Film-forming agent for cosmetic and cosmetic containing the same

Abstract

The present application provides a film forming agent for cosmetic, which can form a film having excellent water resistance, sebum resistance and high cleansing property. The film forming agent for cosmetic of the present application comprises a copolymer polymerized from a monomer composition comprising: (A) an unsaturated monomer having at least one polysiloxane structure in the molecule, and (B) an unsaturated monomer having at least one acidic group or salt thereof in the molecule, and the content of monomer (A) is 30% by weight or more based on the monomer composition.

Description

Technical Field

[0001] This invention relates to a film-forming agent for cosmetics and cosmetics containing the same, and more specifically, to a film-forming agent for cosmetics that provides cosmetics with excellent water resistance, sebum resistance, and washability, and cosmetics containing the same, wherein the film-forming agent for cosmetics contains a copolymer having a polysiloxane structure and acidic groups. Background Technology

[0002] To improve the staying power of cosmetics, especially color cosmetics, efforts are being made to enhance their water and sebum resistance. Previously, it was known to use polymers containing organopolysiloxanes in cosmetics to improve water resistance (e.g., Patent Document 1). However, while cosmetics with improved water and sebum resistance using such film-forming agents offer good staying power, they also present the problem of being difficult to rinse off during makeup removal. This necessitates the use of special cleansers, oil-based makeup removers, or multiple washes with water-based cleansers, which is inconvenient for users.

[0003] It is known that surface-treated powders, which are coated with a hydrophobic agent and a polymer with hydrophilic groups, are used in cosmetics to improve their rinseability (Patent Document 2). However, in this method, once the powder such as titanium dioxide is surface-treated, it must be incorporated into the cosmetic, which is complicated from a manufacturing point of view.

[0004] Background Technology Documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2000-63225

[0007] Patent Document 2: Japanese Patent Application Publication No. 2007-277167 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] Therefore, the object of the present invention is to provide a film-forming agent and a cosmetic containing the same, wherein the film-forming agent forms a film with excellent water resistance, sebum resistance and high washability.

[0010] [Technical means to solve the problem]

[0011] Through diligent research, the inventors discovered that a composition containing a copolymer can form a film with both high water resistance and good washability, the opposite properties of which are achieved by polymerizing a monomer composition comprising a monomer having a polysiloxane structure and a monomer having an acidic group, thus completing the present invention.

[0012] In other words, the first aspect of the present invention is a film-forming agent for cosmetics, characterized by containing a copolymer polymerized from a monomer composition comprising: (A) an unsaturated monomer having at least one polysiloxane structure within its molecule, and (B) an unsaturated monomer having at least one acidic group or a salt thereof within its molecule, wherein the monomer (A) in the monomer composition comprises 30% by weight or more. The acid value of the copolymer is preferably 5 to 300 mgKOH / g. Furthermore, the weight ratio of monomer (A) to monomer (B) (A / B) is preferably 1.0 to 20.0.

[0013] The unsaturated monomer having at least one polysiloxane structure within its molecule is preferably selected from...

[0014] General formula (1)

[0015] [Chemistry 1]

[0016] In the formula, Y is an organic group capable of free radical polymerization, and R... 1 It is an alkyl or aryl group having 1 to 10 carbon atoms; X 1 For i=1, the following formula represents a silane alkyl group; [Chemistry 2]

[0017] (where R) 1 As mentioned above, R 2 It is an alkyl group with 2 to 10 carbon atoms, R 3 X is an alkyl group having 1 to 10 carbon atoms. i＋1 The radical is selected from the group consisting of hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, aryl groups, and silylalkyl groups; i is an integer from 1 to 10 representing the hierarchy of the silylalkyl group, and a i (integers from 0 to 3)} or

[0018] General formula (2)

[0019] [Chemistry 3]

[0020] (In the formula, Y and R) 1 Same as above; m is 0, 1, or 2, and n represents the average degree of polymerization and is a number from 0 to 200.

[0021] Compounds.

[0022] The monomer composition may also contain (C) a monomer having at least one carboxylic acid ester within its molecule. Additionally, monomer (B) is preferably acrylic acid.

[0023] The film-forming agent for cosmetics of the present invention may further contain at least one selected from the group consisting of (D) oils, (E) alcohols and (F) surfactants, and may also contain at least one selected from the group consisting of water, inorganic powders, organic powders, colorants, thickeners, gelling agents, organically modified clay minerals, silicone resins, silicone rubbers, silicone elastomers, organically modified silicones, ultraviolet defense ingredients, water-soluble polymers, organic resins, moisturizers, preservatives, antioxidants, antibacterial agents, fragrances, salts, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients, vitamins, amino acids, nucleic acids, hormones, inclusion compounds, and antistatic agents.

[0024] A second aspect of the present invention is a cosmetic material containing the aforementioned cosmetic film-forming agent.

[0025] [The effects of the invention]

[0026] According to the present invention, a cosmetic film-forming agent and a cosmetic containing the same are provided, wherein the cosmetic film-forming agent is capable of forming a cosmetic film with excellent water resistance, sebum resistance and high cleansing power. Attached Figure Description

[0027] Figure 1 It is a photograph showing the results of the cleaning test 2, and it is a photograph showing that the lower part of the glass plate has been cleaned. Detailed Implementation

[0028] In this specification, "(meth)acrylic acid" means that it contains both acrylic acid and methacrylic acid. Similarly, "(meth)acrylate", "(meth)acryloyloxy", and "(meth)acrylamide" also mean that they contain both acrylate and methacrylate, acryloyloxy and methacryloyloxy, and acrylamide and methacrylamide, respectively.

[0029] In this invention, "cosmetic material" and "cosmetic product" can be used interchangeably.

[0030] In this invention, the term "film-forming agent" refers to a composition containing a component intended to form a polymeric film that adheres closely to and follows the substrate when applied to a substrate, particularly suitable for keratinized materials such as hair or skin. This invention also discloses a composition for forming a film on a substrate and its uses (hereinafter sometimes referred to as a "cosmetic film-forming agent"), wherein the film is formed using a copolymer polymerized from a monomer composition containing monomers (A) and (B). By forming a film on the skin, makeup smudging or fading can be prevented, bias of effective ingredients such as UV (ultraviolet) absorbers can be prevented, and durability can be improved. Furthermore, film-forming agents are mostly polymeric compounds, often using silicone resins, fluorinated resins, or acrylic resins, and are frequently formulated into sunscreens, makeup products, lipsticks, etc.

[0031] The cosmetic film-forming agent of the present invention contains a copolymer polymerized from a monomer composition comprising: an unsaturated monomer having at least one polysiloxane structure within its molecule (component (A)) and an unsaturated monomer having at least one acidic group or its salt within its molecule (component (B)).

[0032] (A) An unsaturated monomer having a polysiloxane structure is used to introduce the polysiloxane structure into the copolymer. The unsaturated monomer is preferably selected from compounds represented by general formula (1) or general formula (2).

[0033] General formula (1)

[0034] [Chemistry 4]

[0035] In general formula (1), Y is an unsaturated group. Specifically, the following general formulas can be used to represent organic groups containing (meth)acryloyloxy groups, organic groups containing (meth)acrylamide groups, organic groups containing styrene groups, or alkenyl groups with 2 to 10 carbon atoms.

[0036] [Chemistry 5]

[0037] [Chemistry 6]

[0038] [Chemistry 7]

[0039] (In the above formula, R) 4 and R 6 R is a hydrogen atom or a methyl group. 5 and R 8 It is an alkyl group with 1 to 10 carbon atoms, R7 α is an alkyl group with 1 to 10 carbon atoms; b is an integer from 0 to 4, and c is 0 or 1). Examples of such organic groups capable of free radical polymerization include: acryloyloxymethyl, 3-acryloyloxypropyl, methacryloyloxymethyl, 3-methacryloyloxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl, 2-(3-vinylphenyl)ethyl, vinyl, allyl, methylallyl, 5-hexenyl. R 1 It is an alkyl or aryl group having 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl, and cyclohexyl. Examples of aryl groups include phenyl and naphthyl. Among these, methyl and phenyl are preferred, and methyl is particularly preferred. 1 It is the silane alkyl group represented by the following formula when i=1.

[0040] [Chemistry 8]

[0041] In the above formula, R 2 The alkyl group has 2 to 10 carbon atoms, and examples include: straight-chain alkyl groups such as ethylene, propane, butane, and hexane; and branched-chain alkyl groups such as methylmethylene, methylethylene, 1-methylpentane, and 1,4-dimethylbutane. Among these, ethylene, methylethylene, hexane, 1-methylpentane, and 1,4-dimethylbutane are preferred. 3 It is an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and isopropyl. R 1 Same as above. X i＋1 It is a group selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups, and silylalkyl groups. i The value is an integer from 0 to 3, preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. i is an integer from 1 to 10, representing the number of strata of the silane group, i.e., the number of repetitions of the silane group. Therefore, when the number of strata is 1, the carbosiloxane dendritic polymer of this composition is expressed by the general formula: [Chemistry 9]

[0042] (In the formula, Y and R) 1 R 2 and R 3 As mentioned above, R 12 With hydrogen atoms or the R 1 Same; a 1 With the a i The same, but the a in 1 molecule 1The average total is expressed as 0-7). In the case of a layer number of 2, the carbosiloxane dendritic polymer of this component is expressed by the general formula: [Chemistry 10]

[0043] (In the formula, Y and R) 1 R 2 R 3 and R 12 Same as above; a 1 and a 2 With the a i The same, but the a in 1 molecule 1 With a 2 The average total number is expressed as 0–25. In the case of a 3-level dendritic polymer, the carboxyl dendritic polymer is expressed by the general formula: [Chemistry 11]

[0044] (In the formula, Y and R) 1 R 2 R 3 and R 12 Same as above; a 1 a 2 and a 3 With the a i The same, but the a in 1 molecule 1 a 2 and a 3 The average total is expressed as 0 to 79.

[0045] Carboxylated dendritic polymers containing organic groups capable of free radical polymerization, which are components of this product, can be exemplified by carbosiloxane dendritic polymers represented by the following average composition formula.

[0046] [Chemistry 12]

[0047] [Chemistry 13]

[0048] [Chemistry 14]

[0049] [Chemistry 15]

[0050] [Chemistry 16]

[0051] [Chemistry 17]

[0052] [Chemistry 18]

[0053] [Chemistry 19]

[0054] [Chemistry 20]

[0055] [Chemistry 21]

[0056] [Chemistry 22]

[0057] [Chemistry 23]

[0058] [Chemistry 24]

[0059] [Chemistry 25]

[0060] This carbosiloxane dendritic polymer can be manufactured according to the method for manufacturing branched siloxane-silane copolymers described in Japanese Patent Application Publication No. 11-1530 (Japanese Patent Application Publication No. 9-171154). For example, it can be manufactured by using the general formula: [Chemistry 26]

[0061] (where R) 1 The product is manufactured by hydrosilylation of a silicon compound containing silicon atoms bonded to hydrogen atoms (represented by Y as described above) with an organosilicon compound containing an alkenyl group. Examples of silicon compounds represented by the above formula include 3-methacryloyloxypropyltris(dimethylsilaneoxy)silane, 3-acryloyloxypropyltris(dimethylsilaneoxy)silane, and 4-vinylphenyltris(dimethylsilaneoxy)silane. Examples of organosilicon compounds containing an alkenyl group include vinyltris(trimethylsilaneoxy)silane, vinyltris(dimethylphenylsilaneoxy)silane, and 5-hexenyltris(trimethylsilaneoxy)silane. Furthermore, the hydrosilylation reaction is preferably carried out in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

[0062] As another preferred form used in this invention, the compound of the unsaturated monomer having a polysiloxane structure is represented by the following general formula (2).

[0063] [Chemistry 27]

[0064] (In the formula, Y and R) 1 Same as above; m is 0, 1, or 2, and n represents the average degree of polymerization and is a number from 0 to 200.

