JP4819332B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to hair cosmetics such as hair waxes. More specifically, the present invention relates to a hair cosmetic such as a hair wax that has excellent usability and feeling during use and exhibits an excellent hair styling function.

  As hair cosmetics for hair styling that are generally used, hair cosmetics for hair styling such as mousse, hair spray, gel, set lotion, etc. for styling hair with a set resin, hair sticks, pomade, hair cream mainly using solid hair styling power, There are hair cosmetics for hair styling such as hair wax. In the former hair cosmetic for hairdressing, a set resin film is formed on the hair along with volatilization of water and alcohol, and the set power is exhibited by bonding and fixing the hairs together. However, although the hair styling containing these set resins can provide an excellent setting power, there is a drawback that a natural texture is lost due to a crisp feel.

  In recent years, the latter hair cosmetics for hair styling, particularly waxy hair styling (hair wax), have been developed as hair styling products that solve the above problems (see, for example, Patent Documents 1 and 2). Hair wax is hair-styled by the viscosity of the wax coating. These hair waxes are not sufficient in terms of hair styling properties and hair style keeping properties, although natural hair styles can be obtained without being crunched.

  Developments to obtain excellent usability have been conducted so far. For example, containing at least 40% by weight of an aqueous or water-alcoholic carrier medium, at least 5% by weight of at least one emulsifier, at least 2% by weight of at least one wax, wherein the emulsifier wax The technique of the hair wax product (refer patent document 3) whose mass ratio with respect to 1 is 1 or more, the technique (refer patent document 4) which mix | blended polyethyleneglycol of high polymerization degree, etc. are disclosed.

  However, conventional hair waxes are not sufficient in terms of hair styling properties and hair style keeping properties, but are still insufficient in usability and are satisfied to date, hair styling properties and hair style keeping properties, usability and usage. A hair wax with a feeling has not been developed.

JP-A-10-45546 JP 2001-316228 A Japanese Patent Laid-Open No. 2004-67678 JP 2002-241243 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hair cosmetic such as a hair wax having excellent usability and usability during use and exhibiting an excellent hair styling function. .

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by containing a wax, a hydrophobically modified polyether urethane, an ionic vinyl polymer, and an alcohol, and making the viscosity within a specific range. As a result, the present invention has been completed.

  That is, the present invention comprises (a) a wax, (b) the following general formula (1)

(In the general formula (1), R ¹ , R ² and R ⁴ each independently represent a hydrocarbon group, R ³ represents a hydrocarbon group which may have a urethane bond, R ⁵ is a straight chain, Represents a hydrocarbon group having a branched chain, m is a number of 2 or more, h is a number of 1 or more, and k and n are each independently a number in the range of 0 to 1000, provided that k and n Both of which are not 0.), (c) an ionic vinyl polymer, and (d) an alcohol having a viscosity of 20,000 to 100,000 mPa · s. It is hair cosmetics characterized by being.

  By adopting the configuration of the present invention, hair cosmetics such as excellent hair waxes having a stringiness, a feeling of elasticity, a usability with a feeling of use, and the like, which are not particularly found in the past, can be obtained.

In the present invention, in the hydrophobic modified polyether urethane represented by the general formula (1), R ¹ is an ethylene group, R ² is an ethylene group, R ³ is an alkylene group having 4 to 8 carbon atoms, and R ⁴ is an ethylene group. , R ⁵ is a branched alkyl group having 16 to 32 carbon atoms, m is 2, h is 1, k and n are each independently a number in the range of 10 to 200.

  The (c) ionic vinyl polymer is an anionic vinyl polymer, a cationic vinyl polymer or an amphoteric vinyl polymer.

  The anionic vinyl polymer is preferably a carbomer and / or an alkyl-modified carboxyvinyl polymer.

  The cationic vinyl polymer is preferably an amine-containing (meth) acrylic monomer copolymer.

  The amphoteric vinyl polymer may be an amphoteric acrylic polymer.

  In the present invention, in these hair cosmetics, preferably (a) the wax is 0.01 to 30% by mass in the total amount of the hair cosmetic, and (b) the hydrophobically modified polyether urethane represented by the general formula (1). 0.1 to 10% by mass in the total amount of the hair cosmetic, (c) 0.001 to 5% by mass of the ionic vinyl polymer in the total amount of the hair cosmetic, and (d) 0.1 to 30% by mass in the total amount of the hair cosmetic. % Hair cosmetic.

  The hair cosmetic composition of the present invention can further contain (e) a polysiloxane compound-supported amphoteric urethane resin. The blending of this component improves the hair-styling effect with a stringiness and elasticity.

  It is preferable that content of the said (e) polysiloxane compound carrying | support amphoteric urethane resin is 0.01-10 mass% in hair cosmetics whole quantity.

  The hair cosmetic composition of the present invention can be a hair wax.

  In the present invention, the wax means an oil component that is solid at normal temperature (1 atm, 20 ° C.), and preferably has a melting point of 30 ° C. or higher.

  In the present invention, the viscosity is a viscosity measured at 30 ° C. with a Brookfield viscometer (spindle number 6, rotation speed 10 rpm).

  In the present invention, in the notation relating to acrylic acid and methacrylic acid, the notation of (meth) acrylic acid indicates that it applies to both methacrylic acid and acrylic acid. As for (meth) acrylamide, it is applied to both methacrylamide and acrylamide, and the description of other related monomers and polymers is the same.

  According to the present invention, a hair wax having excellent usability that gives excellent hairstyle, hairstyle keeping power, and at the same time has good fingering, stringiness and elasticity. Etc. are obtained.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  Examples of the wax (a) used in the present invention include waxes such as higher alcohol waxes, ester waxes, hydrocarbon waxes and higher fatty acid waxes that can be used in cosmetics. Specifically, cetanol, Behenyl alcohol, candelilla wax, beeswax (beeswax), carnauba wax, hydrogenated beef tallow, glyceryl tristearate, cotton wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kabok wax, molasses, shellac wax, solid paraffin (paraffin wax) ), Microcrystalline wax, polyethylene wax, stearic acid and the like. One or more waxes are selected and used.

  The content of the wax is preferably 0.01 to 30% by mass in the total amount of the hair cosmetic. If the content is less than 0.01% by mass, the hair styling and re-styling properties in a natural texture tend to be insufficient, and if it exceeds 30% by mass, the stretch and fingers are bad and heavy finishes are used. There is a tendency to get worse. A more preferable content is 1 to 10% by mass in the total amount of the hair cosmetic.

  The (b) hydrophobically modified polyether urethane used in the present invention is represented by the following general formula (1).

In general formula (1), R ¹ , R ² and R ⁴ each independently represent a hydrocarbon group, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ is linear or branched. It represents a hydrocarbon group having a chain, m is a number of 2 or more, h is a number of 1 or more, and k and n are each independently a number in the range of 0 to 1000. However, k and n are not both 0.

The (b) hydrophobically modified polyether urethane represented by the general formula (1) is, for example, one or more polyether polyols represented by R ¹ -[(O—R ² ) _k —OH] _m , One or more polyisocyanates represented by R ³ — (NCO) _{h + 1} and one or more polyether monos represented by HO— (R ⁴ —O) _n —R ⁵ It can be obtained by reacting with alcohol.

