JP6448079B2 - Cosmetic composition - Google Patents

Description

  The present invention relates to a cosmetic composition, and in particular, suitable as a cosmetic for washing such as hand soap, body soap and hair shampoo, a cosmetic for skin such as moisturizing cream and foundation, and a cosmetic for hair such as hair styling foam. The present invention relates to a cosmetic composition.

  Conventionally, polymers obtained by polymerizing anionic, cationic, amphoteric, or nonionic ethylenically unsaturated monomers have been used as cosmetic additives and bases.

  For example, Patent Document 1 discloses that a moisturizer contains a polymer obtained by polymerizing a monomer containing an amphoteric ethylenically unsaturated monomer.

  Polymers as additives and bases for cosmetics are required to have excellent foaming properties and excellent film forming ability. For this purpose, it is effective to increase the molecular weight of the polymer.

JP 2011-37759 A

  However, when the molecular weight of the polymer is increased, for example, when the polymer is blended in cleaning cosmetics such as hand soaps, body soaps, and hair shampoos, it becomes difficult to rinse off the cleaning cosmetics, or when rinsing and finishing. A squeaky sensation may occur in the later hair or skin. In addition, when the polymer is blended in a skin cosmetic such as a moisturizing cream, the skin may be squeezed or excessively tight. In addition, when the polymer is blended in a hair cosmetic such as a hair styling foam, it may be difficult to wash off the hair cosmetic.

  The present invention has been made in view of the above points, and without actually increasing the molecular weight of the polymer which is a base of cosmetics, it is possible to improve the foaming property, the film forming ability, etc. It aims at providing the cosmetic composition which can produce the advantage when molecular weight increases.

The cosmetic composition according to the present invention comprises a copolymer (A) comprising a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2):
Dicarboxylic acid (B),

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom. Or an alkyl group having 1 to 2 carbon atoms, A represents an oxygen atom or NH,
In formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom or 1 to 2 carbon atoms. Represents an alkyl group, and A represents an oxygen atom or NH.

  The molar ratio of the first structural unit to the second structural unit is preferably in the range of 2/8 to 8/2.

  The dicarboxylic acid (B) preferably contains one or more compounds selected from the group consisting of aspartic acid and glutamic acid.

  The dicarboxylic acid (B) preferably contains one or more compounds selected from the group consisting of oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, malic acid and tartaric acid.

  The ratio of the dicarboxylic acid (B) to the copolymer (A) is preferably in the range of 0.1 to 10% by mass.

  The cosmetic composition preferably contains a nonionic, cationic, anionic or amphoteric surfactant.

  The cosmetic composition according to the present invention is, for example, a cleaning cosmetic.

  The cosmetic composition according to the present invention may be a skin cosmetic.

  The cosmetic composition according to the present invention may be a hair cosmetic.

  According to the present invention, the foaming property or film-forming ability of the cosmetic composition is improved while suppressing the occurrence of disadvantages such as difficulty in rinsing, difficulty in washing off, and squeaky hair or skin, and excessive tension. can do.

  Hereinafter, the cosmetic composition according to an embodiment of the present invention will be described. The cosmetic composition according to the present embodiment contains a copolymer (A) and a dicarboxylic acid (B).

  The copolymer (A) includes a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom. Or a C1-C2 alkyl group is shown, A shows an oxygen atom or NH.

In Formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to ² carbon atoms, and R ⁴ and R ⁵ each independently represents a hydrogen atom or 1 to 2 carbon atoms. Represents an alkyl group, and A represents an oxygen atom or NH.

  Since the cosmetic composition contains the copolymer (A) and the dicarboxylic acid (B), the cosmetic composition was applied to the cleaning cosmetic by the first constituent unit in the copolymer (A). The foaming property at the time can be improved and smoothness at the time of washing can be imparted. In addition, the ability to form a film is enhanced due to the strength of intermolecular force due to the side chain structure, giving a moderate elasticity when applied to skin cosmetics, and good hair styling when applied to hair cosmetics. Can give sex.

  Furthermore, the cosmetic composition has the same advantages as when the molecular weight of the polymer is increased, such as improved foamability and improved film-forming ability. That is, the foamability or film-forming ability of the cosmetic composition is higher than the foamability or film-forming ability predicted from the actual molecular weight of the copolymer (A). Nonetheless, cosmetic compositions have increased polymer molecular weights that are difficult to rinse off, difficult to wash off, poor film retention, and squeaky hair or skin, and excessive tension. The disadvantage that occurs in the case of In addition, the retention strength of a film | membrane is the adhesive force between the film | membrane formed from a cosmetic composition, skin, and hair.

  The effects such as improvement of foamability and improvement of film-forming ability are obtained by the mutual action between the amino group in the second structural unit in the copolymer (A) and the carboxyl group in the dicarboxylic acid (B) in the cosmetic composition. This is considered to be caused by the formation of a pseudo cross-linked structure by the action. Further, unlike the case of increasing the molecular weight of the polymer in a linear manner, it is difficult to cause the disadvantages of being hard to rinse off, difficult to wash off, and the squeaky feeling of hair or skin, and the occurrence of excessive tension. It is considered that a spherical structure can be easily obtained by increasing the molecular weight by a general crosslinking structure. Furthermore, it is considered that the interaction between the amino group and the carboxyl group in the pseudo cross-linked structure is weaker than the cross-linked structure by the covalent bond, and this pseudo cross-linked structure is appropriately eliminated.

  The components in the cosmetic composition will be described in more detail.

  The copolymer (A) may include only the first structural unit and the second structural unit, or may include a structural unit other than these in addition to the first structural unit and the second structural unit.

  The molar ratio of the first structural unit to the second structural unit is preferably in the range of 20/80 to 80/20. When this value is 20/80 or more, the performance resulting from the first structural unit described above is sufficiently exhibited. When this value is 80/20 or less, a pseudo-crosslinked structure due to the interaction between the second structural unit and the dicarboxylic acid (B) is sufficiently formed. More preferably, the molar ratio is in the range of 35/65 to 65/35.