[0065] The monomer represented by general formula (2) can be specifically exemplified by the following compounds.

[0066] [Chemistry 28]

[0067] [Chemistry 29]

[0068] [Chemistry 30]

[0069] [Chemistry 31]

[0070] [Chemistry 32]

[0071] [Chemistry 33]

[0072] [Chemistry 34]

[0073] [Chemistry 35]

[0074] Furthermore, in the general formula (2), when m is 0 and n is 0, the following compounds can be exemplified as a form of the monomer (A) of the present invention.

[0075] [Chemistry 36]

[0076] The content of monomer (A) in the monomer composition is 30% or more, preferably 40% or more, by weight. By containing a certain weight or more of monomer (A), the copolymer obtained has higher water-repellent and oil-repellent properties, and the water resistance and sebum resistance of cosmetics using the copolymer are improved. Meanwhile, the content of monomer (A) in the monomer composition is preferably 70% or less, more preferably 60% or less, by weight.

[0077] Unsaturated monomers having at least one acidic group or its salt within the molecule (component (B)): The unsaturated monomer of component (B) of the present invention having at least one acidic group or its salt in its molecule is a compound having a free radical polymerizable vinyl group and at least one acidic group or its salt in its molecule. Examples of acidic groups include carboxylic acids, sulfonic acids, and phosphonic acids. Examples of salts of these include alkali metal salts, alkaline earth metal salts, basic amino acid salts, ammonium salts, alkylammonium salts, alkylamine salts, and alkanolamine salts. Specifically, examples include sodium salts, potassium salts, magnesium salts, calcium salts, L-arginine salts, L-histidine salts, L-lysine salts, ammonium salts, triethanolamine salts, aminomethylpropylene glycol salts, and complex salts thereof. Compounds having these acidic groups release protons (H+) in aqueous solution at specific pH values. + These compounds can form salts by bonding with cationic components in a liquid, thus altering their hydrophilic-hydrophobic properties. Similarly, compounds with acidic groups exhibit salt dissociation at specific pH levels, resulting in a change in their hydrophilic-hydrophobicity. Therefore, by appropriately incorporating compounds with these acidic groups or their salts into cosmetics, it is possible to achieve a makeup-holding effect that is easy to rinse off.

[0078] Examples of unsaturated monomers having at least one acidic group or its salt in the molecule include: (meth)acrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid, angelic acid, cisic acid, 2-carboxyethyl acrylate oligomer, styrene sulfonic acid, mono[methacrylate(2-hydroxyethyl)] phosphate, mono[acrylate(2-hydroxyethyl)] phosphate, di[methacrylate(2-hydroxyethyl)] phosphate, and di[acrylate(2-hydroxyethyl)] phosphate, and their salts. To achieve washability without compromising the water resistance of the obtained copolymer, the content of monomer (B) must be less than an equivalent amount relative to the content of monomer (A), preferably a small amount. Specifically, the weight ratio of monomer (A) to monomer (B) (A / B) is in the range of 1.0 to 20.0, preferably in the range of 2 to 15, and more preferably in the range of 2 to 12. Furthermore, from the viewpoint of the technical effects of the present invention, among the examples of component (B), (meth)acrylic acid and its salts are preferred, and acrylic acid and its salts are particularly preferred in terms of balancing water resistance and washability. These unsaturated monomers are commercially available and can be used directly or after refining. In addition, compared with copolymers containing monomers derived from methacrylic acid and acrylic acid, copolymers using monomers derived from acrylic acid have a lower Tg, and are confirmed to have a tendency to produce films with excellent flexibility.

[0079] Other monomers ((C) component): In this invention, in addition to components (A) and (B), component (C) may be included as another monomer. Component (C) can be any monomer capable of copolymerizing with components (A) and (B). Examples include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and other lower alkyl methacrylates; glycidyl methacrylate; n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc. Higher (meth)acrylates such as stearyl acrylate, isostearyl acrylate, and behenyl 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, and vinyl stearate; aromatic vinyl monomers such as styrene, vinyltoluene, benzyl acrylate, phenoxyethyl acrylate, and vinylpyrrolidone; and (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, and isobutoxymethyl methacrylate. Vinyl monomers containing amide groups, such as oxy(meth)acrylamide and N,N-dimethyl(meth)acrylamide; vinyl monomers containing hydroxyl groups, such as hydroxyethyl(meth)acrylate and hydroxypropanol(meth)acrylate; vinyl monomers containing ether bonds, such as tetrahydrofurfuryl(meth)acrylate, butoxyethyl(meth)acrylate, ethoxydiethylene glycol(meth)acrylate, polyethylene glycol(meth)acrylate, polypropylene glycol mono(meth)acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether; and (meth)acryloyloxypropyltrimethoxysilane. Silicone compounds containing unsaturated groups, such as polydimethylsiloxanes with single-terminal, double-terminal, and / or side chain (meth)acryloyl groups, and polydimethylsiloxanes with single-terminal styrene groups; butadiene; vinyl chloride; vinylidene chloride; (meth)acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; glycidyl ether (meth)acrylate; quaternary ammonium salts derived from (meth)acrylic acid, such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride; methacrylates of alcohols having tertiary amino groups, such as diethylamine methacrylate; and quaternary ammonium salts of these.

[0080] In addition, multifunctional vinyl monomers can also be used, such as: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, tri(2-hydroxyethyl)isocyanurate di(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, styrene-terminated polydimethylsiloxane, and other silicone compounds containing unsaturated groups.

[0081] As described above, the weight ratio (A / B) of monomer (A) to monomer (B) in the monomer composition is preferably 1.0 to 20.0, more preferably in the range of 2.0 to 15.0, and even more preferably in the range of 2.0 to 12.0. By copolymerizing monomer (A) and monomer (B) at this weight ratio, the resulting copolymer exhibits a good balance of hydrophobicity and hydrophilicity. Furthermore, when using cosmetic raw materials with an A / B ratio of less than 2, depending on the composition, there may be cases where the washability of the formed film cannot be adequately improved.

[0082] Furthermore, the total content of monomer (A) and monomer (B) relative to the monomer composition ([(A) + (B)] / [(A) + (B) + (C)]) is preferably 40% by weight or more, more preferably 50% by weight or more, and even more preferably 55% by weight or more. If the total content of monomer (A) and monomer (B) is within the aforementioned range relative to the monomer composition, then a sufficient amount of hydrophobic and hydrophilic groups will be introduced into the obtained copolymer, and a cosmetic with high water resistance, sebum resistance, and high washability can be obtained.

[0083] The copolymerization method for the copolymer in the film-forming agent can be either free radical polymerization or ionic polymerization, with free radical polymerization being preferred. In this free radical polymerization method, solution polymerization is suitable. This solution polymerization is carried out by reacting a monomer composition containing components (A) and (B), and any component (C), in a solvent at a temperature of 50–150°C for 3–20 hours in the presence of a free radical initiator. Examples of solvents used in polymerization reactions 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.

[0084] As free radical initiators, conventionally known compounds used in free radical polymerization are generally used. Specifically, examples include azodicarbonyl compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylpentanonitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, tert-butyl peroxide-2-ethylhexanoate, and tert-hexyl peroxide-2-ethylhexanoate. This free radical initiator can be used alone or in combination of two or more. The amount of free radical initiator used is preferably in the range of 0.1 to 5 parts by weight relative to 100 parts by weight of the total monomer composition.

[0085] In addition, chain transfer agents can be added during polymerization. Examples of such chain transfer agents include: 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, polydimethylsiloxane containing a mercaptopropyl group, and other mercaptopropyl compounds; and halides such as dichloromethane, chloroform, carbon tetrachloride, bromobutane, and 3-chloropropyltrimethoxysilane.

[0086] The polymer obtained in the above steps is contacted with a palladium catalyst. Contact with the palladium catalyst saturates the vinyl groups of any remaining unreacted monomers in the polymer, reducing irritation or odor when added to cosmetics. Examples of palladium catalysts include palladium compounds such as tetra(triphenylphosphine)palladium (0) and dichlorobis(triphenylphosphine)palladium (II), carbon-supported palladium, carbon-supported palladium hydroxide, and platinum oxide, but these are not limited to. Carbon-supported palladium is preferred. Other metals such as nickel are also considered as catalysts, but because the polymer contains acidic groups, if nickel is used as a catalyst, it will gradually dissolve into the reaction system under acidic conditions, which is undesirable. On the other hand, palladium, as a noble metal, especially carbon-supported palladium catalysts as heterogeneous catalysts, hardly causes this problem and can be well used as the catalyst of the present invention.

[0087] The temperature at which the polymerization reactants contact the palladium catalyst is 50–200°C, preferably 70–130°C. The pressure is 1–1,000 kg / cm³. 2 (Absolute pressure), preferably 2-100 kg / cm² 2 The contact time is 1–15 hours, preferably 3–10 hours. The reaction can be carried out in a solvent, either directly or by solvent displacement. The solvent that can be used is the same as that described for the polymerization reaction.

[0088] Other steps, such as stripping, reprecipitation, and filtration, may be performed between the steps described above. Additionally, after the contact step with the palladium catalyst, steps such as stripping, reprecipitation, filtration, pulverization, and classification may also be performed.

[0089] Whether there are unreacted monomers in the copolymer obtained in the manner described can be determined by... 1 ¹H-NMR analysis confirms the reaction based on the peak integral value (5.5–6.5 ppm) of the vinyl unsaturated group, and the reaction endpoint can be determined by the disappearance or reduction of the peak originating from the vinyl unsaturated group. Specifically, the ratio of the peak integral value of the vinyl unsaturated group relative to the integral value (0–0.3 ppm) of the methyl group originating from the polysiloxane-structured unsaturated monomer to the weight percentage of the polysiloxane-structured unsaturated monomer added (residual unsaturation ratio) can be compared. The residual unsaturation ratio in the copolymer is 0.1 or less, preferably 0.02 or less.

[0090] Furthermore, after polymerization, purification can be carried out by removing residual unreacted vinyl monomers through vacuum treatment under heating; or by odorless treatment utilizing hydrogenation in the presence of a hydrogenation catalyst in a solvent-free or solvent-free environment, followed by distillation removal of light substances by contact with nitrogen under reduced pressure. This purified product is particularly preferred for use in topical agents where reduced odor and compatibility with other cosmetic ingredients are required. The hydrogenation reaction and stripping steps can be performed without particular restriction, using solvents, reaction conditions, and vacuum conditions known for the purification of organopolysiloxane copolymers.

[0091] The copolymer of the present invention has an acid value of 5 to 300 mgKOH / g, preferably 35 to 100 mgKOH / g, as measured according to JIS 1557-5. Furthermore, in the present invention, when the acidic groups in the copolymer are in salt form, the acid value indicates the acid value obtained by exchanging the salt with hydrogen ions to form an acidic form. In addition, the number-average molecular weight of the copolymer is preferably 1,000 to 200,000, more preferably 2,000 to 80,000, for ease of formulation in cosmetics. Furthermore, the copolymer can be in liquid, gel, paste, solid, or powder form.

[0092] The film-forming agent for cosmetics of the present invention can be directly incorporated into cosmetics, or incorporated into cosmetics in the form of a composition dissolved in a solvent or dispersed in a dispersion medium.

[0093] In addition to the copolymer, the film-forming agent of the present invention may contain at least one component selected from the group consisting of (D) oil and (E) alcohol. When formulated into cosmetics containing the copolymer, it can be prepared in advance as a solution dissolved in a solvent, a dispersion dispersed in a dispersion medium, or a solid form such as powder, granules, or lumps. The film-forming agent for cosmetics of the present invention is particularly suitable for dissolving or dispersing in one or more oils or alcohols and being formulated into cosmetics as a copolymer composition containing the copolymer and the oil or alcohol.