In this case, R ^{1 to} R ⁵ in the general formula (1) are R ¹ -[(O—R ² ) _k —OH] _m , R ³ — (NCO) _{h + 1} , HO— (R ⁴ -O) determined by _n -R ⁵ . The charging ratio of the three members is not particularly limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1.4: 1. Is preferred.

The polyether polyol that can be suitably used to obtain the (b) hydrophobically modified polyether urethane represented by the general formula (1) of the present invention is R ¹ -[(O—R ² ) _k —OH] _m. It can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and the like to m-valent polyol.

  As the m-valent polyol, those having 2 to 8 valences are preferable. For example, dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, trioxyisobutane, 1, 2, 3 -Butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butane Triol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethyl Glycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentant Trihydric alcohols such as all, trimethylolethane, trimethylolpropane, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5- Tetravalent alcohols such as pentanetetrol, 1,3,4,5-hexanetetrol, pentahydric alcohols such as adnit, arabit and xylit, hexavalent alcohols such as dipentaerythritol, sorbit, mannitol and exit, Examples thereof include octahydric alcohols such as sugar. In the present invention, a dihydric alcohol, particularly ethylene glycol is particularly preferable.

Therefore, R ¹ is determined by the m-valent polyol.

  In addition, the alkylene oxide, styrene oxide, and the like to be added can exhibit excellent effects, and therefore, alkylene oxide or styrene oxide having 2 to 4 carbon atoms is preferable, and ethylene oxide is particularly preferable.

Therefore, R ² is determined by the alkylene oxide, styrene oxide, etc. to be added.

The alkylene oxide and styrene oxide to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The addition method may be a normal method. Moreover, the polymerization degree k is 0-1000, Preferably it is 1-500, More preferably, it is 10-200. Moreover, the ratio of the ethylene group in R ² is preferably 50 to 100% by mass with respect to all R ² .

The molecular weight of R ¹ -[(O—R ² ) _k —OH] _m is preferably from 500 to 100,000, particularly preferably from 1,000 to 50,000.

The polyisocyanate that can be suitably used for obtaining the (b) hydrophobically modified polyether urethane represented by the general formula (1) of the present invention is represented by R ^3- (NCO) _{h + 1} , There is no particular limitation as long as it has two or more isocyanate groups. For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenylmethane, triisocyanate, tetraisocyanate and the like can be mentioned. In the present invention, aliphatic diisocyanates are preferred.

  Examples of the aliphatic isocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range Isocyanate Include tetramethylxylylene diisocyanate and the like. Of these, hexamethylene diisocyanate is preferably used.

  Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- Examples include naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.

  Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

  Examples of the biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, and 3,3′-dimethoxybiphenyl diisocyanate.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethyl Tan-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, and the like.

  Examples of the triisocyanate include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate, and biphenyl. -2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ', 4' ' -Triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenyl) thiophosphate, etc. Is mentioned.

  Moreover, you may use with the dimer and trimer (isocyanurate coupling | bonding) of these polyisocyanate compounds, and you may make it react with an amine and use it as a biuret.

Further, polyisocyanates having urethane bonds obtained by reacting these polyisocyanate compounds with polyols can also be used. As the polyol, those having 2 to 8 valences are preferable, and a polyol which is a raw material for producing the above-described polyether polyol is preferable. Incidentally, R ³ - (NCO) if the h + ₁ using trivalent or more polyisocyanates, polyisocyanate preferably has the urethane bond.

The polyether monoalcohol that can be suitably used to obtain the (b) hydrophobically modified polyether urethane represented by the general formula (1) of the present invention is HO— (R ⁴ —O) _n —R ⁵ . It can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, etc. to monohydric alcohol. Here, the monohydric alcohol is a monohydric alcohol having a straight chain or a branched chain (hereinafter referred to as “branched”).

Therefore, R ⁵ is a hydrocarbon group excluding the hydroxyl group of the monohydric alcohol, and examples thereof include an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, and a cycloalkenyl group.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl, 2-hexyldecyl, Examples include 2-decyltetradecyl.

  Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

  Examples of alkylaryl groups include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, α-naphthyl, β-naphthyl group and the like.

  Examples of the cycloalkyl group and the cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, and methylcycloheptenyl groups. Etc.

R ⁵ is preferably an alkyl group, and more preferably a branched alkyl group. Moreover, 8-36 are preferable and, as for carbon number of an alkyl group, 12-24 are especially preferable.

  In addition, the alkylene oxide, styrene oxide, and the like to be added can exhibit excellent effects, and therefore, alkylene oxide or styrene oxide having 2 to 4 carbon atoms is preferable, and ethylene oxide is particularly preferable.

Therefore, R ⁴ is determined by the alkylene oxide, styrene oxide, etc. to be added.

Further, the alkylene oxide, styrene oxide and the like to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The addition method may be a normal method. The degree of polymerization n is 0 to 1000, preferably 1 to 200, more preferably 10 to 50. The ratio of ethylene to total R ⁴ is preferably 50 to 100 wt% with respect to all the R ^4, and more preferably from 65 to 100 wt%.

Further, a polyether polyol (a) represented by R ¹ -[(O—R ² ) _k —OH] _m , a polyisocyanate (b) represented by R ³ — (NCO) _{h + 1} , and HO When the polyether monoalcohol (c) represented by — (R ⁴ —O) _n —R ⁵ is reacted, other than the compound having the structure of the general formula (1) may be by-produced. For example, when diisocyanate is used, the main product is a c-b-a-b-c type compound represented by the general formula (1). Compounds such as the b- (ab) _x -abc type may be by-produced. In this case, the compound of the general formula (1) type can be used in the present invention in the form of a mixture containing the compound of the general formula (1) type without separation.

  The hydrophobically modified polyether urethane used in the present invention is a compound known in Japanese Patent Application Laid-Open No. 9-71766, and the one described in the official gazette is used. It can be obtained by a reaction of an ordinary polyether and isocyanate such as a method.

  Below, the manufacture example of the hydrophobic modification polyether urethane used for this invention is given.

(Production Example 1)
480 parts of polyethylene glycol (PEG) 6000 (molecular weight 6000) and 20 moles of ethylene oxide (EO) 20 mol of 2-octyldodecyl alcohol were added to a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. 198 parts were charged and dehydrated at 90-100 ° C. under reduced pressure (10 mmHg or less) for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 80 ° C., 29.6 parts of hexamethylene diisocyanate (HMDI) was added, and the mixture was reacted at 80 to 90 ° C. for 2 hours under a nitrogen stream to confirm that the isocyanate content was 0%. Gave a light yellow solid reaction product. The product is represented by the following formula (1): R ¹ = ethylene group, R ² = ethylene group, R ³ = hexamethylene group, R ⁴ = ethylene group, R ⁵ = 2-octyldodecyl group, h = 1, It was a hydrophobically modified polyether urethane having m = 2, k = 67, and n = 20.

(Production Example 2)
Under the same conditions as in Production Example 1, 522 parts of PEG 6000, 145 parts of EO 10 mol adduct of 2-decyltetradecyl alcohol and 32.2 parts of HMDI gave a pale yellow solid reaction product. The product is represented by the following formula (1): R ¹ = ethylene group, R ² = ethylene group, R ³ = hexamethylene group, R ⁴ = ethylene group, R ⁵ = 2-decyltetradecyl group, h = 1 M = 2, k = 67, and n = 10.