  When the copolymer (A) includes structural units other than the first structural unit and the second structural unit, the ratio of the total of the first structural unit and the second structural unit to all the structural units in the copolymer (A) However, it is preferable that it exists in the range of 50-100 mol%.

  The copolymer (A) includes, for example, various anionic unsaturated monomers, cationic unsaturated monomers, nonionic unsaturated monomers as structural units other than the first structural unit and the second structural unit, And other structural units derived from one or more monomers selected from the group consisting of ethylenically unsaturated monomers.

  Specific examples of anionic unsaturated monomers include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic acid Monoalkyl esters of unsaturated dicarboxylic acids such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, itaconic acid monoalkyl esters; 2- (meth) acryloyloxyethyl succinic acid; 2- (meth) acryloyloxyethyl phthalic acid Β-carboxyethyl (meth) acrylate; 2- (meth) acryloyloxyethyl tetrahydrophthalic acid; 2- (meth) acryloyloxyethyl hexahydrophthalic acid; vinyl sulfonic acid, (meth) allyl sulfonic acid, α-methyl Unsaturated monomer containing sulfonic acid group such as styrene sulfonic acid A sulfonic acid group-containing (meth) acrylamide monomer such as 2- (meth) acrylamide-2-methylpropanesulfonic acid; a phosphate group-containing unsaturated monomer such as (meth) acryloyloxyethyl phosphate; Etc.

  Specific examples of the cationic unsaturated monomer include alkyl (meth) acrylates such as (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, and (meth) acryloyloxyethyldimethylbenzylammonium chloride. Quaternary ammonium salts; alkyl (meth) acrylamide quaternary ammonium salts such as (meth) acryloylaminoethyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Quaternary anions such as dimethyldiallylammonium methylsulfate and trimethylvinylphenylammonium chloride Pyridinium salt group-containing unsaturated monomer; and the like.

  Specific examples of the nonionic unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t-. Butyl, (meth) acrylic acid pill, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid cyclohexyl, Decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, ( Heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters of alcohols having linear, branched or alicyclic hydrocarbon groups such as rail, (meth) acrylic acid behenyl; acrylonitrile; vinyl acetate; styrene; vinyl pyrrolidone; acrylamide, diacetone (Meth) acrylamide having linear, branched or alicyclic hydrocarbon groups such as acrylamide, N, N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide, Nt-octylacrylamide Derivatives; (Meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid isobornyl, (meth) acrylic acid esters such as glycidyl acrylate; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid (Meth) acrylic acid such as 2-hydroxypropyl Droxyalkyl ester; (meth) acrylic acid alkoxyalkyl ester such as (meth) acrylic acid ethoxyethyl and (meth) acrylic acid methoxyethyl; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other poly Monoesters of alkylene glycol and (meth) acrylic acid; hydroxyl groups of monoesters of polyalkylene glycol and (meth) acrylic acid such as methoxypolyethylene glycol mono (meth) acrylate and methoxypolypropylene glycol mono (meth) acrylate Unsaturated monomer having terminal alkyl ether; monofunctional unsaturated monomer such as glyceryl (meth) acrylate and N- (2-methacryloyloxyethyl) ethylene urea; 1,4-butanedio Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) Polyfunctional unsaturated monomers such as acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, methylenebisacrylamide, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate; Etc.

  The copolymer (A) can be obtained, for example, by polymerizing the ethylenically unsaturated monomer (a). In this case, the ethylenically unsaturated monomer (a) comprises a first monomer (a1) represented by the following formula (11) and a second monomer (a2) represented by the following formula (21). It is preferable to contain. When the ethylenically unsaturated monomer (a) contains the first monomer (a1), the first structural unit is formed in the copolymer (A). Further, when the ethylenically unsaturated monomer (a) contains the second monomer (a2), a second structural unit is formed in the copolymer (A).

In formula (11), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom. Or a C1-C2 alkyl group is shown, A shows an oxygen atom or NH.

In Formula (21), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom or 1 to 2 carbon atoms. Represents an alkyl group, and A represents an oxygen atom or NH.

  When the copolymer (A) includes a structural unit other than the first structural unit and the second structural unit, the ethylenically unsaturated monomer (a) includes the first monomer (a1) and the second single unit. In addition to the monomer (a2), a monomer other than the first monomer (a1) and the second monomer (a2) may be contained. Examples of the monomer other than the first monomer (a1) and the second monomer (a2) include the above-mentioned various anionic unsaturated monomers, cationic unsaturated monomers, and nonionic unsaturated monomers. One or more monomers selected from the group consisting of saturated monomers and other ethylenically unsaturated monomers may be mentioned.

  The molar ratio of the first monomer (a1) to the second monomer (a2) is preferably in the range of 20/80 to 80/20.

  When the ethylenically unsaturated monomer (a) includes structural units other than the first monomer (a1) and the second monomer (a2), the ethylenically unsaturated monomer (a) is based on the whole. The total proportion of the first monomer (a1) and the second monomer (a2) is preferably in the range of 50 to 100 mol%.

In preparing the ethylenically unsaturated monomer (a), the second monomer (a2) is prepared, and a part of the second monomer (a2) is amphotericized, An ethylenically unsaturated monomer (a) containing the monomer (a1) and the second monomer (a2) may be obtained. Amphotericization is performed by an appropriate method. For example, while stirring a hydrophilic solvent solution containing the second monomer (a2), a solution containing an amphoteric agent (aqueous solution, hydrophilic solvent solution, suspension, etc.) is dropped into this solution, and then this solution is added. A part of the second monomer (a2) can be amphotericized by heating the solution at 70 to 95 ° C. for 2 to 10 hours. Examples of the amphoteric agent include a compound represented by X—R ³ —COOH (X is a halogen atom), an alkali metal salt of this compound, and the like. When an alkali metal salt is used, a salt generated as a result of amphotericization is removed by an appropriate method such as filtration, ion exchange, or electrodialysis as necessary.

