in the range of 35:65 to 70:30, and the long dimension of the solid primary particles in three directions is in the range of 0.1 μm to 5,000 μm.

2. The solid particle according to claim 1, wherein the glass transition point (Tg) of the solid particle calculated by the FOX formula is in the range of 35 °C to 120 °C.

3. The solid particle according to claim 1 or claim 2, wherein the unsaturated polymerizable monomer (A) is at least one monomer selected from the monomers represented by any one of the following formulas (A-1) to (A-7): Formula (A-1) ： {In the formula, Y is a free-radically polymerizable organic group, R 1 is an alkyl or aryl group having 1 to 10 carbon atoms, and X 1 is a silylalkyl group represented by the following formula, where i = 1. (In the formula, R 1 is the same as above, R 2 is an alkylene group having 2 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, X i+1 is a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer from 1 to 10 representing the order of the above silylalkyl group, and a i is an integer from 0 to 3.)} Formula (A-2) ： (In the above formula, Y and R 1 are the same as above, m is 0, 1 or 2, and n is a number from 0 to 200 representing the average degree of polymerization.) Formula (A-3): Formula (A-4): Formula (A-5): where n = 0 to 120 Formula (A-6): Formula (A-7):

4. The solid particle according to any one of claims 1 to 3, wherein the shape of the solid particle is selected from spherical particles, non-spherical particles, powders, pellets, beads, short fibers, short tubes, and crushed powders.

5. The solid particle according to any one of claims 1 to 3, wherein the shape of the solid primary particle is a spherical particle having a diameter in the range of 0.1 μm to 5,000 μm, and if the particles are aggregated, coagulated, or flocculated, the diameter is in the range of 1 μm to 5,000 μm.

6. A method for manufacturing a solid particle according to any one of claims 1 to 5, the manufacturing method comprising the following steps: Step (I): A step of preparing a solution or dispersion of a silicone-functional copolymer from a monomer composition by a polymerization reaction, the monomer composition being substantially composed of (A) an unsaturated polymerizable monomer having at least one silicone functional group and one polymerizable group in the molecule and (B) an unsaturated polymerizable monomer having no silicon atom or having one silicon atom and one polymerizable group in the molecule, wherein the mass ratio of the monomers (A) and (B) in the monomer composition is in the range of 35:65 to 70:30; and Step (II): A step of removing the carrier fluid of water or solvent from the solution or dispersion of the silicone-functional copolymer prepared in the above step (I).

7. The manufacturing method according to claim 6, the manufacturing method further comprising the following steps: Step (III): After the step (II), a step of forming the solid particle substantially composed of the silicone-functional copolymer using at least one device selected from an extruder, a granulator, a mill, a crusher, a pulverizer, a grinder, an ingotizer, and a drum flaker.

8. The manufacturing method according to claim 7, wherein the manufacturing method further comprises the following steps: Step (IV): A step of classifying the coarse solid particles substantially composed of the organosilicon functional copolymer using at least one device selected from a screen filter, a sieve, a perforated plate, a cyclone separator, and a dynamic air classifier.

9. The manufacturing method according to claim 6, wherein the step (II) is a step of a spray drying method to obtain the spherical particles of the organosilicon functional copolymer by spraying the solution or dispersion to remove the carrier fluid of water or solvent from the solution or dispersion of the organosilicon functional copolymer.

10. The manufacturing method according to claim 6, wherein the step (I) is a step of preparing a solution or dispersion of the organosilicon functional copolymer by at least one liquid phase polymerization reaction selected from solution polymerization, miniemulsion polymerization, and emulsion polymerization.

11. Use of the solid particles according to any one of claims 1 to 5 as a cosmetic ingredient.

12. Use of the solid particles according to any one of claims 1 to 5 as a cosmetic ingredient having a film-forming function on human skin and / or hair.

13. A cosmetic composition, comprising the solid particles according to any one of claims 1 to 5.

14. A method for preparing the cosmetic composition according to claim 13, the preparation method comprising the step of preparing a solution or dispersion of the solid particles according to any one of claims 1 to 5 into at least one cosmetic liquid medium.

15. The method for preparing the cosmetic composition according to claim 13, wherein the cosmetic liquid medium is at least one selected from alcohols, esters, silicone fluids, hydrocarbon oils, fatty acid ester oils, liquid UV protectants, bio-based liquids, biodegradable liquids, cosmetically acceptable solvents, and mixtures thereof.

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