(Production Example 3)
Under the same conditions as in Production Example 1, from 580 parts of PEG 20000, 109 parts of EO35 molar adduct of 2-hexyldecyl alcohol and 11.1 parts of tolylene diisocyanate (TDI), a light yellow solid reaction product was obtained. Obtained. The product is represented by the following formula (1): R ¹ = ethylene group, R ² = ethylene group, R ³ = tolylene group, R ⁴ = ethylene group, R ⁵ = 2-hexyldecyl group, h = 1, m = 2, k = 226, n = 35.

(Production Example 4)
Under the same conditions as in Production Example 1, 603 parts of a compound of the structural formula HO— (C ₂ H ₄ O) ₈₀ — (C ₃ H ₆ O) ₃₀ — (C ₂ H ₄ O) ₈₀ —H A pale yellow solid reaction product was obtained from 82.7 parts of EO 20 mol adduct of decyltetradecyl alcohol and 11.3 parts of HMDI. The product is represented by the following formula (1): R ¹ = propylene group, R ² = (C ₃ H ₆ O) _15- (C ₂ H ₄ O) ₈₀ , R ³ = hexamethylene group, R ⁴ = ethylene Group, R ⁵ = 2-decyltetradecyl group, h = 1, m = 2, n = 20 hydrophobically modified polyether urethane.

  Commercially available products can be used as the hydrophobically modified polyether urethane of the present invention. Examples of commercially available products include Adecanol GT-700 (manufactured by Asahi Denka Co., Ltd.).

  The content of the hydrophobically modified polyether urethane is preferably 0.1 to 10% by mass in the total amount of the hair cosmetic. If the content is less than 0.1% by mass, there is a tendency that the thickening that can realize a feeling of elasticity and stringiness tends to be insufficient. If the content exceeds 10% by mass, the viscosity is too high and the fingers are not easy to stretch. Tend to be. A more preferable content is 0.5 to 3% by mass in the total amount of the hair cosmetic.

  The (c) ionic vinyl polymer used in the present invention is an ionic vinyl polymer such as anionic, cationic or amphoteric.

  Hereinafter, the anionic vinyl polymer will be described in detail. Examples of the anionic vinyl polymer include carbomer (CTFA definition), alkyl-modified carboxyvinyl polymer, poly (meth) acrylic acid, (dimethyl (meth) acrylamide / (meth) acryloyldimethyltaurine alkali metal salt) crosspolymer, etc. Examples include polymers. Among them, a polymer containing a carboxyl group is preferable, and it is more preferable to use a carbomer and an alkyl-modified carboxyvinyl polymer alone or in combination.

  The carbomer is an acrylic acid-based cross-linked copolymer, and is a cross-linked polymer of an acrylic acid-based monomer such as a substituted acrylic acid such as acrylic acid, methacrylic acid, and ethacrylic acid. The acrylic acid monomer is preferably acrylic acid, methacrylic acid or ethacrylic acid, with acrylic acid being most preferred.

  The cross-linking agent in the carbomer is preferably a polyalkenyl polyether of polyhydric alcohol having two or more carbon-carbon double bonds (alkenyl ether groups) per molecule, specifically, sucrose allyl ether, pentaerythritol Examples include allyl ether.

  As the carbomer, a commercially available product can be used, and examples of the commercially available product include Carbopol 910, 934, 940, 941, and 981 (above, Goodrich (BF). Goodrich Chemical), Hibiswako 104, 105 (Wako Pure Chemical Industries, Ltd.), Sinteren K, L (Sigma), and the like.

  The alkyl-modified carboxyvinyl polymer is one or more monomers selected from substituted acrylic acids such as acrylic acid, methacrylic acid and ethacrylic acid, and short-chain alcohols (1 to 4 carbon atoms) of these acrylic acids or substituted acrylic acids. A cross-linked copolymer of an acrylic acid-based first monomer composed of an acrylic acid-based second monomer composed of a long-chain alcohol (carbon number 8 to 40) ester of a substituted acrylic acid such as acrylic acid or methacrylic acid or ethacrylic acid.

  As said short chain alcohol ester, C1-C4 alcohol ester of acrylic acid and C1-C4 alcohol ester of methacrylic acid are preferable.

  The long-chain alcohol ester is preferably an alcohol ester having 8 to 40 carbon atoms of acrylic acid, and more preferably an alcohol ester having 10 to 30 carbon atoms of acrylic acid.

  The cross-linking agent in the alkyl-modified carboxyvinyl polymer is preferably a polyalkenyl polyether of polyhydric alcohol having two or more carbon-carbon double bonds (alkenyl ether groups) per molecule, specifically, sucrose allyl ether. And allyl ether of pentaerythritol.

  Commercially available products can be used as the alkyl-modified carboxyvinyl polymer. Examples of commercially available products include Carbopol R1342, R1382, Pemulen TR-1, and TR-2 ( As mentioned above, Noveon (manufactured by Noveon), Acrine-22 (Rohm & Haas) and the like can be mentioned.

  One or more anionic vinyl polymers are arbitrarily selected and blended.

  Next, the cationic vinyl polymer will be described in detail. Cationic vinyl polymers include amine-containing (meth) acrylic monomer copolymers, poly [dimethyldiallylammonium halide] type cationic polymers, copolymers of dimethyldiallylammonium halide and acrylamide, cationic polymers, vinylpyrrolidone, dimethylamino An ethyl methacrylate copolymer cationized material, etc. are mentioned.

In the present invention, an amine-containing (meth) acrylic monomer copolymer is preferably used. The amine-containing (meth) acrylic monomer copolymer is preferably a cationic vinyl polymer obtained by polymerizing a monomer composition containing the following (F) to (I).
(F) The following general formula (2)

(In the general formula (2), R ⁶ is a hydrogen atom or a methyl group, R ⁷ and R ⁸ are each independently a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A is an oxygen atom or a —NH— group, B represents an alkylene group having 1 to 4 carbon atoms having a straight chain or a side chain.) Amine-containing (meth) acrylic monomer

(G) The following general formula (3)

(In general formula (3), R ⁶ is the same as in general formula (2), R ⁹ is the following general formula (4)

(In the general formula (4), p represents 3 or 4) or a group represented by the following formula (5)

Represents a group represented by ) Vinyl monomer represented by

(H) The following general formula (6)

(In the general formula (6), R ⁶ and A are the same as those in the general formula (2), R ¹⁰ is a C1-C21 alkylene group having a straight chain or a side chain, or the following general formula (7)

(In General Formula (7), n represents an integer of 1 to 4, q represents an integer of 1 to 25), and R ¹¹ represents a hydrogen atom or a methyl group. (Meth) acryloyl group-containing monomer represented by

(I) Crosslinkable vinyl monomer

  The amine-containing (meth) acrylic monomer copolymer is a polymer known from Japanese Patent No. 3488494 and can be used.

In the amine-containing (meth) acrylic monomer, in general formula (2), R ⁷ and R ⁸ are both methyl groups, A is an oxygen atom or —NH— group, and B is an ethylene group or propylene group. Is preferred. The A is more preferably an oxygen atom, and the B is more preferably an ethylene group. Specific examples of the amine-containing (meth) acrylic monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N- Examples include diethylaminopropyl (meth) acrylamide. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) ) Acrylamide is preferable, and N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylamide are more preferable. In particular, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate are preferable. In addition, in this invention, the amine containing (meth) acrylic-type monomer shown by the said General formula (2) is used 1 type or in mixture of 2 or more types, 15-85 mass% containing in the monomer composition whole quantity is contained. It is preferable to do. More preferably, it is 30-70 mass%. In particular, 40 to 55% by mass is preferable.