[0094] The film-forming agent for cosmetics of the present invention exhibits excellent compatibility and dispersibility, particularly with various oils or alcohols, enabling the production of a uniform composition over a prolonged period. This composition can be directly formulated into cosmetics and is extremely useful as a cosmetic ingredient in terms of its operability and shelf-life stability. Specifically, a composition containing 5 to 1000 parts by weight, preferably 50 to 500 parts by weight, and more preferably 100 to 400 parts by weight, relative to 100 parts by weight of the copolymer of the present invention, is suitable. Furthermore, when obtaining a composition comprising the copolymer and an oil or alcohol, mechanical force can be used to uniformly disperse the copolymer, after the polymerization reaction has been cleaned of solvent and unreacted monomers, in the oil or alcohol, or the oil or alcohol can be used to replace the volatile solvent produced during the polymerization reaction. Additionally, when formulated into cosmetics, the formulation amount is not particularly limited; the copolymer of the present invention can be formulated in the range of 0.1 to 50% by weight of the total cosmetic, preferably 1 to 10% by weight. In particular, when formulated within this range, the advantages of the copolymers of the present invention can be effectively utilized: they can impart film-forming properties to cosmetics, and the film has excellent washability.

[0095] (D) Oil

[0096] Examples of oils used in cosmetics include animal oils, vegetable oils, and synthetic oils. These oils can be solid, semi-solid, or liquid, and can be non-volatile, semi-volatile, or volatile. The oils are used to impart lubrication to skin or hair, making the skin soft and moisturized. Additionally, the oils can be used to dilute the copolymers of the present invention to obtain copolymer compositions. They are particularly preferred to be liquid at 5–100°C and selected from at least one of (D1) silicone-based oils and (D2) organic-based oils. The type, viscosity, etc., of these oils can be appropriately selected according to the type and purpose of the cosmetic. These oils are simultaneously formulated into the cosmetic of the present invention along with the aforementioned composition.

[0097] (D1) Silicone-based oils

[0098] Silicone-based oils are generally hydrophobic, and their molecular structures can be linear, cyclic, or branched. The viscosity of silicone oils at 25°C is typically 0.65–100,000 mm⁻¹. 2 The range of / s is preferably 0.65 to 10,000 mm. 2 The range is / s. Additionally, this silicone-based oil agent may be volatile, and is preferably volatile.

[0099] Specifically, examples of silicone oils include cyclic organopolysiloxanes, linear organopolysiloxanes, and branched organopolysiloxanes. Among these, volatile linear organopolysiloxanes, branched organopolysiloxanes, and cyclic organopolysiloxanes are preferred.

[0100] As the silicone oil, for example, the following general formulas (3), (4), or (5) can be used: [Chemistry 37]

[0101] (In the formula, R 9 A group consisting of a hydrogen atom, a hydroxyl group, or a monovalent, unsubstituted or fluorinated or amino-substituted alkyl, aryl, alkoxy, and (CH3)3SiO{(CH3)2SiO}lSi(CH3)2CH2CH2- (where l is an integer from 0 to 1000), where a' is an integer from 0 to 3, b is an integer from 0 to 1000, and c is an integer from 0 to 1000, but 1 ≦ b + c ≦ 2000). [Chemistry 38]

[0102] (where R) 9 As before, d is an integer from 0 to 8, and e is an integer from 0 to 8, but 3 ≤ d + e ≤ 8.

[0103] [Chemistry 39]

[0104] (where R) 9 As before, the organopolysiloxane represented by f (where f is an integer from 1 to 4 and g is an integer from 0 to 500) is used.

[0105] Examples of monovalent, unsubstituted or fluorinated or amino-substituted alkyl, aryl, and alkoxy groups with 1 to 30 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and other straight-chain or branched alkyl groups with 1 to 30 carbon atoms; cyclopentyl, cyclohexyl, and other cycloalkyl groups with 3 to 30 carbon atoms; phenyl, tolyl, xylyl, naphthyl, and other aryl groups with 6 to 30 carbon atoms; methoxy, ethoxy, propoxy, and other alkoxy groups with 1 to 30 carbon atoms; and groups in which the hydrogen atoms bonded to the carbon atoms of these groups are at least partially substituted with fluorine or amino groups. Unsubstituted alkyl or aryl groups are preferred, unsubstituted alkyl or aryl groups with 1 to 6 carbon atoms are more preferred, and methyl, ethyl, or phenyl are particularly preferred.

[0106] More specifically, examples of silicone oils having these structures, and more specifically, examples of cyclic organopolysiloxanes, include: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, 1,1-diethylhexamethylcyclotetrasiloxane, 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, and 1,3,5,7-tetra(3-methacryloyloxypropyl)tetramethyl... Examples of cyclotetrasiloxanes include 1,3,5,7-tetra(3-acryloyloxypropyl)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.

[0107] Examples of linear organopolysiloxanes include: trimethylsiloxy-terminated dimethylpolysiloxane (viscosity 2 mPa). s or 6 mPa Low viscosity (e.g., s) up to 1 million mPa (e.g., high viscosity dimethyl silicone), organohydrogen polysiloxane, trimethylsiloxy-terminated methylphenyl polysiloxane, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymer, trimethylsiloxy-terminated diphenyl polysiloxane, trimethylsiloxy-terminated dimethylsiloxane-diphenylsiloxane copolymer, trimethylpentaphenyltrisiloxane, phenyl(trimethylsiloxy)siloxane, trimethylsiloxy-terminated methylalkyl polysiloxane, trimethylsiloxy-terminated dimethyl polysiloxane-methylalkylsiloxane copolymer, trimethylsiloxy-terminated dimethylsiloxane-methyl(3,3,3-trifluoropropyl) α,ω-dihydroxypolydimethylsiloxane copolymers, 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, tri-trimethylsilaneoxymethylsilane, tri-trimethylsilaneoxyalkylsilane, tetra-trimethylsilaneoxysilane, tetramethyl-1,3-dihydroxydisiloxane, octamethyl-1,7-dihydroxytetrasiloxane, hexamethyl-1,5-diethoxytrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, higher alkoxy-modified silicones, higher fatty acid-modified silicones, etc.

[0108] Examples of branched organopolysiloxanes include: methyltri-trimethylsilaneoxysilane, ethyltri-trimethylsilaneoxysilane, propyltri-trimethylsilaneoxysilane, tetra-trimethylsilaneoxysilane, phenyltri-trimethylsilaneoxysilane, etc.

[0109] When using the cosmetics or compositions of the present invention as cosmetic ingredients, the presence of at least one of these silicone-based oils improves their long-term stability and achieves the refreshing feel characteristic of silicone oils. Particularly preferred are decamethylcyclopentasiloxane, linear organopolysiloxanes, and silicone-based oils with a viscosity of 2–6 mPa. Silicone-based oils in the low viscosity range of s, 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane (also known as "octyl polymethylsiloxane"), tri-trimethylsiloxymethylsilane (also known as "M3T"), etc.

[0110] (D2) Organic oils

[0111] Representative organic oils include (D2-1) hydrocarbon oils, (D2-2) fatty acid ester oils, higher alcohols, higher fatty acids, oils, and fluorinated oils. No particular limitation is made in this invention. The organic oils are preferably liquid at 5–100°C. Hydrocarbon oils and / or fatty acid ester oils are further preferred. These can be used alone or in combination, or in combination with the aforementioned silicone oils. By combining appropriate oils, the long-term stability of the composition and / or cosmetic can be improved, and the desired feel can be imparted to each cosmetic. By formulating the aforementioned silicone oils, the characteristic refreshing feel of silicone oils can be imparted. Furthermore, by using highly volatile oils, a refreshing feel can be imparted to the skin. Additionally, by using hydrocarbon oils and / or fatty acid ester oils in combination with the aforementioned silicone oils, a moisturizing feel (also known as a "wet feel") or a smooth feel can be imparted to the skin or hair.

[0112] Examples of (D2-1) hydrocarbon oils include: liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, petrolatum, normal paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin, microcrystalline wax, solid paraffin, polyethylene wax, polyethylene-polypropylene wax, squalane, squalene, pterostilbene, polyisoprene, etc. In particular, isododecane is preferred in the compositions of the present invention due to its excellent volatility, excellent compatibility and affinity (formulation stability) with other cosmetic ingredients, and its ability to impart a refreshing feel to the skin.

[0113] Examples of (D2-2) fatty acid ester oils include: hexyl decyl octanoate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleic acid ester, decyl oleate, octyl dodecyl myristate, hexyl decyl dimethyl octanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, di-trimethylolpropane tri ... Methylpropane (isostearic acid / sebacic acid) ester, Trimethylolpropane trioctanoate, Trimethylolpropane triisostearate, Diisopropyl adipate, Diisobutyl adipate, 2-hexyldecyl adipate, Di-2-heptylundecyl adipate, Diisostearate malate, Hydrogenated castor oil monoisostearate, N-alkyl glycol monoisostearate, Octyldodecyl isostearate, Isopropyl isostearate, Isoceridyl isostearate, Ethyl glycol di-2-ethylhexanoate, Cetyl 2-ethylhexanoate, Pentaerythritol tetra-2-ethylhexanoate, Octyldodecyl gum, Ethyl oleate, Octyldodecyl oleate, Neopentyl glycol didecyl ester, Triethyl citrate, Amber 2-Ethylhexyl sebacate, dioctyl succinate, isocetyl stearate, diisopropyl sebacate, di(2-ethylhexyl) sebacate, diethyl sebacate, dioctyl sebacate, di(butyloctyl) sebacate, cetyl palmitate, octyl dodecyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyl decyl palmitate, 2-heptyl undecyl palmitate, 12-hydroxystearate cholesterol, dipentaerythritol fatty acid ester, 2-hexyl decyl myristate, ethyl laurate, N-lauroyl-L-glutamic acid-2-octyl dodecyl ester, N-lauroyl-L-glutamic acid di(cholesterol / behenyl / octyl dodecyl) ester, N -Lauroyl-L-glutamic acid di(cholesterol / octyldodecyl) ester, N-Lauroyl-L-glutamic acid di(phytosterol / behenyl / octyldodecyl) ester, N-Lauroyl-L-glutamic acid di(phytosterol / octyldodecyl) ester, N-Lauroylsarcosine isopropyl ester, diisostearyl malate, neopentyl glycol dioctyl ester, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, isotridecyl isononanoate, diethylpentyl dipentanoate, dimethylpentyl dipentanoate, octyldodecyl neodecanoate, 2-butyl-2-ethyl-1, dioctanoate3-Propanediol ester, Pentaerythritol tetracaprylate, Hydrogenated rosin pentaerythritol ester, Pentaerythritol triethylhexanoate, Dipentaerythritol (hydroxystearic acid / stearic acid / rosin acid) ester, Tetraisostearic acid polyglycerol ester, Nonaisostearic acid polyglycerol-10 ester, Deca(sinapic acid / isostearic acid / ricinoleic acid) polyglycerol-8 ester, (hexyldecanoic acid / sebacic acid) diglyceride oligoester, Distearate diol ester (distearate ethylene glycol ester), Diisopropyl dilinoleate, Diisostearate dilinoleate, Dimeric linoleic acid di(isostearyl / phytosterol) ester, Dimeric linoleic acid (phytosterol / behenyl) ester, Dimeric linoleic acid (phytosterol / isostearyl / cetyl / stearyl / behenyl) ester, Dimeric linoleyl alcohol dimeric linoleate, Dimeric linoleyl alcohol diisostearate, Hydrogenated rosin dimeric linoleyl alcohol ester condensate, Hydrogenated castor oil dimeric linoleate, Hydroxyalkyl dimeric linoleyl ether, Triisocaprylic acid glyceride, Triisostearic acid glyceride, Trimyristic acid glyceride, Triisopalmitic acid glyceride, Tri... Caprylic acid glyceride, trioleic acid glyceride, diisostearate glyceride, tri(caprylic / capric acid) glyceride, tri(caprylic / capric acid / myristic acid / stearic acid) glyceride, hydrogenated rosin triglyceride (hydrogenated ester), rosin triglyceride (ester), eicosanoic acid glyceride, di-2-heptylundecanoic acid glyceride, myristic acid isostearate diglyceride, cholesterol acetate, cholesterol nonanoate, cholesterol stearate, cholesterol isostearate, cholesterol oleate, cholesterol 12- Hydroxystearate, cholesterol macadamia nut oil fatty acid ester, phytosterol macadamia nut oil fatty acid ester, phytosterol isostearate, cholesterol soft lanolin fatty acid ester, cholesterol hard lanolin fatty acid ester, cholesterol long-chain branched fatty acid ester, cholesterol long-chain α-hydroxy fatty acid ester, octyl dodecyl ricinoleate, octyl dodecyl lanolin fatty acid ester, octyl dodecyl sinapicate, hydrogenated castor oil isostearate, avocado oil fatty acid ethyl ester, lanolin fatty acid isopropyl ester, etc. Lanolin and its derivatives can also be used as fatty acid ester oils.