  The polymerization method of the ethylenically unsaturated monomer (a) is not particularly limited, and various known methods can be employed. In particular, it is preferable to radically polymerize the ethylenically unsaturated monomer (a) in a hydrophilic solvent or a mixed solvent containing water and a hydrophilic solvent. As the polymerization method, for example, a solution polymerization method, an emulsion polymerization method and the like can be employed. The copolymer (A) may be a block copolymer or a graft copolymer.

  Specific examples of the hydrophilic solvent include lower alcohols such as methanol and ethanol; lower ketones such as acetone; and the like. Of these solvents, only one kind may be used, or two or more kinds may be used in combination.

  In the polymerization of the ethylenically unsaturated monomer (a), it is also preferable to use a polymerization initiator. The polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4- Azo compounds such as dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine); benzoyl peroxide, lauroyl peroxide Organic peroxides such as potassium persulfate; ammonium persulfate; hydrogen peroxide solution;

  The reaction temperature for polymerizing the ethylenically unsaturated monomer (a) depends on the composition of the ethylenically unsaturated monomer (a), the type of polymerization initiator, the type of solvent, etc., but is 20 to 200 ° C. Within the range of is preferable. The reaction time depends on the composition of the ethylenically unsaturated monomer (a), the type of polymerization initiator, the type of solvent, etc., but is preferably in the range of 2 to 24 hours.

  An intermediate comprising the second structural unit is synthesized by polymerizing the ethylenically unsaturated monomer (a) containing the second monomer (a2), and one of the second structural units in the intermediate is synthesized. The copolymer (A) may be obtained by amphotericizing the part. Amphotericization is performed by an appropriate method. For example, while stirring a hydrophilic solvent solution containing an intermediate, a solution containing an amphoteric agent (aqueous solution, hydrophilic solvent solution, suspension, etc.) is dropped into this solution, and then this solution is added at 70 to 95 ° C. A part of the second structural unit can be amphotericized by heating for 2 to 10 hours.

  The weight average molecular weight of the copolymer (A) is preferably in the range of 100,000 to 1,000,000 as the weight average molecular weight in terms of protein as measured by gel filtration chromatography. When the weight average molecular weight is 1,000,000 or less, it is possible to suppress a squeaky feeling after rinsing or after finishing the cosmetic for cleaning, and to suppress an excessive feeling of skin cosmetics. It is possible to increase the retention of the skin cosmetics and hair cosmetics. In addition, when the weight average molecular weight is 100,000 or more, it is possible to sufficiently obtain the excellent foaming property of the cleaning cosmetic and to enhance the film forming ability of the skin cosmetic and the hair cosmetic. Can do. More preferably, the weight average molecular weight of the copolymer (A) is in the range of 150,000 to 900,000.

  The dicarboxylic acid (B) in the cosmetic composition according to the present embodiment may be a compound having two carboxyl groups in one molecule.

  The molecular weight of the dicarboxylic acid (B) is preferably in the range of 90 to 250. When the molecular weight is 90 or more, two carboxyl groups can be provided in one molecule. When the molecular weight is 250 or less, the water-solubility of the dicarboxylic acid (B) is appropriately maintained, so that the hydrophilicity of the copolymer (A) and the dicarboxylic acid (B) in the cosmetic composition is high. And sufficient interaction occurs between the copolymer (A) and the dicarboxylic acid (B).

  The dicarboxylic acid (B) preferably contains one or more compounds selected from the group consisting of aspartic acid and glutamic acid. Since these compounds have biocompatibility, the cosmetic composition has a high affinity for skin and hair, and when the cosmetic composition is used, a good feel can be obtained on the skin. Furthermore, since these compounds are also natural moisturizing factors, it is possible to impart moisturizing properties to the cosmetic composition.

  The dicarboxylic acid (B) may contain one or more compounds selected from the group consisting of oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, malic acid and tartaric acid. preferable. Since these compounds can be used as cosmetic raw materials, there are few concerns about danger to the living body even if they are blended in a cosmetic composition.

  The ratio of the dicarboxylic acid (B) to the copolymer (A) is preferably in the range of 0.1 to 10% by mass. When the proportion is 0.1% by mass or more, the foamability or film forming ability of the cosmetic composition is particularly excellent. Moreover, since stability of cosmetic composition is not inhibited as this ratio is 10 mass% or less, precipitation and aggregation of a copolymer (A) and another component can be prevented. More preferably, this ratio is in the range of 0.2 to 5 mass%.

  The cosmetic composition preferably contains at least one surfactant selected from nonionic, cationic, anionic or amphoteric surfactants.

  The nonionic surfactant is not particularly limited as long as it can be applied to cosmetic applications. For example, polyoxyalkylene addition type nonionic surfactant, mono- or diethanolamide type nonionic surfactant, sugar-based nonionic surfactant Surfactant, glycerin-type nonionic surfactant, etc. are mentioned.

  The polyoxyalkylene addition type nonionic surfactant includes a type in which one kind of polyoxyalkylene is added and a type in which two or more kinds of polyoxyalkylene are added. Specifically, the former includes, for example, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate, polyethylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil, and the latter includes, for example, polyoxypropylene / polyoxyethylene Examples include lauryl ether.

  Examples of the mono- or diethanolamide-based nonionic surfactant include lauric acid monoethanolamide, coconut oil fatty acid diethanolamide, and N-polyhydroxyalkyl fatty acid amide.

  Examples of sugar-based nonionic surfactants include sugar ether-based alkyl saccharides, sugar amides, sorbitan fatty acid esters, and sucrose fatty acid esters. More specific examples of the sugar amide-based nonionic surfactant include N-methylalkylglucamide such as N-methyllaurylglucamide, and more specific examples of the sorbitan fatty acid ester-based nonionic surfactant. Examples include sorbitan monoisostearate and sorbitan monooleate. More specific examples of the sucrose fatty acid ester nonionic surfactant include lauric acid sucrose ester, sucrose monostearate, POP sucrose monolaurate and the like.

  Examples of the glycerin-based nonionic surfactant include monoglycerin fatty acid ester-based nonionic surfactants such as glyceryl sesquioleate and polyoxyethylene glyceryl monostearate, and fatty acid ester-type polyglycerin-based nonionic surfactants such as polyglyceryl monoisostearate. Examples of the surfactant include alkyl ether type polyglycerin-based nonionic surfactants such as polyglyceryl and polyoxybutylene stearyl ether.