  Examples of the vinyl monomer represented by the general formula (3) include N-vinylpyrrolidone and (meth) acrylamide. Of these, N-vinylpyrrolidone is preferably used. In the present invention, the vinyl monomer is used singly or in combination of two or more, and is preferably contained in an amount of 0 to 80% by mass in the total amount of the monomer composition. The vinyl monomer represented by the general formula (3) may not be contained, but more preferably 5 to 80% by mass in the total amount of the monomer composition. More preferably, it is 20-70 mass%. 35-55 mass% is especially preferable.

In the (meth) acryloyl group-containing monomer, in general formula (6), R ¹⁰ is preferably an alkylene group having 11 to 17 chain carbon atoms and R ¹¹ is a methyl group. R ¹⁰ is more preferably an alkylene group having 15 to 17 chain carbon atoms. Specific examples of the (meth) acryloyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate Hydroxybutyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate. Among these, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate are preferable, stearyl (meth) acrylate is preferable, and stearyl (meth) acrylate is more preferable. In the present invention, the (meth) acryloyl group-containing monomer represented by the general formula (6) is used singly or in combination of two or more, and 0.5 to 20% by mass in the total amount of the monomer composition. It is preferable to contain. More preferably, it is 0.5-10 mass%. 1-5 mass% is especially preferable.

  The crosslinkable vinyl monomer is a compound having two or more carbon-carbon unsaturated double bonds in one molecule, and has a property of crosslinking with other monomers. Examples of the crosslinkable vinyl monomer include ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tripropylene glycol di (meth). ) (Meth) acrylic monomer having two or more carbon-carbon unsaturated double bonds in one molecule such as polypropylene glycol di (meth) acrylate such as acrylate; methylene bis (meth) acrylamide, 1,2-bis (meth) ) (Meth) acrylamide monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as acrylamide ethane, 1,5-bis (meth) acrylamide pentane; two or more in one molecule such as divinylbenzene Carbon-carbon unsaturated double bonds Vinyl monomers and the like having a. Among these, (meth) acrylic monomers having two or more carbon-carbon unsaturated double bonds in one molecule are preferable, and polypropylene glycol di (meth) acrylate is more preferable, and tripropylene glycol di (meth) is particularly preferable. ) Acrylate is preferred. In the present invention, the crosslinkable vinyl monomer is used alone or in combination of two or more, and is preferably contained in an amount of 0.1 to 20% by mass based on the total amount of the monomer composition. More preferably, it is 1-15 mass%, and especially 1-10 mass% is preferable.

  The polymerization reaction of the monomer composition containing the (F) amine-containing (meth) acrylic monomer, (G) vinyl monomer, (H) (meth) acryloyl group-containing monomer and (I) crosslinkable vinyl monomer is generally used. For example, it can be obtained by the method described in Japanese Patent No. 3488494.

  Hereinafter, production examples of the cationic vinyl polymer will be shown.

(Production Example 5)
In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube, 50 g of N, N-dimethylaminoethyl methacrylate, 47.5 g of N-vinylpyrrolidone, 2.5 g of stearyl acrylate and tripropylene glycol diacrylate as monomers 1.9 g and a mixed solvent of 23.1 g of ethanol and 554.3 g of cyclohexane (mixing ratio (mass ratio) 4:96) were added, and the mixture was stirred for 2 hours under a nitrogen stream while refluxing at 80 ° C. And deaerated. Next, 0.41 g of 2,2′-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. After 45 minutes from the start of polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after further 45 minutes, 1.9 g of tripropylene glycol diacrylate was added. After carrying out the polymerization reaction for about 10 hours with stirring under a nitrogen stream, the obtained polymer slurry solution was filtered under reduced pressure, and the solid content was dried under reduced pressure. The obtained dry polymer was pulverized by a pulverizer to obtain a white powdery cationic vinyl polymer.

(Production Example 6)
A white powdery cationic vinyl polymer was obtained in the same manner as in Production Example 5 except that N, N-dimethylaminopropylmethacrylamide was used instead of N, N-dimethylaminoethyl methacrylate in Production Example 5.

(Production Example 7)
In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube, 50 g of N, N-dimethylaminoethyl methacrylate, 47.5 g of methacrylamide, 2.5 g of stearyl acrylate, tripropylene glycol diacrylate 9 g and 376.2 g of ethanol were added, the monomer concentration was adjusted to 21% by mass, and the mixture was deaerated by stirring for 2 hours in a nitrogen stream while refluxing at 80 ° C. Next, 0.41 g of 2,2′-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. After 45 minutes from the start of polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after further 45 minutes, 1.9 g of tripropylene glycol diacrylate was added. After carrying out the polymerization reaction for about 10 hours with stirring under a nitrogen stream, the resulting polymer slurry solution was filtered under reduced pressure, and the solid content was dried under reduced pressure. The dried polymer was pulverized with a pulverizer to obtain a white powdery cationic vinyl polymer.

  One or more cationic vinyl polymers are arbitrarily selected and blended.

  Commercially available products can be used as the cationic vinyl polymer of the present invention, and examples of commercially available products include Koscut GA467 (Osaka Organic Industry Co., Ltd.), Marcote 100, 550 (above, manufactured by Merck & Co., USA). ), H. C. Polymer 1, 1N, 2, HCP-3A (Osaka Organic Chemical Industries, Ltd.), Guff Coat 755, 734 (IS, ISP), and the like.

  Next, the amphoteric vinyl polymer will be described in detail. Examples of the amphoteric vinyl polymer include amphoteric acrylic polymers. Examples of amphoteric acrylic polymers include N- (meth) acryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine / (meth) acrylic acid alkyl ester copolymer, N, N-dimethyl- N- (2- (meth) acryloyloxyethyl) amine / (meth) acrylic acid alkyl ester copolymer, (meth) acrylic acid / (meth) acrylic acid alkyl ester / (meth) methacrylic acid ethylamine oxide) copolymer, ( (Meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / (meth) acrylic acid copolymer, N, N-dimethyl-N- (2-methacryloyloxyethyl) amine = N-oxide / (meth) acrylic Acid alkyl ester copolymer, acrylamide, acrylic acid, dimethyl chloride Luzia Lil ammonium copolymer (polyquaternium over 39), and the like.

  The alkyl ester of (meth) acrylic acid alkyl ester in these copolymers is preferably an alkyl ester having 1 to 18 carbon atoms such as methyl ester. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate and the like. It is done.

  Since amphoteric acrylic polymers are generally commercially available, commercially available products can be used. Examples of commercially available products include N-methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer, Yucaformer R205, R205S, 510, SM, 301, 104D, 202, AMPHOSET (Mitsubishi Chemical Corporation), RAM Resin 2000, 3000, 4000 (Osaka Organic Chemical Industry Co., Ltd.), N, N-dimethyl-N- (2-methacryloyloxy) Ethyl) amine / methacrylic acid alkyl ester copolymer Diaformer Z-711, Z-712, Z-631, Z-632, Z-651 (above, manufactured by Mitsubishi Chemical Corporation), etc. (Acrylates / stearyl acrylate / ethylamine oxide methacrylate) Is mer diamond former Z-772 (manufactured by Mitsubishi Chemical Co., Ltd.), and the like.