[0114] In addition to the above, oils, higher alcohols, higher fatty acids, fluorinated oils, etc., may also be used as oiling agents. Furthermore, two or more of the above-mentioned types may be used in combination. For example, two or more of the oiling agents shown below may also be used in combination. Hereinafter, other oiling agents that can be used in this invention will be illustrated more specifically. Specifically, examples include the use of one or more types selected from oils, higher alcohols, higher fatty acids, and fluorinated oiling agents.

[0115] As for oils and fats, including natural animal and vegetable oils and semi-synthetic oils, the following can be listed: avocado oil, flaxseed oil, almond oil, insect wax, perilla oil, olive oil, cocoa butter, kapok wax, torreya nut oil, carnauba wax, liver oil, candelilla wax, butter, beef foot fat, beef bone fat, hydrogenated butter, almond oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, camellia oil (sasanqua oil), safflower oil, shea butter, tung oil, Ceylon cinnamon oil, jojoba wax, olive squalane, shellac wax, turtle oil, soybean oil, tea seed oil, and camellia oil (Camellia) oil. Oils include evening primrose oil, corn oil, lard, rapeseed oil, Japanese tung oil, rice bran wax, wheat germ oil, horse fat, peach kernel oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower seed oil, grapeseed oil, lauryl wax, jojoba oil, hydrogenated jojoba ester, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, wood wax, wood wax kernel oil, lignite wax, coconut oil, hydrogenated coconut oil, tri-coconut oil fatty acid glycerides, lanolin, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl ester, POE lanolin alcohol ether, POE lanolin alcohol acetate, polyethylene glycol lanolin fatty acid ester, POE hydrogenated lanolin alcohol ether, egg yolk oil, etc. POE refers to polyoxyethylene.

[0116] Higher alcohols are, for example, higher alcohols with 10 to 30 carbon atoms. These higher alcohols are saturated or unsaturated monovalent aliphatic alcohols, and their hydrocarbon groups can be either straight-chain or branched, preferably straight-chain. Examples of higher alcohols with 10 to 30 carbon atoms include: lauryl alcohol, myristyl alcohol, palmitol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecyl alcohol, octyldodecyl alcohol, cetearyl alcohol, 2-decyltetradecyl alcohol, cholesterol, sitosterol, phytosterol, lanosterol, lanolin alcohol, hydrogenated lanolin alcohol, POE cholesterol ether, monostearate glyceryl ether (squalene), monooleyl glyceryl ether (squalene), etc. Furthermore, in this invention, it is preferable to use a higher alcohol with a melting point of 40 to 80°C alone, or a combination of multiple higher alcohols with a melting point of 40 to 70°C. These higher alcohols, together with surfactants, form aggregates known as α-gels, which increase the viscosity of formulations and stabilize emulsions, making them particularly useful as bases for emulsion-form cosmetics.

[0117] Examples of high-grade fatty acids include: lauric acid, myristic acid, palmitic acid, stearic acid, benzyl acid, undecenoic acid, oleic acid, linolenic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0118] Examples of fluorinated oils include perfluoropolyether, perfluorodecahydronaphthalene, and perfluorooctane.

[0119] (E) alcohol

[0120] The copolymers of the present invention can be dispersed or dissolved in alcohols for use. Furthermore, because the copolymers of the present invention have excellent affinity with alcohols, which are common ingredients in cosmetics, they can also coexist in cosmetic formulations. One or more polyols and / or lower monohydric alcohols can be used as the alcohol. Examples of lower alcohols include ethanol, isopropanol, n-propanol, tert-butanol, dibutanol, etc., with ethanol being preferred. Examples of polyols include: 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, 1,2-propanediol, trimethylolamine, tetramethylolamine, 2,3-butanediol, pentamethylolamine, 2-buten-1,4-diol, dibutylene glycol, pentanediol, hexanediol, octanediol, and other diols; glycerol, trimethylolpropane, 1,2,6-hexanetriol, and other triols; pentaerythritol, xylitol, and other polyols with four or more members; and sugar alcohols such as sorbitol, mannitol, maltitol, maltotriose, sucrose, erythritol, glucose, fructose, starch breakdown products, maltose, xylitol, and starch breakdown sugar reducing alcohols. Furthermore, in addition to these low-molecular-weight polyols, examples include diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerol, polyethylene glycol, triglycerol, tetraglycerol, polyglycerol, and other polyol polymers. Among these, ethanol, 1,3-propanediol, 1,3-butanediol, sorbitol, dipropylene glycol, glycerol, and polyethylene glycol are particularly preferred.

[0121] The second aspect of the present invention relates to a cosmetic containing the aforementioned film-forming agent. The cosmetic of the present invention may contain various cosmetic raw materials in addition to the aforementioned film-forming agent. The cosmetic includes two cases: it is formulated into a cosmetic after a film-forming agent containing the aforementioned components (D) to (E) has been prepared; or it is formulated into a cosmetic separately with a copolymer serving as a film-forming agent and other cosmetic raw materials. The components (D) to (E) described in the film-forming agent aspect of the present invention can also be used as other cosmetic raw materials. Examples of such other cosmetic raw materials include: the aforementioned components (D) to (E), (F) surfactant, (G) powder or colorant, (H) thickener or gelling agent, (I) organically modified clay mineral, (J) silicone resin, (K) silicone rubber, (L) silicone elastomer, (M) organically modified silicone, (N) ultraviolet defense component, and (O) water-soluble polymer, water, etc.

[0122] The cosmetic containing a film-forming agent of the present invention may contain (F) surfactant as an arbitrary ingredient. The (F) surfactant may be used in combination with one or more surfactants selected from the group consisting of (F1) silicone surfactants, (F2) anionic surfactants, (F3) cationic surfactants, (F4) nonionic surfactants, (F5) amphoteric surfactants, and (F6) semipolar surfactants, depending on the purpose.

[0123] Examples of (F1) silicone-based surfactants include: polyglycerol-modified silicone, diglycerol-modified silicone, glycerol-modified silicone, sugar-modified silicone, fluorinated polyether-modified silicone, polyether-modified silicone, carboxylic acid-modified silicone, linear silicone-polyether block copolymers (such as polysilicone-13), long-chain alkyl-polyether co-modified silicone, polyglycerol-modified silicone elastomers, diglycerol-modified elastomers, glycerol-modified elastomers, polyether-modified elastomers, etc. Furthermore, surfactants obtained by simultaneously applying alkyl branches, linear silicone branches, siloxane dendritic polymer branches, etc., to the aforementioned silicones or elastomers, along with hydrophilic groups, may also be used as needed. Commercially available products include: SH 3771 M, SH 3772 M, SH 3773 M, SH3775 M, BY 22-008M, BY 11-030, ES-5373 FORMULATION AID, ES-5612 FORMULATION AID, ES-5300 FORMULATION AID, and ES-5600 SILICONE GLYCEROL EMULSIFIER (all manufactured by Toray Industries, Inc.).

[0124] Examples of (F2) anionic surfactants include: saturated or unsaturated fatty acid salts (e.g., sodium laurylate, sodium stearate, sodium oleate, sodium linoleate, etc.), alkyl sulfates, alkylbenzene sulfonic acids (e.g., hexylbenzene sulfonic acid, octylbenzene sulfonic acid, dodecylbenzene sulfonic acid, etc.) and their salts, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyethylene alkyl sulfates, alkyl sulfosuccinates, alkyl polyoxyalkylene sulfosuccinates, polyoxyalkylene alkylphenyl ether sulfates, alkyl sulfonates, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, and alkyl sulfonates. Polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether acetates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, acylglutamate salts, α-acylsulfonates, alkylsulfonates, alkylallyl sulfonates, α-olefin sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl or alkenyl sulfates, alkylamide sulfates, alkyl or alkenyl phosphates, alkylamide phosphates, enoyl alkyl taurine salts, N-acyl amino acid salts, sulfosuccinates, alkyl ether carboxylates, amide ether carboxylates, α-sulfo fatty acid ester salts, alanine derivatives, glycine derivatives, arginine derivatives. As salts, examples include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkylolamine salts such as triethanolamine salts, and ammonium salts.

[0125] Examples of (F3) cationic surfactants include: alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium bromide, distearate dimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di(POE)oleylmethylammonium chloride (2EO), benzylalkylammonium chloride, alkylbenzylalkylammonium chloride, alkyldimethylbenzylalkylammonium chloride, benzyl chloride, stearyldimethylbenzylammonium chloride, lanolin-derived quaternary ammonium salts, diethylaminoethylamide stearate, dimethylaminopropylamide stearate, benzylaminopropyldimethylhydroxypropylammonium chloride, stearylcholinecarbamoylmethylpyridinium chloride, cetylpyridinium chloride, talluloalkylbenzylhydroxyethylimidazolineonium chloride, and benzylammonium salts.

[0126] Examples of (F4) nonionic surfactants include: diisostearate polyglycerol or polyhydroxystearate diglycerol, isostearylglycerol ether, polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin esters, polyoxyalkylene (hydrogenated) castor oil, polyoxyalkylene alkylphenols, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene phenylphenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, and polyoxyalkylene sorbitan alkyl esters. Classes include: polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene glycerol fatty acid esters, polyglycerol alkyl ethers, polyglycerol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxyalkylene fatty acid biphenyl ethers, polypropylene glycol, diethylene glycol, polyoxyethylene-polyoxypropylene block polymers, alkyl polyoxyethylene-polyoxypropylene block polymer ethers, polyoxyethylene-polyoxypropylene block polymers, alkyl polyoxyethylene-polyoxypropylene block polymer ethers, fluorinated surfactants, etc.

[0127] Examples of (F5) amphoteric surfactants include: imidazoline type, amide betaine type, alkyl betaine type, alkylamide betaine type, alkyl sulfonyl betaine type, amide sulfonyl betaine type, hydroxysulfonyl betaine type, carbonyl betaine type, phosphate ester betaine type, aminocarboxylic acid type, and amide amino acid type amphoteric surfactants. Specifically, examples include: imidazoline type amphoteric surfactants such as sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline and disodium 2-cocoyl-2-imidazolineonium hydroxide-1-carboxyethoxy; alkyl betaine type amphoteric surfactants such as lauryl dimethylaminoacetic acid betaine and myristyl betaine; coconut oil fatty amide propyl dimethylaminoacetic acid betaine, palm kernel oil fatty amide propyl dimethylaminoacetic acid betaine, tallow fatty amide propyl dimethylaminoacetic acid betaine, hydrogenated tallow fatty amide propyl dimethylaminoacetic acid betaine, etc. Amide betaine-type amphoteric surfactants such as lauromamide propyl dimethylaminoacetic acid betaine, myristamidopropyl dimethylaminoacetic acid betaine, palmitamidopropyl dimethylaminoacetic acid betaine, stearamidopropyl dimethylaminoacetic acid betaine, and oleamidopropyl dimethylaminoacetic acid betaine; alkyl sulfonyl betaine-type amphoteric surfactants such as coconut oil fatty acid dimethyl sulfonyl betaine; alkyl hydroxy sulfonyl betaine-type amphoteric surfactants such as lauryl dimethylaminohydroxy sulfonyl betaine; phosphate betaine-type amphoteric surfactants such as lauryl hydroxyphosphate betaine; N-lauroyl-N' Sodium N-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-oleoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-cocoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-lauroyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, Potassium N-oleoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, Potassium N-oleoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-lauroyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-oleoyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-cocoyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine, Sodium N-cocoyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine Sodium, N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine monosodium, N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine monosodium, N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine monosodium, N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine disodium, N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine disodium, N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine disodium, etc., are amide amino acid-type amphoteric surfactants.