  The cationic surfactant is not particularly limited as long as it can be applied for cosmetic use. For example, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, stearyltrimethylammonium. Examples include saccharin, cetyltrimethylammonium saccharin, and behenyltrimethylammonium methylsulfate.

  Examples of alkyltrimethylammonium chlorides include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride.

  Examples of alkyltrimethylammonium bromides include cetyltrimethylammonium bromide and stearyltrimethylammonium bromide.

  The anionic surfactant is not particularly limited as long as it can be applied to cosmetics applications. For example, higher fatty acid salt type surfactants, sulfonate type surfactants, sulfate ester type surfactants, alkyl phosphorus An acid ester salt type surfactant is mentioned.

  Examples of the higher fatty acid salt type surfactant include C12 to C18 saturated or unsaturated fatty acid, coconut oil fatty acid, hydrogenated coconut oil fatty acid, palm oil fatty acid, hydrogenated palm oil fatty acid, beef tallow fatty acid, hardened tallow fatty acid and the like (potassium Fatty acid soap such as salt (potassium base), sodium salt (sodium base), triethanolamine salt, ammonium salt, etc .; alkyl ether carboxylate, N-acyl sarcosine salt, N-acyl glutamate, etc. It is done. More specifically, for example, potassium laurate, sodium lauryl ether carboxylate, sodium N-lauroyl sarcosine, sodium N-lauroyl glutamate, N-lauroylmethyl-β-alanine triethanolamine and the like can be mentioned. In addition, when the fatty acid soap is contained in the cosmetic composition, the fatty acid soap itself may be blended in the cosmetic composition, or the fatty acid and alkali are separately blended in the cosmetic composition. It may be neutralized in the product.

  Examples of the sulfonate surfactant include N-acylaminosulfonate and polyoxyethylenesulfosuccinate. More specifically, for example, sodium N-cocoylmethyl taurate, sodium polyoxyethylene alkylsulfosuccinate and the like can be mentioned.

  Examples of the sulfate ester type surfactant include higher alkyl sulfates and polyoxyethylene alkyl ether sulfates.

  Examples of the alkyl phosphate ester type surfactant include monolauryl phosphate triethanolamine and monolauryl dipotassium phosphate.

The amphoteric surfactant is not particularly limited as long as it can be applied to cosmetics. For example, carboxylic acid types such as imidazoline type (amidoamine type), amide amino acid salt, carbobetaine type (alkylbetaine, alkylamidobetaine), etc. Examples include amphoteric surfactants, sulfobetaine types (alkyl sulfobetaines, alkylhydroxysulfobetaines), phosphobetaine types, acyl tertiary amine oxides, acyl tertiary phosphine oxides, and the like.
More specifically, examples of the carboxylic acid type amphoteric surfactant include an imidazoline type such as coconut oil alkyl-N-hydroxyethyl imidazolinium betaine; an alkyl betaine such as lauryl dimethylaminoacetic acid betaine; Examples thereof include coconut oil fatty acid amidopropyl betaine.
Examples of the alkylsulfobetaine include coconut oil fatty acid dimethylsulfopropylbetaine. Examples of the alkylhydroxysulfobetaine include lauryldimethylaminohydroxysulfobetaine.

  Examples of the phosphobetaine type include lauryl hydroxyphosphobetaine. Examples of the acyl tertiary amine oxide include lauryl dimethylamine oxide.

  Examples of the acyl tertiary phosphine oxide include lauryl dimethyl phosphine oxide.

  In this embodiment, when a trifunctional or higher polyfunctional carboxylic acid such as a tricarboxylic acid is used instead of the dicarboxylic acid (B), the cosmetic composition has an excessively high acidity. The product becomes extremely unstable, and as a result, components such as the copolymer (A) in the cosmetic composition may be precipitated or aggregated. In addition, when a trifunctional or higher polyfunctional carboxylic acid is used, the pseudo-crosslinked structure is excessively formed, so that the user feels squeaky hair or skin, or a film formed from a cosmetic composition. There is a risk that the holding power of the lowering.

  The cosmetic composition may further contain known additives such as a solvent, a dispersion stabilizer, a preservative, and a light stabilizer depending on the specific application.

  The cosmetic composition is prepared, for example, as a skin cosmetic. Skin cosmetics are, for example, makeup cosmetics such as liquid foundations and cream foundations, or skin care cosmetics such as moisturizing serums, emulsions, moisturizing creams and the like.

  When the cosmetic composition is prepared as a skin cosmetic, the film-forming ability of the skin cosmetic is improved. For this reason, the firmness of the skin is improved and the stickiness is reduced without excessive tension. Furthermore, the skin cosmetics can easily take in moisture, and the moisture retention of the skin cosmetics is improved.

  Makeup cosmetics can contain, for example, extender pigments, colorants (color pigments), pearl agents, lame agents, oils, waxes, moisturizers and the like. Skin care cosmetics can contain, for example, polyhydric alcohols, vegetable oils, amino acids, peptides, proteins, sugars, emulsifiers, moisturizers, alkali agents, thickeners, colorants, fragrances and the like.

  The ratio of the total amount of the copolymer (A) and the dicarboxylic acid (B) in the skin cosmetic is, for example, in the range of 0.01 to 30% by mass. This ratio may be in the range of 0.1 to 20% by mass or in the range of 0.5 to 15% by mass.

  The cosmetic composition may be prepared as a hair cosmetic. The cosmetic for hair is, for example, a hair spray, hair mist, hair gel, hair cream, hair wax, hair lotion, non-gas aerosol agent (hair mist agent), hair styling foam (hair mousse), curler water, or hair treatment.

  When the cosmetic composition is prepared as a hair cosmetic, especially when the hair cosmetic is a foam-like preparation such as a hair styling foam, the amount of foam and the foam retention of the hair cosmetic are improved. . That is, the quality of the foam formed from the cosmetic for hair is improved. Nevertheless, it does not happen that the retention of the film is reduced or the hair cosmetic is difficult to wash off.