  One or two or more amphoteric vinyl polymers are arbitrarily selected and used.

  As for content of the ionic vinyl polymer in this invention, 0.001-5 mass% is preferable in the hair cosmetics whole quantity. If the content is less than 0.001% by mass, the thickening tends to be insufficient, and if it exceeds 5% by mass, the viscosity tends to be high and the finger tends to be poor. A more preferable content is 0.05 to 2% by mass in the total amount of the hair cosmetic.

  The alcohol (d) used in the present invention is preferably a monovalent alcohol having 1 to 5 carbon atoms, and examples thereof include ethanol, n-propanol, isopropanol, butanol, and pentanol. In the present invention, ethanol is preferred. One or more alcohols are arbitrarily selected and blended.

  As for content of alcohol, 0.1-30 mass% is preferable in hair cosmetics whole quantity. A more preferable content is 1 to 15% by mass in the total amount of the hair cosmetic.

  The hair cosmetic composition according to the present invention needs to contain the above components and have a viscosity of 20,000 to 100,000 mPa · s. If the viscosity is less than 20,000 mPa · s, not only the stability as a preparation (creaming of the inner layer oil) is impaired, but there is a concern that any finger or the like when used as a cosmetic container will get worse. On the other hand, if it exceeds 100,000 mPa · s, it is difficult to handle in use (boiled, stretched, etc.), and the hair does not fit well.

  In the hair cosmetic composition of the present invention, in addition to the above-described components, other components that are usually used in cosmetics, quasi drugs, pharmaceutical products, and the like can be appropriately blended within a range that does not impair the effects of the present invention. As the optional blending component, (e) a polysiloxane compound-carrying amphoteric urethane resin can be blended, and the blending of this component improves the hair-styling effect with a stringiness and elasticity.

  The polysiloxane compound-carrying amphoteric urethane resin is preferably an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule carrying a polysiloxane compound.

As the amphoteric urethane resin constituting the polysiloxane compound-carrying amphoteric urethane resin, an amphoteric urethane resin produced by reacting at least the following compounds (A) to (D) is preferable.
(A) Polyol compound (B) Polyisocyanate compound (C) Compound having at least one selected from hydroxyl group, primary amino group and secondary amino group and carboxyl group (D) Hydroxyl group, primary Compound having at least one selected from amino group and secondary amino group and tertiary amino group

  The polyol compound (hereinafter also referred to as compound (A)) is not particularly limited as long as it is a polyol compound generally used for the production of urethane resins. Examples of the compound (A) include, for example, polyester polyols, polyether polyols, low molecular polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, polyolefin polyols, polyacrylic ester polyols, and the like. Or two or more of them are used in combination. Among these, polyester polyols, polyether polyols, and low molecular polyols are preferably used.

  Examples of the polyester polyol include at least one dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol, trimethylolpropane, etc. And polyester polyols obtained by polycondensation with at least one kind of a monohydric alcohol, and polyester polyols obtained by ring-opening polymerization of lactones.

  Examples of the polyether polyol include, in addition to water and polyhydric alcohols used for the synthesis of the polyester polyol, phenols such as bisphenol A and hydrides thereof, and primary amines or secondary amines. Examples include polyether polyols obtained by ring-opening addition polymerization of cyclic ethers such as ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran. Furthermore, polyoxypropylene polyol, polyoxytetramethylene polyol, and bisphenol A are polyether polyols obtained by ring-opening addition polymerization of at least one of propylene oxide or ethylene oxide (in the case of copolymers, block copolymers, random Any of copolymers may be used.

  Examples of the low molecular polyol include 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol, isopropylene glycol, 1,4-butanediol, 1,3-butanediol, butylene glycol, and 1,6-hexanediol. , Neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol, spiroglycol, trimethylolpropane, glycerin, diglycerin, triglycerin and the like.

  Compound (A) can be used alone or in combination. Among the compounds (A), 1,4-cyclohexanedimethanol is preferable.

  In addition, in this invention, when it overlaps with the compound (E) mentioned later in a compound (A), the compound is contained in a compound (E) and is not contained in a compound (A). Furthermore, in this invention, when it overlaps with the compound (C) mentioned later in a compound (A), the compound is contained in a compound (C) and is not contained in a compound (A). Moreover, in this invention, when it overlaps with the compound (D) mentioned later in a compound (A), the compound is contained in a compound (D) and is not contained in a compound (A).

  The polyisocyanate compound (hereinafter also referred to as compound (B)) used in the present invention is not particularly limited as long as it is a polyisocyanate compound generally used for the production of urethane resins. As an example of a compound (B), organic diisocyanate compounds, such as an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, and an aromatic diisocyanate compound, are mentioned, for example, These are used individually or in combination of 2 or more types.

  Examples of the aliphatic diisocyanate compound include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate compound include hydrogenated 4,4′-diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, and norbornane diisocyanate.

  Examples of the aromatic diisocyanate compound include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate.

  Among these compounds (B), 1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and the like are preferable in terms of excellent weather resistance and low cost. Compound (B) can be used alone or in combination.

  As a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group used in the present invention and a carboxyl group (hereinafter also referred to as compound (C)), it is contained in the molecule. Particularly, a compound having at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group and at least one carboxyl group, and capable of obtaining a target amphoteric urethane resin It is not limited. Preferred examples of the compound (C) include carboxylic acids having 3 to 26 carbon atoms, preferably 3 to 12 carbon atoms having a dialalkylol group such as dimethylol, diethanol, and dipropanol. Specific examples include dimethylolpropanoic acid (DMPA), dimethylolbutanoic acid, and the like. In addition, a carboxyl group-containing polycaprolactone diol is also used. These may be used alone or in combination of two or more.

  As a compound (hereinafter also referred to as compound (D)) having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a tertiary amino group used in the present invention, A compound having at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group in the molecule and at least one tertiary amino group, and obtaining a target amphoteric urethane resin The compound is not particularly limited as long as it is a compound that can be used. Examples of the compound (D) include the same dialkyrol group as the compound (C), for example, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-methyldipropanolamine. N-alkyl dialkanolamine compounds such as The N-alkyl alkyl group of the N-alkyl dialkanolamine compound preferably has 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Further, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dialkylalkanolamine compounds such as N, N-dibutylethanolamine, and triethanolamine can be mentioned. These may be used alone or in combination of two or more.

  The polysiloxane compound constituting the polysiloxane compound-supported amphoteric urethane resin (hereinafter also referred to as compound (S)) is a polysiloxane compound that can be blended in cosmetics, and has hydroxyl groups at both ends or one end of the siloxane chain. The polysiloxane compound does not have at least one selected from a primary amino group and a secondary amino group, and is not particularly limited as long as it is a compound capable of obtaining a target amphoteric urethane resin. . Examples of the polysiloxane compound include dimethylpolysiloxane, polyether-modified silicone, cyclic silicone, phenyl-modified silicone, alkyl-modified silicone, and alkoxy-modified silicone. One or more of these polysiloxane compounds are arbitrarily selected and blended.

  Examples of dimethylpolysiloxane include compounds represented by the following general formula (8).