[0128] Examples of (F6) semi-polar surfactants include alkyl amine oxide surfactants, alkyl amine oxides, alkyl amide amine oxides, alkyl hydroxy amine oxides, etc., with alkyl dimethyl amine oxides with 10 to 18 carbon atoms and alkoxyethyl dihydroxyethyl amine oxides with 8 to 18 carbon atoms being preferred. Specifically, examples include: dodecyl dimethylamine oxide, dimethyl octylamine oxide, diethyl decylamine oxide, bis-(2-hydroxyethyl) dodecylamine oxide, dipropyl tetradecylamine oxide, methyl ethyl hexadecylamine oxide, dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, isostearyl dimethylamine oxide, coconut fatty acid alkyl dimethylamine oxide, octamidopropyl dimethylamine oxide, decanamidopropyl dimethylamine oxide, lauramidopropyl dimethylamine oxide, myristamidopropyl dimethylamine oxide, palmitamidopropyl dimethylamine oxide, etc. Amine oxides, stearamide propyl dimethylamine oxide, isostearamide propyl dimethylamine oxide, oleamide propyl dimethylamine oxide, ricinoleamide propyl dimethylamine oxide, 12-hydroxystearamide propyl dimethylamine oxide, coconut fat amide propyl dimethylamine oxide, palm kernel oil amide propyl dimethylamine oxide, castor oil amide propyl dimethylamine oxide, lauramide ethyl dimethylamine oxide, myristamide ethyl dimethylamine oxide, coconut fat amide ethyl dimethylamine oxide, lauramide ethyl diethylamine oxide, myristamide ethyl diethylamine oxide, coconut fat amide ethyl diethylamine oxide, lauramide ethyl dihydroxyethylamine oxide, myristamide ethyl dihydroxyethylamine oxide, and coconut fat amide ethyl dihydroxyethylamine oxide.

[0129] The amount of surfactant (F) in the film-forming agent or cosmetic of the present invention is not particularly limited. In order to stabilize the film-forming agent or cosmetic, it can be formulated in the range of 0.05% to 90% by weight in the film-forming agent or cosmetic, preferably 0.1% to 50% by weight, and more preferably 0.5% to 25% by weight.

[0130] (G) Powder or colorant

[0131] The film-forming agent or cosmetic of the present invention can also be formulated with powders or colorants, particularly any powders used in cosmetics (including powders and pigments used as colorants).

[0132] Powders or colorants can be used in any way, regardless of their shape (spherical, rod-shaped, needle-shaped, plate-shaped, flake-shaped, irregular shape, spindle-shaped, bowl-shaped, raspberry-shaped, etc.), particle size (smoky, microparticle, pigment-grade, etc.), or particle structure (porous, non-porous, secondary agglomeration, etc.). When these powders and / or colorants are formulated as pigments, it is preferable to formulate one or more of inorganic pigment powders, organic pigment powders, and resin powders with an average particle size in the range of 1 nm to 20 μm.

[0133] Powders or colorants can specifically include inorganic powders, organic powders, surfactant metal salt powders (metallic soaps), colored pigments, pearlescent pigments, metallic powder pigments, silicone elastomer powders, etc., and may also be composites of these. Furthermore, these powders or colorants contain components that function as UV-protective agents.

[0134] Specifically, inorganic powders include: titanium dioxide, 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, silicic anhydride, aluminum silicate, sodium silicate, sodium magnesium silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, tungstate metal salts, hydroxyapatite, vermiculite, higilite, bentonite, montmorillonite, lithium bentonite, zeolite, ceramic powder, dicalcium hydrogen phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, etc.; organic powders include: polyamide powder, polyester powder, polyethylene powder, polypropylene powder, etc. Polystyrene powder, polyurethane powder, benzomelamine powder, polymethyl benzomelamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, 12 nylon, 6 nylon, silicone powder, silicone rubber powder, silicone elastomer spherical powder obtained by coating surfaces with polymethyl silsesquioxane, polymethyl silsesquioxane spherical powder, styrene-acrylic acid 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, lauroyl lysine, etc.; as surfactant metal salt powder Examples of organic pigments include: zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, etc. Examples of inorganic pigments include: iron oxide, iron oxide, iron hydroxide, and iron titanate (inorganic red pigments); γ-iron oxide and other inorganic brown pigments; iron oxide yellow and yellow ochre and other inorganic yellow pigments; iron oxide black and carbon black and other inorganic black pigments; manganese violet and cobalt violet and other inorganic purple pigments; chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate and other inorganic green pigments; iron blue and ultramarine and other inorganic blue pigments; and red pigments such as No. 3, No. 104, No. 106, No. 201, No. 202, and red... Pigments obtained by laked pigments such as Color 204, Red 205, Red 220, Red 226, Red 227, Red 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404, Green 3, Green 201, Green 204, Green 205, Orange 201, Orange 203, Orange 204, Orange 206, and Orange 207, etc.; pigments obtained by laked natural pigments such as carmine acid, laccasein, safflower pigment, brassicatinol, and crocin, etc.Examples of pearlescent pigments include: titanium dioxide-coated mica, titanium mica, iron oxide-treated titanium mica, titanium dioxide-coated mica, bismuth oxychloride, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, and titanium dioxide-coated colored mica. Examples of metallic powder pigments include: aluminum, gold, silver, copper, platinum, and stainless steel powders.

[0135] Silicone elastomer powder is the powdered component of the following (L) silicone elastomers. They are crosslinked products of linear organosiloxanes mainly composed of diorganosilane alkoxy units (D units), and can be suitably obtained by crosslinking organohydrogen polysiloxanes with silicon-bonded hydrogen atoms on the side chains or at the ends with diorganopolysiloxanes with unsaturated hydrocarbon groups such as alkenyl groups on the side chains or at the ends under a hydrosilylation catalyst. Compared to silicone resin powders containing T and Q units, silicone elastomer powder is softer and more elastic; furthermore, it has excellent oil absorption, thus absorbing oil from the skin and preventing makeup from smudging.

[0136] Silicone elastomer powder can take various shapes, such as spherical, flat, or irregular shapes. Silicone elastomer powder can also be in the form of an oil dispersion. The cosmetic of the present invention can be suitably formulated with silicone elastomer powder having a particle shape, and under observation using an electron microscope, the average primary particle size, measured by primary particle size and / or laser diffraction / scattering methods, is in the range of 0.1 to 50 μm, and the primary particle shape is spherical. The silicone elastomer constituting the silicone elastomer powder is preferably a silicone elastomer with a hardness of 80 or less obtained using a Type A hardness tester according to JIS K 6253 "Hardness Test Method for Vulcanized Rubber and Thermoplastic Rubber", more preferably a silicone elastomer with a hardness of 65 or less.

[0137] Furthermore, silicone elastomer powder can also be used in the cosmetics of the present invention in the form of an aqueous dispersion. Examples of commercially available such aqueous dispersions include BY 29-129 and PF-2001 PIF Emulsion manufactured by Toray Dow Corning.

[0138] Silicone elastomer powders can also be surface-treated using silicone resins, silica, or other materials. Examples of such surface treatments include those described in Japanese Patent Application Publications Nos. 2-243612, 8-12545, 8-12546, 8-12524, 9-241511, 10-36219, 11-193331, and 2000-281523. Furthermore, the cross-linked silicone powders listed in the "Cosmetic Category Formulation Ingredient Standard" conform to these standards. Commercially available silicone elastomer powders include, for example, Trefil E-506S, Trefil E-508, 9701 Cosmetic Powder, and 9702 Powder manufactured by Toray Dow Corning.

[0139] Furthermore, these powders or colorants are particularly preferably partially or entirely subjected to a water-repellent treatment. This allows them to be stably formulated into the oil phase. Alternatively, powders or colorants obtained by compounding these powders or colorants together, or those that have undergone surface treatment using general oils, silicone compounds other than the organopolysiloxane copolymers of the present invention, or fluorinated compounds, surfactants, etc., can also be used.

[0140] As examples of other water-repellent treatments, various water-repellent surface treatment agents can be used to treat the powder or colorant. Examples include: organosiloxane treatment such as methylhydropolysiloxane treatment, silicone resin treatment, silicone rubber treatment, acrylic silicone treatment, fluorinated silicone treatment, metal soap treatment such as zinc stearate treatment, silane treatment such as silane coupling agent treatment, silane treatment such as alkylsilane treatment, fluorine compound treatment such as perfluoroalkylsilane, perfluoroalkyl phosphate salt, perfluoropolyether treatment, amino acid treatment such as N-lauroyl-L-lysine treatment, oil treatment such as squalane treatment, acrylic treatment such as alkyl acrylate treatment, etc., and one or more of these can be used in combination.

[0141] The powder or colorant is preferably treated with other powder dispersants or surface treatment agents, particularly those published by the inventors in this case in International Publication No. WO2009 / 022621, Japanese Patent Application Publication No. 2011-148784, Japanese Patent Application Publication No. 2011-149017, Japanese Patent Application Publication No. 2011-246704, Japanese Patent Application Publication No. 2011-246705, and Japanese Patent Application Publication No. 20 The novel powder treatment agents and methods disclosed in Publication No. 11-246706, International Publication No. WO2009 / 022621, International Publication No. WO2011 / 049246, International Publication No. WO2011 / 049248, and Japanese Patent Application No. 2011-286973 can be used for dispersion or surface treatment, or for slurry formation by using these novel powder treatment agents and the oils. Because these novel treatment agents have excellent inherent properties such as improved feel and dispersion stability, further improvements in the function, feel, and storage stability of cosmetics can be expected when used in conjunction with the novel cosmetic raw materials of this invention.

[0142] Furthermore, these powders or colorants can be partially or completely hydrophilized. This allows for the formulation of powders or colorants in an aqueous phase.

[0143] Furthermore, these powders or colorants can be partially or completely hydrophobically and hydrophilically treated. This imparts emulsifying properties to the powder itself. Commercially available examples include, for instance, Tayca's MZY-500SHE.

[0144] The powder or colorant (G) in the film-forming agent or cosmetic of the present invention may be used in one or more forms as needed, and the amount of these forms is not particularly limited. It may be formulated in the range of 0.1% to 99.5% by weight of the total film-forming agent or cosmetic, preferably 1% to 99% by weight. In particular, when used as a powder solid cosmetic, the amount of these forms is suitable to be in the range of 80% to 99% by weight of the total cosmetic.

[0145] (H) Gelatinizer or tackifier

[0146] As a gelling agent, oil-soluble gelling agents are preferred. Specifically, 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-di-n-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. One or more of these may be used as needed.

[0147] (I) Organically modified clay minerals

[0148] Examples of organically modified clay minerals include: dimethylbenzyl dodecylammonium montmorillonite clay, dimethyl dioctadecylammonium montmorillonite clay, dimethyl alkylammonium lithium bentonite, benzyl dimethyl stearylammonium lithium bentonite, and distearyl dimethylammonium chloride-treated magnesium aluminum silicate. Commercially available products of these include BENTONE 27 (benzyl dimethyl stearylammonium chloride-treated lithium bentonite: manufactured by National Lead) and BENTONE 38 (distearyl dimethylammonium chloride-treated lithium bentonite: manufactured by National Lead).