  The cosmetic for hair can contain various additives, such as a polyhydric alcohol, surfactant, silicone, an ultraviolet-ray inhibitor, antioxidant, and a hair nourishing agent.

  The ratio of the total amount of the copolymer (A) and the dicarboxylic acid (B) in the hair cosmetic is, for example, in the range of 0.01 to 30% by mass. This ratio may be in the range of 0.1 to 20% by mass or in the range of 1 to 15% by mass.

  The cosmetic composition may be prepared as a cleaning cosmetic. The cosmetic for cleaning is, for example, hand soap, body soap, hair shampoo or the like.

  When the cosmetic composition is prepared as a cleaning cosmetic, the foaming speed, the amount of foam, and the foam thickness of the cleaning cosmetic are improved. That is, the quality of the foam formed from the cleaning cosmetic is improved. Moreover, it becomes easy to rinse off the cleaning cosmetic. Furthermore, it becomes difficult to produce a squeaky feeling on the hair and skin washed with the washing cosmetic.

  Cosmetics for washing include, for example, fatty acid soaps, surfactants, oils, lanolin derivatives, protein derivatives, water-soluble polymer compounds, acrylic resin dispersions, vitamins, bactericides, preservatives, pH adjusters, antioxidants, metals You may contain sequestering agent, a ultraviolet absorber, animal and plant extracts or its derivative (s), pigment | dye, fragrance | flavor, a pigment, etc.

  The ratio of the total amount of the copolymer (A) and the dicarboxylic acid (B) in the cleaning cosmetic is, for example, in the range of 0.01 to 10% by mass. This ratio may be in the range of 0.05 to 5% by mass or in the range of 0.1 to 1% by mass.

[Production Example 1]: Production of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution As a reactive monomer mixture, N-methacryloyloxyethyl-N , N-dimethylammonium-α-carboxybetaine and 2- (dimethylamino) ethyl methacrylate were prepared as follows.

  800 parts by mass of ethanol was charged into a 10 L capacity reaction vessel equipped with a cooling pipe, a thermometer, a gas introduction pipe and a stirrer, and nitrogen gas was aerated for 30 minutes while stirring, and then 320 parts by mass of potassium hydroxide. Was added and the reflux state was maintained for 30 minutes. Next, potassium monochloroacetate was prepared by adding dropwise a solution prepared by dissolving 756.8 parts of monochloroacetic acid in 400 parts by mass of ethanol to the reaction vessel. During the dropping, the temperature inside the reaction vessel was adjusted to 60 ° C. by appropriately removing the heat generated by neutralization. After adding 1264 parts by mass of 2- (dimethylamino) ethyl methacrylate to the obtained potassium monochloroacetate solution, the reflux state was maintained for 5 hours while ventilating air gas, and then 147.2 parts by mass while cooling. Part of potassium hydroxide was added and aged for 30 minutes. By-product potassium chloride and unreacted potassium monochloroacetate are removed from the resulting slurry solution by filtration, and then diluted with ethanol so that the content of the reactive monomer mixture is 50% by mass. Thus, a mixed solution of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl was obtained.

  Moreover, as a result of calculating reaction efficiency by quantifying unreacted 2- (dimethylamino) ethyl methacrylate by gas chromatography, 65 mol% of 2- (dimethylamino) ethyl methacrylate was N-methacryloyloxyethyl. It was found that it was converted to -N, N-dimethylammonium-α-carboxybetaine.

[Production Example 2]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 65/35) Production of N-methacryloyloxyethyl-N, N-dimethylammonium-α- obtained in Production Example 1 in a 1 L capacity reaction vessel equipped with a cooling pipe, a thermometer, a gas introduction pipe and a stirrer Carrying out 200 parts by mass of a carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by mass as an unsaturated monomer), aerating nitrogen gas for 30 minutes, and then maintaining the reflux state with heating to 0.5% 2,2′-Azobisisobutyronitrile in parts by mass was added, and the polymerization reaction was allowed to proceed by aging at reflux for 4 hours. Subsequently, while distilling a solvent off from the solution in reaction container, the solvent content in a solution is adjusted by adding water and ethanol in this reaction solution, N-methacryloyloxyethyl-N with a solid content concentration of 30% , N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 65/35) was obtained. The weight average molecular weight of this copolymer was 530,000.

[Production Example 3]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 50/50) In Production Example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / 2- (dimethylamino) ethyl methacrylate mixed solution, N-methacryloyl 161 parts by mass of an oxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by mass as an unsaturated monomer), 2- (dimethylamino) ethyl methacrylate A mixture of 19.5 parts by weight and 19.5 parts by weight of ethanol was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and a 30% solid content concentration of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer A solution having a molar ratio of the first structural unit to the second structural unit: 50/50 was obtained. The weight average molecular weight of this copolymer was 550,000.

[Production Example 4]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 35/65) In Production Example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / 2- (dimethylamino) ethyl methacrylate mixed solution, N-methacryloyl 118.2 parts by weight of oxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by weight as an unsaturated monomer), 2- (dimethylamino) methacrylic acid ) A mixture of 40.9 parts by weight of ethyl and 40.9 parts by weight of ethanol was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and a 30% solid content concentration of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer A solution (molar ratio of the first structural unit to the second structural unit: 35/65) was obtained. The copolymer had a weight average molecular weight of 570,000.

[Production Example 5]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 20/80) In Production Example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / 2- (dimethylamino) ethyl methacrylate mixed solution, N-methacryloyl Oxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by mass as an unsaturated monomer) 71.0 parts by mass, methacrylic acid 2- (dimethylamino) ) A mixture of 64.5 parts by weight of ethyl and 64.5 parts by weight of ethanol was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and a 30% solid content concentration of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer A solution (molar ratio of the first structural unit to the second structural unit: 20/80) was obtained. The weight average molecular weight of this copolymer was 580,000.