(In general formula (8), n represents an integer of 1 or more.)

  N in the general formula (8) is preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 3 to 30.

  Commercially available products can be used as the dimethylpolysiloxane of the present invention. Examples of commercially available products include SH200 series (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. KF96 series (brand name) etc. are mentioned.

  Examples of the polyether-modified silicone include a compound represented by the following general formula (9).

(In general formula (9), m represents an integer of 0 or more, n represents an integer of 1 or more, and R ¹² represents a group represented by the following general formula (10).)

(In General Formula (10), R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 1 to 10, b represents an integer of 1 to 300, and c represents 0 to 0. Represents an integer of 300.)

In the general formula (9), m is preferably an integer of 0 to 300, more preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50. n is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50. Furthermore, in the general formula (10), R ¹³ is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 5, and particularly preferably an integer of 2 to 4. b is preferably an integer of 2 to 50, more preferably an integer of 2 to 40, and particularly preferably an integer of 2 to 30. c is preferably an integer of 0 to 50, more preferably an integer of 0 to 40, and particularly preferably an integer of 0 to 30.

As a general formula (9) compound represented by (S), in the general formula (9), m is an integer of 1 to 300, n is an integer of 1 to 300, R ¹² is the formula (10) Preferred are compounds in which a is an integer of 1 to 5, b is an integer of 2 to 50, and c is an integer of 0 to 50.

As a general formula (9) compound represented by (S), in the general formula (9), m is an integer of 1 to 100, n is an integer of 1 to 100, R ¹² is the formula (10) It is the group shown, Comprising: The compound whose a is an integer of 2-4, b is an integer of 2-40, and c is an integer of 0-40 is more preferable.

As a general formula (9) compound represented by (S), in the general formula (9), m is an integer of 1 to 50, n is an integer of 1 to 50, R ¹² in the general formula (10) Particularly preferred are compounds in which a is an integer of 2 to 4, b is an integer of 2 to 30, and c is an integer of 0 to 30.

  Examples of the polyether-modified silicone represented by the general formula (9) include SH3746, SH3771C, SH3772C, SH3773C, SH3775C, SH3748, SH3749, SH3771M, SH3772M, SH3773M, and SH3775M (trade names) manufactured by Toray Dow Corning Silicone Co., Ltd. And KF351A, KF353A, KF945A, KF352A, KF615A, KF6011, KF6012, KF6013, KF6015, KF6016, KF6017 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Examples of the phenyl-modified silicone include a compound represented by the following general formula (11).

(In General Formula (11), R ¹⁴ and R ¹⁵ are each independently a hydrocarbon group having 1 to 12 carbon atoms (for example, a linear or branched saturated hydrocarbon group having 1 to 12 carbon atoms),- OSi (CH ₃ ) ₃ or a phenyl group, provided that at least one of R ¹⁴ and R ¹⁵ is a phenyl group, m represents an integer of 0 or more, and n represents an integer of 1 or more.

In the general formula (11), m is preferably an integer of 0 to 300, more preferably an integer of 0 to 100, and particularly preferably an integer of 0 to 50. n is preferably an integer of 1 to 500, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50. As the phenyl-modified silicone, a methylphenyl polysiloxane represented by the general formula (11) in which R ¹⁴ = CH ₃ or -OSi (CH ₃ ) ₃ , R ¹⁵ = C ₆ H ₅ , m = 0, n = 1 to 100 Particularly preferred.

  As the phenyl-modified silicone represented by the general formula (11), for example, SH556, SF557, SF558, SH559 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., and KF50-100cs, KF50 manufactured by Shin-Etsu Chemical Co., Ltd. -1000cs, KF53, KF54, KF56 (trade name), and the like.

  Examples of the alkyl-modified silicone include compounds represented by the following general formula (12).

(In General Formula (12), R ^{16 to} R ¹⁸ each independently represents a hydrocarbon group having 1 to 50 carbon atoms, provided that at least one of R ^{16 to} R ¹⁸ is carbonized having 5 to 30 carbon atoms. A hydrogen group, m represents an integer of 1 or more, and n represents an integer of 1 or more.)

In the general formula (12), as R ¹⁶ to R ^18, a hydrocarbon group having 1 to 50 carbon atoms can be exemplified by straight-chain or branched saturated hydrocarbon group. The hydrocarbon group preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and particularly preferably 10 to 20 carbon atoms. Moreover, m is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50. n is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50.

  Examples of the alkyl-modified silicone represented by the general formula (12) include SF8416 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., and KF-412, KF-413, KF-414 manufactured by Shin-Etsu Chemical Co., Ltd. (Product name) and the like.

  Examples of the alkoxy-modified silicone include compounds represented by the following general formula (13).

(In General Formula (13), R ^{19 to} R ²¹ each independently represent a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. However, at least one of R ^{19 to} R ²¹ Is an alkoxy group having 1 to 50 carbon atoms, m represents an integer of 0 or more, and n represents an integer of 1 or more.)

In the general formula (13), R ^{19 to} R ²¹ are each a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. Or a branched saturated hydrocarbon group can be illustrated and a linear or branched alkoxy group can be illustrated as a C1-C50 alkoxy group. The number of carbon atoms of the alkoxy group having 1 to 50 carbon atoms is preferably 1 to 30, more preferably 1 to 25, and particularly preferably 1 to 20. Moreover, m is preferably an integer of 0 to 500, more preferably an integer of 1 to 500, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50. . n is preferably an integer of 1 to 100, more preferably an integer of 1 to 80, and particularly preferably an integer of 1 to 50.

  Examples of the alkoxy-modified silicone represented by the general formula (13) include KF-851 and X-22-801B (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.

  As cyclic silicone, the compound shown, for example by following General formula (14) can be mentioned.

(In the general formula (14), R ²² represents a hydrocarbon group having 2 to 12 carbon atoms, and each repeating unit may be the same or different. M represents an integer of 1 or more, n represents an integer of 0 or more, and m + n = 3 to 10.

In General formula (14), R < ²² > is a C1-C12 hydrocarbon group, and can illustrate a linear or branched saturated hydrocarbon group. R ²² preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 5 carbon atoms. M is preferably an integer of 1 to 8, more preferably an integer of 3 to 8, more preferably an integer of 4 to 8, and particularly preferably an integer of 4 to 6. . n is preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and particularly preferably an integer of 0 to 3. m + n is preferably from 3 to 8, more preferably from 4 to 8, and particularly preferably from 4 to 6.

  Examples of the cyclic silicone represented by the general formula (14) include SH244, SH344, SH245, DC345, DC246 (trade name) manufactured by Toray Dow Corning Silicone, and KF994, KF995 manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include KF9937 (trade name).

  The repeating unit portion of the compounds represented by the general formula (9) and the general formulas (11) to (14) may be in any polymerization form such as random polymerization or block polymerization.

The viscosity of the compound (S) at 25 ° C. (kinematic viscosity) is preferably 1 to 5,000 mm ² / s, more preferably 1 to 2,000 mm ² / s, Particularly preferred is 000 mm ² / s. As the compound (S), dimethylpolysiloxane and polyether-modified silicone are preferable. Compound (S) can be used alone or in combination.