[0149] (J) Silicone Resin

[0150] Silicone resins are organopolysiloxanes with highly branched, network, or cage-like structures, and are liquid or solid at room temperature. Any silicone resin commonly used in cosmetics may be used, provided it does not deviate from the purpose of this invention. Examples of solid silicone resins include: MQ resins, MDQ resins, MTQ resins, MDTQ resins, TD resins, TQ resins, and TDQ resins, which contain any combination of trimethylsiloxane units (M units) (organic groups are methyl, methyl and vinyl, or phenyl), diorganosiloxane units (D units) (organic groups are methyl, methyl and vinyl, or phenyl), monoorganosiloxane units (T units) (organic groups are methyl, vinyl, or phenyl), and siloxane units (Q units). Furthermore, examples include trimethylsiloxane silica, polyalkylsiloxane silica, trimethylsiloxane silica containing dimethylsiloxane units, and alkyl (perfluoroalkyl)siloxane silica. These silicone resins are oil-soluble, and silicone resins soluble in D4 or D5 are particularly preferred. When applied to skin, hair, etc., silicone resin forms a uniform film, providing protection against dryness and low temperatures. Furthermore, silicone resin with these branched units can firmly bond with skin, hair, etc., imparting a glossy and transparent appearance to the skin and hair.

[0151] (K) Silicone rubber

[0152] In this invention, 1,000,000 mm 2High-viscosity organopolysiloxanes with a viscosity of / s or higher, referred to as silicone rubber, can also be used as silicone oils. Silicone rubber is a linear diorganopolysiloxane with an ultra-high degree of polymerization, also known as silicone raw rubber or organopolysiloxane rubber. Due to its high degree of polymerization, silicone rubber differs from oily silicones in that it has a measurable degree of plasticity. Examples of such silicone raw rubbers include substituted or unsubstituted organopolysiloxanes having dialkylsiloxy units (D units), such as dimethyl polysiloxane, methylphenyl polysiloxane, amino polysiloxane, methylfluoroalkyl polysiloxane, etc., or silicone raw rubbers having their micro-crosslinked structures. A representative example is the general formula: R10(CH3)2SiO{(CH3)2SiO}s{(CH3)R11SiO}tSi(CH3)2R10 (where R11...). It is a silicone raw rubber selected from vinyl, phenyl, alkyl with 6 to 20 carbon atoms, aminoalkyl with 3 to 15 carbon atoms, perfluoroalkyl with 3 to 15 carbon atoms, and alkyl containing a quaternary ammonium salt with 3 to 15 carbon atoms. The terminal group R10 is selected from alkyl with 1 to 8 carbon atoms, phenyl, vinyl, aminoalkyl with 3 to 15 carbon atoms, hydroxyl, and alkoxy with 1 to 8 carbon atoms. In addition, it is a silicone raw rubber represented by s = 2,000 to 6,000, t = 0 to 1,000, s + t = 2,000 to 6,000. Among them, dimethyl polysiloxane raw rubber with a degree of polymerization of 3,000 to 20,000 is preferred. These silicone rubbers can be formulated directly or in the form of a liquid gel dispersion (oil dispersion of silicone rubber) dispersed in oily silicone into the film-forming agent or cosmetic of the present invention.

[0153] Examples of such silicone raw rubbers include substituted or unsubstituted organopolysiloxanes having dialkylsiloxane units (D units), such as dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, methylfluoroalkylpolysiloxane, etc., or organopolysiloxanes having their micro-crosslinked structures, etc. A representative example is the general formula: R 10 (CH3)2SiO{(CH3)2SiO} s {(CH3)R 12 SiO} t Si(CH3)2R 10 (where R) 12 It is a group selected from vinyl, phenyl, alkyl with 6 to 20 carbon atoms, aminoalkyl with 3 to 15 carbon atoms, perfluoroalkyl with 3 to 15 carbon atoms, and alkyl containing a quaternary ammonium salt with 3 to 15 carbon atoms, with the terminal group R. 10It is a group selected from alkyl, phenyl, vinyl, aminoalkyl, hydroxyl, and alkoxy groups having 1 to 8 carbon atoms; and also an organopolysiloxane represented by s = 2,000 to 6,000, t = 0 to 1,000, s + t = 2,000 to 6,000. Among these, dimethyl polysiloxane raw rubber with a degree of polymerization of 3,000 to 20,000 is preferred. Furthermore, amino-modified methyl polysiloxane raw rubber having 3-aminopropyl, N-(2-aminoethyl)3-aminopropyl, etc., as the molecular side chain or terminal is preferred. In addition, in this invention, one or more types of silicone rubber may be used as needed.

[0154] Because silicone rubber has an ultra-high degree of polymerization, it forms a protective film that is both highly resistant to residue and highly breathable on the skin and hair. Therefore, it is an ingredient with the following functions: particularly imparting shine and luster to the skin and hair, and providing a firming and shaping feel to the skin and hair during and after use.

[0155] The amount of silicone rubber incorporated is, for example, in the range of 0.05 to 30% by weight (mass) of the total film-forming agent or cosmetic, preferably in the range of 1 to 15% by weight (mass). Furthermore, if the silicone rubber is used in the form of an emulsified composition prepared by a pre-emulsification step (including emulsification polymerization), it is easy to formulate and can be stably incorporated into the film-forming agent or cosmetic of the present invention. If the amount of silicone rubber incorporated is less than the aforementioned lower limit, there is a concern that the effect of imparting shine to the skin and hair may become insufficient.

[0156] (L) Silicone elastomer

[0157] Silicone elastomers can be formulated into film-forming agents or cosmetics in any form, depending on their purpose. In particular, besides the silicone elastomer powders described in "(G) Powders," they are preferably formulated in the form of cross-linked organopolysiloxanes. Even when formulated into an aqueous dispersion, the silicone elastomer powder can be used in the cosmetics of the present invention. Commercially available examples of such aqueous dispersions include, for instance, BY 29-129 and PF-2001 PIF Emulsion manufactured by Toray Dow Corning. Formulating these aqueous dispersions (suspensions) of silicone elastomer powders is extremely useful in further improving the user experience of the cosmetics of the present invention.

[0158] As a crosslinked organopolysiloxane, it is preferable to form a three-dimensional crosslinked structure through the reaction of organopolysiloxane chains with crosslinking components, etc., and to be a non-emulsifiable crosslinked organopolysiloxane without hydrophilic parts such as polyoxyalkylene supporting units. If it is such a crosslinked organopolysiloxane, it can be used without limitation regardless of physical form or manufacturing method such as dilution or properties. As a particularly preferred crosslinked organopolysiloxane, examples include the α,ω-diene crosslinked silicone elastomers described in U.S. Patent No. 5,654,362 (commercially available products, DC 9040 Silicone Elastomer Blend, DC 9041 Silicone Elastomer Blend, DC 9045 Silicone Elastomer Blend, DC 9046 Silicone Elastomer Blend, manufactured by Dow Corning Incorporated). Alternatively, crosslinked organopolysiloxanes that are fluid at room temperature may be used appropriately, such as 3901 LIQUID SATIN BLEND (manufactured by Dow Corning).

[0159] (M) Organic modified silicone

[0160] Organically modified silicones are preferably lipophilic. Specifically, in addition to the aforementioned, examples include: amino-modified silicones, amino-polyether-modified silicones, epoxy-modified silicones, carboxyl-modified silicones, amino acid-modified silicones, methanol-modified silicones, acrylic-modified silicones, phenol-modified silicones, amide-alkyl-modified silicones, amino-diol-modified silicones, and alkoxy-modified silicones. These organically modified silicones, in addition to having a polysiloxane bond as the main chain, may have alkyl chains, amino-alkyl chains, or polyether chains with a degree of hydrophilicity. The organic modification group may be present on one or both sides of the side chain or end of the polysiloxane chain. When using the cosmetic of the present invention as a hair cosmetic, amino-modified silicones, methanol-modified silicones, amino-polyether-modified silicones, or amino-diol-modified silicones can be suitably used. Examples of amino-modified silicones typically containing 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, etc., are also mentioned.

[0161] The following describes highly preferred organic modified silicones, including advanced alkyl-modified silicones, alkyl-modified silicone resins, and polyamide-modified silicone resins. Advanced alkyl-modified silicones are waxy at room temperature and are useful ingredients as raw materials for cosmetics. Therefore, they can be suitably used in the cosmetics of the present invention. Examples of such advanced alkyl-modified silicone waxes include, for instance, trimethylsiloxy-terminated methyl long-chain alkyl polysiloxanes, trimethylsiloxy-terminated dimethyl polysiloxane-methyl long-chain alkyl siloxane copolymers, and long-chain alkyl-modified dimethyl polysiloxanes. Commercially available examples of these include AMS-C30 Cosmetic Wax and 2503 Cosmetic Wax (manufactured by Dow Corning).

[0162] In the cosmetics of the present invention, the advanced alkyl-modified silicone wax preferably has a melting point of 60°C or higher in terms of makeup retention and high-temperature stability.

[0163] Alkyl modified silicone resins are ingredients that impart sebum durability, moisturizing properties, and a smooth texture to cosmetics. Alkyl modified silicone resins that are waxy at room temperature are suitable for use. For example, silsesquioxane resin waxes described in Japanese Patent Publication No. 2007-532754 are preferred. Commercially available examples of these include SW-8005 C30 RESINWAX (manufactured by Dow Corning).

[0164] Examples of polyamide-modified silicones include siloxane-based polyamide compounds described in U.S. Patent No. 5,981,680 (Japanese Patent Application Publication No. 2000-038450) or Japanese Patent Publication No. 2001-512164. Commercially available examples include 2-8178 Gellant and 2-8179 Gellant (manufactured by Dow Corning Incorporated). These polyamide-modified silicones also function as thickeners / gelling agents for oily raw materials, particularly silicone oils.

[0165] (N) Ultraviolet protection ingredients

[0166] Ultraviolet (UV) defense ingredients can be inorganic or organic. If the cosmetic material of this invention is a sunscreen, it preferably contains at least one inorganic or organic, particularly organic, UV defense ingredient. The film-forming agent of this invention generally exhibits excellent compatibility with poorly soluble organic UV defense ingredients, such as diethylaminohydroxybenzoyl benzoate (known as "Uvinul A"), bis(ethylhexyloxyphenol) methoxyphenyl triazine (known as "Tinosorob S"), 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester (known as "Octocrylene"), and other cinnamic acid-based UV absorbers, thereby improving the formulation stability with the film-forming agent of this invention.

[0167] The inorganic ultraviolet defense component can be formulated using inorganic pigment powders, metal powder pigments, etc., as ultraviolet dispersants. Examples include metal oxides such as titanium oxide, zinc oxide, cerium oxide, low-valent titanium oxide, and iron-doped titanium oxide; metal hydroxides such as iron hydroxide; plate-shaped iron oxide; metal flakes such as aluminum flakes; and ceramics such as silicon carbide. Among these, at least one type of granular, plate-shaped, needle-shaped, or fibrous microparticle metal oxide and microparticle metal hydroxide with an average particle size in the range of 1 to 100 nm is particularly preferred. These powders are preferably subjected to conventionally known surface treatments, such as fluorine compound treatment (preferably perfluoroalkyl phosphate treatment or perfluoroalkyl silane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment), silicone treatment (preferably methylhydropolysiloxane treatment, dimethylpolysiloxane treatment, fumed tetramethyltetrahydrocyclotetrasiloxane treatment), silicone resin treatment (preferably trimethylsiloxysilicic acid treatment), side chain treatment (methods such as adding alkyl chains after fumed 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 stearic acid or myristate), acrylic resin treatment, metal oxide treatment, etc., preferably by a combination of these treatments. For example, coating the surface of microparticle titanium oxide with a metal oxide such as silicon oxide or aluminum oxide and then surface treating it with an alkylsilane can be cited. The amount of surface treatment is preferably in the range of 0.1 to 50% by mass relative to the powder.