[Production Example 6]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 80/20) Production In Production Example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution, N-methacryloyl 84.6 parts by mass of oxyethyl-N, N-dimethylammonium-α-carboxybetaine (purified solid from which unreacted substances and solvent have been removed), 15.4 parts by mass of 2- (dimethylamino) ethyl methacrylate, and ethanol 100 parts by weight of the mixture was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and a 30% solid content concentration of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer A solution (molar ratio of the first structural unit to the second structural unit: 80/20) was obtained. The copolymer had a weight average molecular weight of 510,000.

[Production Example 7] N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl / methacrylic acid 2-hydroxyethyl copolymer (first structural unit and Mole ratio of two structural units: 65/35) In Production Example 2, 200 parts by mass of a mixed solution of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl Instead of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by mass as an unsaturated monomer) 160 parts by mass, methacrylic acid Mixture of 20 parts by mass of 2-hydroxyethyl and 20 parts by mass of ethanol It was used.

  Otherwise, the synthesis was carried out under the same conditions as in Production Example 2, and a solid content concentration of 30% N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl / methacrylic acid A solution of 2-hydroxyethyl copolymer (molar ratio of the first structural unit to the second structural unit: 65/35) was obtained. The weight average molecular weight of this copolymer was 540,000.

[Production Example 8]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl · 2- (methacryloyloxy) ethyltrimethylammonium chloride copolymer (first Mole ratio of structural unit to second structural unit: 65/35) In Production Example 2, mixed N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine and 2- (dimethylamino) ethyl methacrylate Instead of 200 parts by mass of the solution, N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by mass as an unsaturated monomer) 168% Part, 2- (methacryloyloxy) ethyltrimethyl A mixture of 20 parts by mass of ruammonium chloride (an aqueous solution containing 80% by mass of the active ingredient) and 12 parts by mass of ethanol was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine having a solid content concentration of 30%, 2- (dimethylamino) ethyl methacrylate, 2- A solution of (methacryloyloxy) ethyltrimethylammonium chloride copolymer (molar ratio of the first structural unit to the second structural unit: 65/35) was obtained. The weight average molecular weight of this copolymer was 580,000.

[Production Example 9] N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl / N- (2-methacryloyloxyethyl) ethylene urea copolymer (No. Mole ratio of one constituent unit to second constituent unit: 65/35) In Production Example 2, N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine · 2- (dimethylamino) ethyl methacrylate In place of 200 parts by mass of the mixed solution, N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution (50% by mass as an unsaturated monomer) 160 Parts by mass, N- (2-methacryloyloxyethyl) ethylene urea 40 parts by weight of a mixture was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine having a solid content concentration of 30%, 2- (dimethylamino) ethyl methacrylate, 2- A solution of (methacryloyloxy) ethyltrimethylammonium chloride copolymer (molar ratio of the first structural unit to the second structural unit: 65/35) was obtained. The weight average molecular weight of this copolymer was 580,000.

[Production Example 10]: N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (molar ratio of the first structural unit to the second structural unit: 65/35) In Production Example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution, N-methacryloyl 100 parts by mass of oxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixture (viscous liquid from which the solvent was removed from the mixed solution of Production Example 1) and 15 parts by mass of ethanol Of 2,2′-azobisisobutyronitrile in place of 0.5 part by mass. Te, 2,2'-azobis (2,4-dimethylvaleronitrile) were used 0.1 parts by weight.

  Otherwise, the synthesis was carried out under the same conditions as in Production Example 2, and an N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine polymer having a solid content concentration of 30% (the first constituent unit and the second constituent unit) A solution with a molar ratio of 65/35) was obtained. The weight average molecular weight of this polymer was 1,000,000.

[Production Example 11]: Production of N-methacryloylaminopropyl-N, N-dimethylammonium-α-carboxybetaine / N- (3-dimethylaminopropyl) methacrylamide mixed solution In Production Example 1, 2- (dimethyl methacrylate) Instead of 1264 parts by weight of amino) ethyl, 1369 parts by weight of N- (3-dimethylaminopropyl) methacrylamide were used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 1 to obtain a mixed solution of N-methacryloylaminopropyl-N, N-dimethylammonium-α-carboxybetaine / N- (3-dimethylaminopropyl) methacrylamide.

  As a result of calculating reaction efficiency by quantifying unreacted N- (3-dimethylaminopropyl) methacrylamide by gas chromatography, 65 mol% of N- (3-dimethylaminopropyl) methacrylamide was N-methacryloyl. It was found that it was converted to aminopropyl-N, N-dimethylammonium-α-carboxybetaine.

[Production Example 12]: N-methacryloylaminopropyl-N, N-dimethylammonium-α-carboxybetaine · N- (3-dimethylaminopropyl) methacrylamide copolymer (mole of the first structural unit and the second structural unit) Ratio: 65/35) Production In production example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution, production 200 parts of N-methacryloylaminopropyl-N, N-dimethylammonium-α-carboxybetaine / N- (3-dimethylaminopropyl) methacrylamide mixed solution (50% by mass as an unsaturated monomer) obtained in Example 11 used.

  Otherwise, the synthesis was carried out under the same conditions as in Production Example 2, and both N-methacryloylaminopropyl-N, N-dimethylammonium-α-carboxybetaine / N- (3-dimethylaminopropyl) methacrylamide having a solid content of 30% were obtained. A solution of a polymer (molar ratio of the first structural unit to the second structural unit: 65/35) was obtained. The weight average molecular weight of this copolymer was 490,000.

[Production Example 13] N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl copolymer (first constituent unit ratio 65 mol%, second constituent unit) In Production Example 2, instead of 200 parts by mass of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / 2- (dimethylamino) ethyl methacrylate mixed solution, N- 100 parts by mass of methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixture (viscous liquid from which the solvent was removed from the mixed solution of Production Example 1) and 5 parts by mass of ethanol 2,2′-azobisisobutyronitrile 0.5 mass Instead of 2,2'-azobis (2,4-dimethylvaleronitrile) were used 0.05 parts by weight.