  A preferred polysiloxane compound-carrying amphoteric urethane resin in the present invention is an amphoteric urethane resin produced by reacting at least the compounds (A) to (D) in the presence of the compound (S). In producing the polysiloxane compound-carrying amphoteric urethane resin according to the present invention, at least the compounds (A) to (D) and (S) are used, and the compounds (A), (B) and (C) are used. And a second step of reacting the isocyanate group-containing prepolymer with the compound (D), and the first step. In at least one of the second steps, the compound (S) can be present in the presence. Moreover, it can also manufacture even if the reaction order of the said compound (C) and compound (D) is replaced.

  The mass ratio of the compound (S) to the compounds (A), (B), (C) and (D), that is, (S) / ((A) + (B) + (C) + (D)) is 0.1 / 100 to 30/100 is preferable, 0.5 / 100 to 25/100 is more preferable, and 1/100 to 20/100 is particularly preferable.

  The molar ratio of the compound (B) to the compounds (A), (C) and (D), that is, (B) / ((A) + (C) + (D)) is 2.0 / 1. It is preferably 8 to 2.0 / 0.8, more preferably 2.0 / 1.8 to 2.0 / 1.0, and 2.0 / 1.8 to 2.0 / 1. .2 is particularly preferred.

  In the present invention, it is preferable to use a polysiloxane compound-carrying amphoteric urethane resin having a structural unit derived from RO in the resin structure from the viewpoint of improving the stability and properties of the cosmetic composition. Examples of the structural unit derived from RO include an EO unit and a PO unit, and preferably an EO unit.

  The compound having a structural unit derived from RO in the structure is not particularly limited as long as the structural unit derived from RO can be introduced into the structure of the polysiloxane compound-supported amphoteric urethane resin.

  As a preferred compound having a structural unit derived from RO in the structure, at least one selected from a hydroxyl group, a primary amino group and a secondary amino group, and a structure represented by the following general formula (15) A compound having a unit (hereinafter also referred to as compound E).

(In general formula (15), p represents an integer of 1 to 500, and q represents an integer of 0 to 400.)

In general formula (15), when q is 0, it is a polymer of C ₂ H ₄ O (polyoxyethylene), and when q is not 0, a copolymer of C ₂ H ₄ O and C ₃ H ₆ O It is. In the case of this copolymer, it may be a random copolymer or a block copolymer.

  In General formula (15), p is an integer of 1-500. Further, whether q is not 0 or 0, p is preferably 3 to 250, more preferably 3 to 120, and particularly preferably 3 to 50. When p is less than 1, EO units introduced into the amphoteric urethane resin are too small, so that sufficient hydrophilicity cannot be imparted. The hydrophilicity becomes insufficient and the hair washability of the hair is deteriorated. On the other hand, when n exceeds 500, the hydrophilicity of the amphoteric urethane resin itself is too strong when the polysiloxane compound is supported, which adversely affects moisture resistance and the like.

  Moreover, in General formula (15), the repeating number q of PO unit is an integer of 0-400, Preferably q = 0. When q is not 0, q is preferably set in the range of 3 to 200, more preferably 3 to 100. Especially preferably, it is 3-40. Note that, whether q is not 0 or 0, it is preferably set in the range of p + q = 3 to 300, more preferably p + q = 10 to 120. Particularly preferably, p + q = 3-50.

  Further, whether q is not 0 or 0, the ratio of EO units to PO units is preferably in the range of EO units / PO units = 10/0 to 2/8 on a mass basis. More preferably, it is EO unit / PO unit 10/0 to 3/7. Particularly preferred is EO unit / PO unit 10/0 to 4/6.

The compound (E) is preferably a both-end OH group introduction type, a both-end NH ₂ group introduction type, a one-end OH group introduction type, or a one-end NH ₂ group introduction type. When the both-end OH group introduction type or the both-end NH ₂ group introduction type is used, an amphoteric urethane resin having a structural unit represented by the general formula (15) in the main chain is obtained. In addition, when the one-terminal OH group introduction type or the one-terminal NH ₂ group introduction type is used, an amphoteric urethane resin having the structural unit represented by the general formula (15) in the side chain or the terminal can be obtained.

  The mass average molecular weight of the compound (E) is preferably in the range of 200 to 20,000, more preferably 200 to 5,000. Particularly preferred is 500 to 2,000.

  Examples of the compound (E) include polyethylene glycol (PEG), polyethylene polypropylene glycol, polyethylene polypropylene block copolymer, and the like. Of these, polyethylene glycol is preferable. Compound (E) can be used alone or in combination.

  When the compound (E) is added, the polysiloxane compound-carrying amphoteric urethane resin is preferably an amphoteric urethane resin produced by reacting at least the compounds (A) to (E) in the presence of the compound (S).

  The polysiloxane compound-carrying amphoteric urethane resin of the present invention has a carboxyl group and a tertiary amino group in one molecule. The ratio of the carboxyl group to the tertiary amino group (ratio of the number of both functional groups), the carboxyl group / tertiary amino group is preferably 1/50 to 50/1, more preferably 1/1 to 50/1. Preferably, 1/1 to 25/1 is particularly preferable. When the ratio between the carboxyl group and the tertiary amino group in the polysiloxane compound-carrying amphoteric urethane resin is 1/50 to 50/1, using a hair styling compounded with the polysiloxane compound-carrying amphoteric urethane resin, It will have a better texture. In the reaction, the ratio (molar ratio) between the compound (C) and the compound (D) and the compound (C) / compound (D) is preferably 1/50 to 50/1, and preferably 1/1 to 50 /. 1 is more preferable, and 1/1 to 25/1 is particularly preferable.

  The polysiloxane compound-carrying amphoteric urethane resin according to the present invention does not necessarily contain the polysiloxane chain of the polysiloxane compound in the skeleton through a covalent bond, but “restrains the polysiloxane compound by the skeleton of the amphoteric urethane resin”. Or the skeleton of the amphoteric urethane resin is physically entangled with the polysiloxane chain of the polysiloxane compound to contain the polysiloxane chain. This restriction or entanglement is thought to be more complicated by the progress of the polymerization reaction of the amphoteric polyurethane, making it difficult to separate the polysiloxane compound from the obtained amphoteric urethane resin.

  In this invention, such a restraint or entangled state of the amphoteric urethane resin skeleton and the polysiloxane compound is referred to as a state in which the amphoteric urethane resin skeleton “supports” the polysiloxane compound. Here, “supporting” differs depending on whether the amphoteric urethane resin is in the form of an aqueous solution or in the form of an aqueous dispersion. The skeleton of the amphoteric urethane resin is usually a straight chain structure, but may have a branched structure or a crosslinked structure. When the amphoteric urethane resin is in the form of an “aqueous solution”, a polysiloxane chain is present between the skeletons of the amphoteric urethane resin. It is considered to have entered.

  On the other hand, when the amphoteric urethane resin is in the form of an “aqueous dispersion”, the amphoteric urethane resin is considered to be in the form of particles dispersed in water. Such a form is conceivable. First, the first form is a form in which the whole or part of the polysiloxane chain is enclosed in the particles. The second form is a form in which the end of the polysiloxane chain is encapsulated inside the particle. Garage. The third form is a form in which polysiloxane chains are attached to the surface of the particles. The first to third forms all correspond to “restraint”, and those in which the first to third forms are mixed are considered to be “restraint”.