[0168] Organic UV-protective ingredients are lipophilic UV-protective ingredients. Examples include: para-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 diethylaminohydroxybenzoylbenzoate, etc., which are benzoic acid-based UV absorbers; N-acetyl-o-aminobenzoic acid homomethyl ester, etc.; and pentyl salicylate, menthyl salicylate, homomethyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanol phenyl salicylate. Salicylic acid-based ultraviolet absorbers such as esters; 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), ethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate, mono-2-ethylhexanoyl-di-p-methoxycinnamate, 3,4,5 Cinnamon acid-based ultraviolet absorbers such as 3-methyl-4-[methylbis(trimethylsiloxy)silyl]butyl trimethoxycinnamic acid; 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-carboxylic acid ester, hydroxy-4-n-octyloxy Benzophenone, 4-hydroxy-3-carboxybenzophenone, and other benzophenone-based ultraviolet absorbers; 3-(4'-methylbenzylene)-d,l-camphor, 3-benzylene-d,l-camphor, uric acid, ethyl uric acid, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, dibenzylazine, bifenthionylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornyl)-3-pentane-2-one, etc.

[0169] Alternatively, a hydrophobic polymer powder containing the aforementioned organic UV-defense component can also be used. The polymer powder may or may not be hollow, and an average primary particle size in the range of 0.1–50 μm is acceptable; the particle size distribution can be wide or narrow. Examples of polymers include acrylic resins, methacrylic resins, styrene resins, polyurethane resins, polyethylene, polypropylene, polyethylene terephthalate, silicone resins, nylon, acrylamide resins, and silanized polypeptide resins. Preferably, the polymer powder contains an organic UV-defense component in the range of 0.1–30% by mass, and particularly preferably, a polymer powder containing a UV-A absorber, namely 4-tert-butyl-4'-methoxydibenzoylmethane.

[0170] Alternatively, a product made by dispersing the aforementioned organic UV-protective components in water can also be used. Tinosorb A2B (manufactured by BASF) is an example of a commercially available product.

[0171] In the cosmetics of the present invention, the suitable UV-protective ingredient is selected from at least one of the following groups: microparticle titanium dioxide, microparticle zinc oxide, 2-ethylhexyl p-methoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, diethylaminohydroxybenzoylhexylbenzoate, bis(ethylhexyloxyphenol)methoxyphenyltriazine, 2-ethylhexyl 2-cyano-3,3-diphenylprop-2-enoic acid, and other benzophenone-based UV absorbers. These UV-protective ingredients are versatile, readily available, and have high UV-protective efficacy, and are therefore suitable for use. It is particularly preferred to use inorganic and organic UV-protective ingredients in combination, and even more preferred to use a UV-A corresponding UV-protective ingredient in combination with a UV-B corresponding UV-protective ingredient.

[0172] (O) Water-soluble polymers

[0173] On the other hand, the film-forming agent or cosmetic of the present invention can be an aqueous or emulsion type containing a large amount of water-soluble components, and can also be formulated with water-soluble polymers according to its dosage form, which is preferred. As a water-soluble polymer, one or more water-soluble polymers can be used. Examples of natural water-soluble polymers include: gum arabic, tragacanth gum, galactopolysaccharide, guar gum, locust bean gum, ebony gum, carrageenan, pectin, agar, quince seeds (quince), seaweed extract (brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid and other plant-based polymers; xanthan gum, dextran, succinyl polysaccharide, pullulan and other microbial polymers; collagen, casein, albumin, gelatin and other animal-based polymers. In addition, examples of semi-synthetic water-soluble polymers include: starch-based polymers such as carboxymethyl starch and methyl hydroxypropyl starch; cellulose-based polymers such as methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose, and cellulose powder; and alginate-based polymers such as sodium alginate and propylene glycol alginate. Examples of synthetic water-soluble polymers include: vinyl-based polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, and carboxyvinyl polymers (CARBOPOL 940, 941; BFGoodrich); polyoxyethylene-based polymers such as polyethylene glycol 20,000, polyethylene glycol 6,000, and polyethylene glycol 4,000; copolymer-based polymers such as polyoxyethylene-polyoxypropylene copolymers and PEG / PPG methyl ether; acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide; and polyethyleneimine and cationic polymers. Other cationic water-soluble polymers, especially those suitable for formulation into hair cosmetics, include: quaternary nitrogen-modified polysaccharides (e.g., cationic modified cellulose, cationic modified hydroxyethyl cellulose, cationic modified guar gum, cationic modified locust bean gum, cationic modified starch, etc.), dimethyl diallyl ammonium chloride derivatives (e.g., dimethyl diallyl ammonium chloride-acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), and vinylpyrrolidone derivatives (e.g., vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer salt, vinylpyrrolidone-methacrylamidepropyltrimethylammonium chloride copolymer, vinylpyrrolidone-methylvinylimidazolium chloride copolymer, etc.).

[0174] In the cosmetics of the present invention, other ingredients commonly used in cosmetics may be added to the product without hindering the effects of the present invention, such as organic resins, moisturizers, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients (whitening agents, cell activators, skin roughness improvers, blood flow promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, etc. Specific examples of these are common to the ingredients specifically disclosed in paragraphs 0100 to 0113 of Japanese Patent Application Publication No. 2011-149017, but are not limited thereto.

[0175] The cosmetics of the present invention can be formulated with natural plant extracts, seaweed extracts, and natural medicinal ingredients, depending on the intended use. Two or more of these ingredients can be formulated. Specific examples of these ingredients are common to those specifically disclosed in paragraph 0115 of Japanese Patent Application Publication No. 2011-149017, but are not limited thereto.

[0176] In the cosmetics of the present invention, in addition to purified water, mineral water and other water, solvents such as light isomeric paraffin, ethers, LPG (liquefied petroleum gas), N-methylpyrrolidone, and next-generation chlorofluorocarbons may be formulated as needed.

[0177] In addition, the cosmetics of the present invention may use at least one ingredient selected from the group consisting of acrylic silicone dendritic polymer copolymers and alkyl-modified silicone resin waxes, besides the copolymers of the present invention. These are film-forming ingredients like the copolymers of the present invention, but unlike the copolymers of the present invention, they are not also cleansing ingredients, and therefore it is preferable to formulate them within the range that does not impair the technical effects of the present invention.

[0178] As an acrylic silicone dendritic polymer copolymer, a vinyl polymer having a carbosiloxane dendritic polymer structure as described in Japanese Patent No. 4009382 (Japanese Patent Application Publication No. 2000-063225) is particularly preferred. Examples of commercially available products include FA 4001 CM SiliconeAcrylate and FA 4002 ID SiliconeAcrylate manufactured by Toray Dow Corning.

[0179] As an alkyl-modified silicone resin wax, the sesquioxane resin wax described in Japanese Patent Publication No. 2007-532754 is preferred, for example.

[0180] The cosmetic material of the present invention can be in any form, such as liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, or spray.

[0181] The film-forming agent of the present invention can form a film on the skin or hair that is water-resistant, sebum-resistant, and has excellent cleansing properties, and can be used to design cosmetics that impart these functional films.

[0182] Examples of cosmetic products that can be exemplified by the present invention include: skin cleansing products, skin care products, makeup products, antiperspirant products, ultraviolet protection products, and other skin cosmetics; hair cleansing products, hair styling products, hair coloring products, hair nourishing products, hair conditioner products, hair conditioning products, hair repair products, and other hair cosmetics; bath cosmetics; hair growth agents, hair regrowth agents, analgesics, bactericides, anti-inflammatory agents, cooling agents, and skin aging prevention agents, but are not limited to these.

[0183] The aforementioned skin cosmetics can also be used on the scalp, face (including lips, eyebrows, and cheeks), fingers, nails, and any part of the body. Specifically, examples include: cleansing gels, cleansing creams, cleansing foams, facial cleansers, eye makeup removers, facial foams, liquid soaps (shower gels), hand soaps, gel soaps, shaving creams, nail polish removers, acne treatment cosmetics, and other skin cleansing products; skin creams, scalp conditioners, skim milk, milk lotions, emulsions, face masks, talcum powder, fragrances, facial cleansing liquids, massage lotions, and other skin care products; pressed powders, liquid foundations, oil-based foundations, primers, loose powders, face powders, blushes, lipsticks, blushes, lip glosses, eye creams, mascaras, eyebrow pencils, eyelash cosmetics, and other makeup products; deodorants and other antiperspirants; sunscreens and sun protection agents (anti-tanning agents), and other UV protection products.

[0184] Examples of hair cosmetics include: shampoos, 2-in-1 shampoos, and other hair cleansing agents; hair waxes, curl-holding agents, styling agents, hair creams, styling sprays, and styling liquids; hair dyes, hair dye sprays, hair dye liquids, and hair dye sticks; hair care products such as hair tonics, repair fragrances, and hair masks; and hair conditioners or conditioning products such as hair oils, conditioners, repair liquids, and conditioning gels. Additionally, examples of bath cosmetics include bubble baths.

[0185] Because the film-forming agent of the present invention has universal film-forming properties, it can also be formulated into various other products besides cosmetics, such as topical agents, coatings, application agents, defoamers, and deodorants. The film-forming agent of the present invention is useful in applications other than cosmetics, as it can also form functional films on substrates.

[0186] [Example]

[0187] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0188] 1. Preparation of copolymers and their liquid compositions

[0189] Example 1

[0190] Add 115.0 g of isopropanol (IPA) to a 500 mL four-necked flask equipped with a stirrer, thermometer, and reflux tube. Purge with nitrogen to degas completely and heat to 80 °C. Add 4.0 g (5 wt%) of acrylic acid, 26.4 g (33 wt%) of methyl methacrylate, and 9.6 g (12 wt%) of n-butyl acrylate to a dropping funnel, according to the following formula (A-1): [Chemistry 40]

[0191] 40.0 g (50 wt%) of the carbosiloxane dendritic polymer monomer and 0.8 g of 2,2'-azobis-2-methylbutyronitrile (V-601, manufactured by Otsuka Chemicals) were dissolved. Under a nitrogen atmosphere, the monomer mixture was added dropwise from a dropping funnel over 3 hours at 80°C. After the addition was complete, the mixture was heated and stirred under a nitrogen atmosphere for 3 hours. Gas chromatography was used to analyze the polymerization rate of the reaction product after stirring, and the results showed a polymerization conversion rate of 95%, indicating that a vinyl polymer was obtained. Furthermore, GPC (gel permeation chromatography) analysis revealed that the polymer had a number average molecular weight of 19,500. An isopropanol solution of this vinyl polymer was added to a rotary evaporator and stripped at 160°C or below 10 mmHg to obtain a solid. Octyl polymethylsiloxane (FZ-3196) was added to the obtained solid to obtain a film-forming agent for cosmetics with a non-volatile content of 39.4%.

[0192] <Analysis>

[0193] Number-average molecular weight Mn: Tetrahydrofuran was used as the dissolution solvent, and the analysis was performed using a calibration curve based on standard polystyrene.

[0194] Viscosity measurement: The viscosity of the composition at 25°C was measured using a Type E viscometer (VISCOMIC EMD) manufactured by Tokyo Keiki Co., Ltd.

[0195] Non-volatile concentration: Weigh 1 g of the sample on an aluminum pan with a diameter of 6 cm and determine the concentration from the residue remaining after heating at 150°C for 1 hour.

[0196] <Evaluation>

[0197] Film hardness: A 1 g sample is weighed onto a 6 cm diameter aluminum disc and heated at 150°C for 1 hour to form a film. The hardness is determined by whether cracks appear in the film after bending it together with the aluminum disc.

[0198] Sticky coating: This is determined by whether the aluminum disc, which is integrated with the coating, is lifted when touched with a finger.

[0199] Contact angle (water): After coating a vinyl copolymer IPA solution onto a glass plate, the solvent was dried and removed at room temperature to obtain a vinyl polymer coating. A 5 μL water droplet was placed on the surface of this coating, and the contact angle with water was measured. The measurement was performed using a drop shape analysis system (KRUSS DSA10 Mk-2), and the average value for n=5 or higher was calculated.