  Otherwise, the synthesis was carried out under the same conditions as in Production Example 2, and an N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine polymer having a solid content concentration of 30% (the first constituent unit and the second constituent unit) A solution with a molar ratio of 65/35) was obtained. The weight average molecular weight of this polymer was 1,400,000.

[Comparative Production Example 1]: Production of N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine polymer (first constituent unit ratio 100 mol%) In Production Example 2, N-methacryloyloxyethyl-N , N-dimethylammonium-α-carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution instead of 200 parts by mass, N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine (unreacted product) And a purified solid from which the solvent was removed). A mixture of 100 parts by mass and 100 parts by mass of ethanol was used.

  Otherwise, the synthesis was performed under the same conditions as in Production Example 2, and the N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine polymer having a solid content concentration of 30% (first constituent unit ratio: 100 mol%) A solution was obtained. The weight average molecular weight of this polymer was 500,000.

[Comparative Production Example 2]: Production of 2- (dimethylamino) ethyl methacrylate polymer (100% by mol of second structural unit) In Production Example 2, N-methacryloyloxyethyl-N, N-dimethylammonium-α- Instead of 200 parts by mass of a carboxybetaine / methacrylic acid 2- (dimethylamino) ethyl mixed solution, a mixture of 100 parts by mass of 2- (dimethylamino) ethyl methacrylate and 100 parts by mass of ethanol was used.

  Other than that, it synthesize | combined on the same conditions as manufacture example 2, and obtained the solution of the 2- (dimethylamino) ethyl methacrylate polymer (100 mol% of 2nd structural unit ratio) of solid content concentration 30%. The weight average molecular weight of this polymer could not be measured under the same conditions as the polymer of the above production example.

  The composition of the ethylenically unsaturated monomer, which is a raw material in each production example and comparative production example, is shown in Tables 1 and 2 below.

[Performance evaluation of cleaning cosmetics]
The component shown in Tables 2-5 was mix | blended, the hand soap for evaluation was adjusted, and 1.5 g of foams were created by discharging the hand soap for evaluation with a pump former. The feeling (foaming property, foam thickness, smoothness during rinsing) when five subjects wash their hands using this foam was evaluated according to the following criteria. Further, the stability of the preparation was evaluated by the following method.

  (1) Foaming property: It evaluated in five steps of 1-5 points so that it might become a high score, so that foaming is favorable.

  (2) Bubble thickness: Evaluation was made in 5 stages of 1 to 5 points so that the foam thickness was high enough to feel good.

  (3) Smoothness at the time of rinsing: Evaluation was made in 5 stages of 1 to 5 points so that the score was high enough to make the skin feel smooth.

For each of the evaluation items (1) to (3), the average score of the evaluations of five subjects was calculated, and the results were evaluated as follows. The evaluation results are shown in Tables 1 to 4.
A: 4.5 points or more and 5 points or less.
B: 3.5 points or more and less than 4.5 points.
C: 2.5 points or more and less than 3.5 points.
D: 1.5 points or more and less than 2.5 points.
E: Less than 1.5 points.

(4) Stability of the preparation: The condition of the preparation after the evaluation hand soap was stored in an environment of 50 ° C. for 30 days was visually evaluated based on the following criteria. The evaluation results are shown in Tables 3-6.
○: The state did not change.
X: State change (aggregation, precipitation, etc.) occurred.

As shown in the above table, when the cleaning cosmetics of Examples 1 to 6 containing the polymer of Production Example 2 including the first structural unit and the second structural unit and glutamic acid which is a dicarboxylic acid are used, the dicarboxylic acid is used. It was found that the foaming property and the foam thickness were improved without impairing the smoothness during rinsing as compared with the cleaning cosmetic of Comparative Example 1 containing no acid. When the cleaning cosmetics of Examples 7 to 9 containing a compound other than glutamic acid as the dicarboxylic acid were used, the foam quality was improved as in Example 5, while the polymer of Production Example 2 When the cleaning cosmetic of Comparative Example 2 containing acetic acid, which is a monocarboxylic acid, was used, an improvement in performance was observed with respect to the cleaning cosmetic of Comparative Example 1 containing neither dicarboxylic acid nor monocarboxylic acid. I couldn't.

  In addition, when the cleaning cosmetic of Comparative Example 3 containing the polymer of Production Example 2 and citric acid, which is a tricarboxylic acid, was used, an improvement in performance was observed, but the stability of the preparation was significantly impaired. .

The cleaning cosmetics of Examples 10 to 13 containing the polymers of Production Examples 3 to 6 having the first structural unit and the second structural unit in proportions different from Production Example 2 and glutamic acid which is a dicarboxylic acid were used. In this case, it was found that the foaming property and the foam thickness were improved without impairing the smoothness at the time of rinsing as compared with the cleaning cosmetics of Comparative Examples 4 to 7 containing no dicarboxylic acid.
Washing cosmetics of Examples 14 to 16 containing the polymers of Production Examples 7 to 9 containing unsaturated monomers other than these in addition to the first and second structural units and glutamic acid which is a dicarboxylic acid It was found that the foaming properties and the foam thickness were improved when the material was used, as compared with the cleaning cosmetics of Comparative Examples 8 to 10 not containing dicarboxylic acid, without impairing the smoothness during rinsing.

  When the cleaning cosmetic of Example 17 containing the polymer of Production Example 10 having an increased weight average molecular weight and glutamic acid, which is a dicarboxylic acid, is used, the cleaning cosmetic of Comparative Example 11 containing no dicarboxylic acid It was found that foamability and foam thickness were improved without impairing smoothness during rinsing.

  When the cleaning cosmetic of Example 18 containing the polymer of Production Example 12 having a first structural unit and a second structural unit different from the polymer of Production Example 2 and glutamic acid which is a dicarboxylic acid is used. It was found that the foaming property and the foam thickness were improved without impairing the smoothness during rinsing as compared with the cleaning cosmetic of Comparative Example 12 containing no dicarboxylic acid.

  In addition, when the cleaning cosmetic of Example 19 containing the polymer of Production Example 13 having a weight average molecular weight increased from 1,000,000 and glutamic acid which is a dicarboxylic acid was used, the dicarboxylic acid was contained. It was found that the foaming property and the foam thickness were improved as compared with the cleaning cosmetic of Comparative Example 17 which was not.