[0200] Contact angle (artificial sebum): After coating a vinyl copolymer IPA solution onto a glass plate, the solvent was removed by drying at room temperature to obtain a vinyl polymer coating. A 5 μL droplet of artificial sebum (a mixture of trioleic acid glyceride, oleic acid, and squalane in a ratio of 3:1:1) was placed on the surface of this coating, and the contact angle with the artificial sebum was measured. The measurement was performed using a droplet shape analysis system (KRUSS DSA10 Mk-2), and average values ​​for n=5 and above were obtained.

[0201] Cleanability Test 1: 0.2 g of 0.5 wt% toluene solution of Sudan III (CAS# 85-86-9) was added to 1 g of FZ-3196 solution of the vinyl copolymer and mixed. The resulting solution was coated onto a glass plate, and the solvent was removed by drying at 80°C for 1 hour to obtain a colored vinyl polymer coating. A 0.05 mol / L potassium hydroxide aqueous solution was added to a beaker equipped with a magnetic stirrer. The coating and glass plate were immersed halfway into the solution, and stirred for 3 minutes. After 3 minutes, the glass plate was removed, rinsed with deionized water using a wash bottle, and air-dried. Samples where the coating portion immersed in the potassium hydroxide aqueous solution was removed by washing were designated as "no," and samples where the coating remained after washing were designated as "yes."

[0202] Comparative Example 1

[0203] A commercially available Dow Corning® FA 4002 ID SILICONE ACRYLATE solvent (a carbosiloxane dendritic polymer with an acid value of 0 mgKOH / g and no acidic groups) was added to a rotary evaporator and stripped at 160°C or below 10 mmHg to obtain a solid. Octyl polymethylsiloxane (FZ-3196) was added to the obtained solid to obtain a gel-like composition with a solid content concentration of 42.5%.

[0204] Comparative Example 2

[0205] In the same manner as Comparative Example 1, commercially available Dow Corning® FA 4004 ID SILICONE ACRYLATE (acid value 0 mgKOH / g, without acidic groups) was added to a rotary evaporator and stripped at 160°C or below 10 mmHg to obtain a solid. Octyl polymethylsiloxane was added to the obtained solid to obtain a liquid composition with a solid content concentration of 40.5%.

[0206] Examples 2-18, Comparative Examples 3-6

[0207] The monomer raw materials and weight percentages of Example 1 were changed as shown in Tables 1-6 below, and the preparation was carried out in the same manner otherwise. Furthermore, the abbreviations in the tables are as follows. Additionally, in Example 18, the same amount of isopropanol (IPA) was used instead of octyl polymethylsiloxane for evaluation.

[0208] (B) Ingredients: AA: Acrylic acid MAA: Methacrylic acid (C) Ingredients: MMA: Methyl methacrylate n-Bu-A: n-Butyl acrylate 2EHMA: 2-Ethylhexyl methacrylate ISA: Isostearyl acrylate SA: Stearyl acrylate SMA: Stearyl methacrylate BMA: Benzyl methacrylate (A) Ingredients: A-1: [Chemistry 41]

[0209] A-2: [Chemistry 42]

[0210] A-3: [Chemistry 43]

[0211] [Table 1]

[0212] [Table 2]

[0213] [Table 3]

[0214] ※Evaluation was performed using IPA solution.

[0215] [Table 4]

[0216] *The raw materials do not contain ingredient (B).

[0217] [Table 5]

[0218] *The raw materials do not contain ingredient (B).

[0219] In addition to the results mentioned above, all films exhibited the characteristic smoothness and slipperiness of silicone. The copolymers of this invention, due to their moderate film stiffness, possess not only durability but also flexibility in bending, resulting in a non-sticky texture. They are also water-resistant, sebum-resistant, and demonstrate good washability against ionic aqueous solutions.

[0220] Cleanability Test 2

[0221] Furthermore, to confirm versatility, the composition of Example 4 was used, and commercially available cleaning agents, "Additive-Free Soap Foaming Shower Gel (manufactured by MIYOSHI SOAP)" or "Dove Moisturizing Cleansing Foam (manufactured by Unilever)," were used instead of the 0.05 mol / L potassium hydroxide aqueous solution in Cleansing Test 1. The tests were conducted similarly, and the results are as follows: Figure 1 As shown, the impregnated portion has been cleaned. The left side of the photo uses an additive-free soap-foaming shower gel, while the right side uses Dove Moisturizing Cleansing Foam. Therefore, it can be seen that the copolymer composition of the present invention exhibits cleaning properties not only for simple ionic aqueous solutions, but also for commercially available general-purpose cleaning agents.

[0222] 2. Preparation of powder compositions

[0223] Examples 19-26, Comparative Examples 7-11

[0224] 70.8 parts by weight of titanium dioxide (product name: Si-TiO2-CR50, manufactured by Miyoshi Chemical Co., Ltd.), 14.2 parts by weight of iron oxide (product name: SA-rouge, manufactured by Miyoshi Chemical Co., Ltd.), 5.0 parts by weight of silicone surfactant (product name: ES-5600 SILICONE GLYCEROL EMULSIFIER, manufactured by Dow Corning Incorporated), 10.0 parts by weight of FZ-3196 solution prepared in Examples 1-11 and Comparative Examples 1-5, and 7.0 parts by weight of FZ-3196 were mixed and a paste-like pigment composition was obtained using a three-roll mill (EXAKT M-50I).

[0225] [Average Particle Size]

[0226] The powder composition was diluted 500 times with D5 (SH245), and the average particle size was determined by the cumulative method using an ELSZ-2000ZS (manufactured by Otsuka Electronics).

[0227] Cleanability Test 3: After coating the powder composition onto a glass plate, it was dried at 50°C for 2 hours to obtain a powder coating film. One drop of Biore U Foam Hand Sanitizer (manufactured by Kao Corporation) was added to the surface of this coating film, and then gently swirled 10 times with a finger to allow it to blend. Then, a JK scraper (manufactured by NIPPON PAPER CRECIA Corporation) was pressed against the coating area, and the presence or absence of powder on the scraper was used for determination.

[0228] Water resistance: After coating the powder composition onto a glass plate, it is dried at 50°C for 2 hours to obtain a powder coating film. One drop of ion-exchanged water is added to the surface of the powder coating film, and the mixture is gently swirled 10 times with a finger to allow it to fuse. Then, a JK scraper is pressed against the coated area, and the presence or absence of powder on the scraper is used to determine its resistance.

[0229] [Table 6]

[0230] [Table 7]

[0231] As mentioned above, not only do films made from raw materials exhibit water resistance and washability, but films containing pigments used in cosmetics also exhibit water resistance and washability. Furthermore, it is known that the average particle size is smaller than that of film-forming agents that do not contain carboxylic acids, resulting in excellent dispersibility.

[0232] Examples 27-29

[0233] [Emulsifying Ability Evaluation]

[0234] Using the copolymer compositions obtained in Examples 2, 3, 9, and 10, water-in-oil emulsion compositions with the compositions shown in the table were prepared as follows, and the emulsion compositions were confirmed to be obtained. The results of viscosity measurements along with microscopic observations are shown in the table. In addition, in the table, parts represent parts by weight (mass).

[0235] Using the copolymer compositions obtained in Examples 3, 8, and 16, water-in-oil emulsion compositions with the compositions shown in Table 10 were prepared as described below, and the emulsion compositions were confirmed to be obtained. The results of viscosity measurements along with microscopic observations are shown in Table 10. Furthermore, in the tables, parts represent parts by weight (mass).

[0236] [Preparation method of water-in-oil emulsion composition]

[0237] Add the oil (product name SH200 2cst, manufactured by Dow Corning®) and the silicone surfactant (product name ES-5300 FORMULATION AID, manufactured by Dow Corning®) to a 1.200 ml container.

[0238] 2. Stir to ensure the surfactant is evenly dispersed or dissolved in the oil (oil phase A).

[0239] 3. Add salt and deionized water to another container, and mix and dissolve using a spatula. Then, mix in 1,3-butanediol and dissolve it (aqueous phase B).

[0240] 4. Immerse the saw teeth of the homogeneous disperser in oil phase A, and while stirring at 1000 rpm, inject aqueous phase B into oil phase A at a roughly uniform speed over approximately 45 seconds.

[0241] 5. Increase the speed of the homogeneous disperser to 3500 rpm and stir for 2 minutes to homogenize the contents into an emulsion.

[0242] 6. Stop temporarily, scrape off the oil adhering to the inner wall of the container with a scraper, and mix it with the generated emulsion.

[0243] 7. Stir at 3500 rpm for 3 minutes using a homogeneous disperser to emulsify the contents into a homogeneous emulsion.

[0244] [Viscosity Measurement]

[0245] The viscosity of the emulsion composition at 25°C was measured using a VISCOMIC EMD (Type E viscometer) manufactured by Tokyo Keiki Co., Ltd.

[0246] [Table 8]

[0247] *OMC: 2-Ethylhexyl p-methoxycinnamate

[0248] As described above, a water-in-oil emulsion containing the copolymer of the present invention was prepared, and its change over 3 months at room temperature was confirmed. Since the viscosity remained almost unchanged, this indicates that it can be used without any problems with emulsion systems.

Claims

1. A film-forming agent for cosmetics, characterized in that... A copolymer comprising a monomer composition polymerized from the following monomer composition: (A) Unsaturated monomers having at least one polysiloxane structure within their molecules, and (B) An unsaturated monomer having at least one acidic group or its salt within its molecule, and The monomer (A) in the monomer composition is 30% by weight or more.

2. The film-forming agent for cosmetics according to claim 1, wherein the acid value of the copolymer is 5 to 300 mgKOH / g.

3. The film-forming agent for cosmetics according to claim 1, wherein the weight ratio (A / B) of monomer (A) to monomer (B) is 1.0 to 20.

0.

4. The film-forming agent for cosmetics according to any one of claims 1 to 3, wherein the unsaturated monomer having at least one polysiloxane structure within the molecule is selected from... General formula (1) [Chemistry 1] In the formula, Y is an organic group capable of free radical polymerization, and R... 1 It is an alkyl or aryl group having 1 to 10 carbon atoms; X 1 For i = 1, the following formula represents a silane alkyl group; [Chemistry 2] (where R) 1 As mentioned above, R 2 It is an alkyl group with 2 to 10 carbon atoms, R 3 X is an alkyl group having 1 to 10 carbon atoms. i＋1 The radical is selected from the group consisting of hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, aryl groups, and silylalkyl groups; i is an integer from 1 to 10 representing the hierarchy of the silylalkyl group, and a i (integers from 0 to 3) or General formula (2) [Chemistry 3] (In the formula, Y and R) 1 Same as above; m is 0, 1, or 2, and n represents the average degree of polymerization and is a number from 0 to 200.

5. The film-forming agent for cosmetics according to any one of claims 1 to 4, wherein the monomer composition further comprises (C) a monomer having at least one carboxylic acid ester within its molecule.

6. The film-forming agent for cosmetics according to any one of claims 1 to 5, wherein monomer (B) is acrylic acid.

7. The cosmetic film-forming agent according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of (D) oils and (E) alcohols.

8. The cosmetic film-forming agent according to any one of claims 1 to 7, further comprising (F) a surfactant.

9. The film-forming agent for cosmetics according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of water, inorganic powder, organic powder, colorant, thickener, gelling agent, organic modified clay mineral, silicone resin, silicone rubber, silicone elastomer, organic modified silicone, ultraviolet defense ingredient, water-soluble polymer, organic resin, moisturizer, preservative, antioxidant, antibacterial agent, fragrance, salt, pH adjuster, chelating agent, cooling agent, anti-inflammatory agent, skin-beautifying ingredient, vitamin, amino acid, nucleic acid, hormone, inclusion compound, and antistatic agent.

10. A cosmetic material comprising a film-forming agent for cosmetics according to any one of claims 1 to 9.

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