  On the other hand, when the cleaning cosmetic of Comparative Example 14 containing the polymer of Comparative Production Example 1 that does not include the second structural unit and glutamic acid is used, the cleaning cosmetic of Comparative Example 13 that does not contain glutamic acid is used. There was no improvement in performance.

  In addition, when using the cleaning cosmetic of Comparative Example 15 containing the polymer of Comparative Production Example 2 that does not include the first structural unit, compared with the cleaning cosmetic of Comparative Example 18 not containing a polymer, No difference in performance was observed, and no improvement in performance was observed even when glutamic acid was added as in Comparative Example 16.

[Performance evaluation of hair washing cosmetics]
A hair shampoo was prepared by blending the components shown in Table 7, and the feel and foaming property when the test subject washed the hair bundle using this hair shampoo were evaluated.

  As a result, when the hair shampoo of Example 20 containing the polymer of Production Example 2 comprising the first structural unit and the second structural unit and glutamic acid which is a dicarboxylic acid was used, the hair of Comparative Example 19 containing no dicarboxylic acid was used. Compared with the case of using a hair shampoo, the foaming property was excellent without impairing the smoothness of the hair bundle during rinsing.

[Performance evaluation of skin cosmetics]
The ingredients shown in Table 8 were blended to prepare an O / W cream, and the feel when the test subject applied the O / W cream to the face was evaluated.

  As a result, when the O / W cream of Example 21 containing the polymer of Production Example 3 having the first structural unit and the second structural unit and glutamic acid which is a dicarboxylic acid was used, a comparative example containing no dicarboxylic acid was used. Compared to the case of using 20 O / W cream, it gave a good feeling of firmness, had less stickiness, and was excellent in the moisturizing feeling of the skin after use.

[Performance evaluation of hair cosmetics]
The ingredients shown in Table 9 were blended to adjust the hair styling foam, and the elasticity of the foam created by the subject ejecting the hair styling foam from the container and the feel when the hair bundle was trimmed with this foam were evaluated. .

  As a result, when the hair styling foam of Example 22 containing the polymer of Production Example 2 having the first structural unit and the second structural unit and glutamic acid which is a dicarboxylic acid was used, Comparative Example 21 containing no dicarboxylic acid was used. Compared with the case of using no hair styling foam, the foam was excellent in elasticity and styling.

Claims (14)

A copolymer (A) comprising a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2);
Dicarboxylic acid (B) ,
A cosmetic composition containing one or more compounds selected from the group consisting of the dicarboxylic acid (B) consisting of aspartic acid and glutamic acid ;
In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom. Or an alkyl group having 1 to 2 carbon atoms, A represents an oxygen atom or NH,
In formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom or 1 to 2 carbon atoms. Represents an alkyl group, and A represents an oxygen atom or NH. A copolymer (A) comprising a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2);
Dicarboxylic acid (B),
A cosmetic composition containing at least one compound selected from the group consisting of oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid,
  In formula (1), R ¹ Represents a hydrogen atom or a methyl group, R ² And R ^Three Each independently represents an alkylene group having 1 to 3 carbon atoms, and R ^Four And R ^Five Each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, A represents an oxygen atom or NH,
In formula (2), R ¹ Represents a hydrogen atom or a methyl group, R ² Represents an alkylene group having 1 to 3 carbon atoms, and R ^Four And R ^Five Each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and A represents an oxygen atom or NH. The cosmetic composition according to claim 1, wherein the cosmetic composition is a cleaning cosmetic. The cosmetic composition according to claim 1, wherein the cosmetic composition is a skin cosmetic. The cosmetic composition according to claim 1 or 2, which is a hair cosmetic. A copolymer (A) comprising a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2);
Dicarboxylic acid (B),
A cosmetic composition which is a cosmetic for cleaning;
  In formula (1), R ¹ Represents a hydrogen atom or a methyl group, R ² And R ^Three Each independently represents an alkylene group having 1 to 3 carbon atoms, and R ^Four And R ^Five Each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, A represents an oxygen atom or NH,
In formula (2), R ¹ Represents a hydrogen atom or a methyl group, R ² Represents an alkylene group having 1 to 3 carbon atoms, and R ^Four And R ^Five Each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and A represents an oxygen atom or NH. A copolymer (A) comprising a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2);
Dicarboxylic acid (B),
A cosmetic composition which is a cosmetic for skin,
  In formula (1), R ¹ Represents a hydrogen atom or a methyl group, R ² And R ^Three Each independently represents an alkylene group having 1 to 3 carbon atoms, and R ^Four And R ^Five Each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, A represents an oxygen atom or NH,
In formula (2), R ¹ Represents a hydrogen atom or a methyl group, R ² Represents an alkylene group having 1 to 3 carbon atoms, and R ^Four And R ^Five Each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and A represents an oxygen atom or NH. The cosmetic composition according to claim 6 or 7, wherein the dicarboxylic acid (B) contains one or more compounds selected from the group consisting of aspartic acid and glutamic acid. The dicarboxylic acid (B) contains one or more compounds selected from the group consisting of oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, malic acid and tartaric acid. 8. The cosmetic composition according to 7. The cosmetic composition according to any one of claims 1 to 9, wherein a value of a molar ratio of the first structural unit to the second structural unit is in a range of 2/8 to 8/2. The cosmetic composition according to any one of claims 1 to 10, wherein the copolymer (A) has a weight average molecular weight in the range of 100,000 to 1,000,000. The cosmetic composition according to any one of claims 1 to 11 , wherein the molecular weight of the dicarboxylic acid (B) is in the range of 90 to 250. The cosmetic composition according to any one of claims 1 to 12 , wherein a ratio of the dicarboxylic acid (B) to the copolymer (A) is in a range of 0.1 to 10% by mass. The cosmetic composition according to any one of claims 1 to 13 , wherein the cosmetic composition contains a nonionic, cationic, anionic or amphoteric surfactant.