  Thus, the skeleton of the polysiloxane compound-carrying amphoteric urethane resin according to the present invention carries the polysiloxane compound. For this reason, the polysiloxane chain is considered to be difficult to separate from the amphoteric urethane resin while having a property of being relatively easy to move.

  The polysiloxane compound-carrying amphoteric urethane resin used in the present invention is a compound known in Japanese Patent Application Laid-Open No. 2003-12440, and the one described in the official gazette is used. What is obtained by the manufacturing method currently used is used.

  Below, the manufacture example of the polysiloxane compound carrying | support amphoteric urethane resin used for this invention is given.

(Production Example 8)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 70 g of isophorone diisocyanate (IPDI), 63 g of polypropylene glycol (PPG, mass average molecular weight 1,000), 1,4-cyclohexanedimethanol (CHDM) 7 g, dimethylpolysiloxane (viscosity at 25 ° C. is 10 mm ² / s, 8 g SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) and dimethylolbutanoic acid (DMBA) 20 g Then, 50 g of ethyl acetate was added as a solvent, and the mixture was heated to 80 ° C. using an oil bath and reacted for 3 hours. Thereafter, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 3 hours to obtain a prepolymer having a remaining isocyanate group. The prepolymer having the isocyanate groups remaining is cooled to 50 ° C. and then dispersed in 700 g of water containing 10 g of potassium hydroxide at a high speed, followed by a chain extension reaction at 50 ° C. for 3 hours to increase the molecular weight. It was. The ethyl acetate was recovered from the obtained aqueous liquid to obtain an aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin substantially free of a solvent.

(Production Example 9)
Instead of 8 g of dimethylpolysiloxane (SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) having a viscosity of 10 mm ² / s at 25 ° C. in the production method described in Production Example 8. Polysiloxane using the same method as in Production Example 8 except that 8 g of modified silicone (SH3775C (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., having a viscosity at 25 ° C. of 1,600 mm ² / s) was used. An aqueous liquid of the compound-carrying amphoteric urethane resin was obtained.

(Production Example 10)
In the production method described in Production Example 8, instead of 8 g of dimethylpolysiloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone), cyclic silicone (Polysiloxane compound-carrying amphoteric urethane by using the same method as in Production Example 8 except that 8 g (viscosity at 25 ° C. is 4 mm ² / s, SH245 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.)) An aqueous resin liquid was obtained.

(Production Example 11)
In the production method described in Production Example 8, instead of 8 g of dimethylpolysiloxane (SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., having a viscosity at 25 ° C. of 10 mm ² / s), phenyl-modified Except for using 8 g of silicone (SH556 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., having a viscosity of 22 mm ² / s at 25 ° C.), the polysiloxane compound-carrying amphotericity using the same method as in Production Example 8 An aqueous liquid of urethane resin was obtained.

(Production Example 12)
In the production method described in Production Example 8, instead of 8 g of dimethylpolysiloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone), alkyl-modified A polysiloxane compound-carrying amphoteric urethane was used in the same manner as in Production Example 8 except that 8 g of silicone (KF-412 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., having a viscosity of 500 mm ² / s at 25 ° C.) was used. An aqueous resin liquid was obtained.

(Production Example 13)
In the production method described in Production Example 8, instead of 8 g of dimethylpolysiloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone), alkoxy-modified A polysiloxane compound-supported amphoteric urethane was used in the same manner as in Production Example 8, except that 8 g of silicone (KF-851 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., having a viscosity of 80 mm ² / s at 25 ° C.) was used. An aqueous resin liquid was obtained.

(Production Example 14)
In the production method described in Production Example 8, dimethylpolysiloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) instead of 8 g was used. Polysiloxane compound using the same method as in Production Example 8 except that 20 g of siloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) was used. An aqueous liquid of a supported amphoteric urethane resin was obtained.

(Production Example 15)
Instead of 8 g of dimethylpolysiloxane (SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) having a viscosity of 10 mm ² / s at 25 ° C. in the production method described in Production Example 8. A polysiloxane compound is supported using the same method as in Production Example 8, except that 20 g of modified silicone (SH3775C (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., having a viscosity of 1600 mm ² / s at 25 ° C.) is used. An aqueous solution of an amphoteric urethane resin was obtained.

(Production Example 16)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 70 g of isophorone diisocyanate (IPDI), 55 g of polypropylene glycol (PPG, mass average molecular weight 1,000), polyethylene glycol (PEG, mass average) Molecular weight 1,000) 8 g, 1,4-cyclohexanedimethanol (CHDM) 7 g, dimethylpolysiloxane (viscosity at 25 ° C. is 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) 8 g and 20 g of dimethylolbutanoic acid (DMBA) were added, 50 g of ethyl acetate was added as a solvent, and the mixture was heated to 80 ° C. using an oil bath and reacted for 3 hours. Thereafter, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 3 hours to obtain a prepolymer having a remaining isocyanate group. The prepolymer having the isocyanate groups remaining is cooled to 50 ° C. and then dispersed in 700 g of water containing 10 g of potassium hydroxide at a high speed, followed by a chain extension reaction at 50 ° C. for 3 hours to increase the molecular weight. It was. The ethyl acetate was recovered from the obtained aqueous liquid to obtain an aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin substantially free of a solvent.

(Production Example 17)
In the production method described in Production Example 16, in place of 8 g of dimethylpolysiloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.), modified with polyether A polysiloxane compound-supported amphoteric acid using the same method as in Production Example 16 except that 8 g of silicone (SH3775C (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., having a viscosity at 25 ° C. of 1600 mm ² / s) is used. An aqueous liquid of urethane resin was obtained.

(Production Example 18)
In the production method described in Production Example 16, instead of 8 g of dimethylpolysiloxane (viscosity at 25 ° C. is 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.), dimethylpolysiloxane (The viscosity at 25 ° C. is 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.) An aqueous solution of an amphoteric urethane resin was obtained.

(Production Example 19)
In the production method described in Production Example 16, in place of 8 g of dimethylpolysiloxane (viscosity at 25 ° C. of 10 mm ² / s, SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.), modified with polyether A polysiloxane compound-carrying amphoteric acid using the same method as in Production Example 16 except that 20 g of silicone (SH3775C (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., having a viscosity of 1600 mm ² / s at 25 ° C.) was used. An aqueous liquid of urethane resin was obtained.

  One or more polysiloxane compound-carrying amphoteric urethane resins are arbitrarily selected and blended.

  The content of the polysiloxane compound-carrying amphoteric urethane resin is preferably 0.01 to 10% by mass in the total amount of the hair cosmetic. If the content is less than 0.01% by mass, a sufficient addition effect cannot be obtained, and even if the content exceeds 10% by mass, an effect commensurate with the blending amount cannot be obtained.

  Furthermore, as other optional compounding components, it is a partially overlapping description, for example, other than the above oil, surfactant, moisturizer, polyhydric alcohol such as propylene glycol, 1,3-butylene glycol, glycerin, Thickeners, other polymers, oil gelling agents, powders, pigments, dyes, lakes, saccharides, UV absorbers, amino acids, vitamins, blood circulation promoters, plant extracts, organic acids, organic Examples include amines, sequestering agents, pH adjusters, antioxidants, antibacterial agents, preservatives, astringents, refreshing agents, perfumes, and water.

  The hair cosmetic composition of the present invention can be prepared according to a conventional method by blending the above components. In addition, pH of the hair cosmetics prepared has the preferable range of 4-8. For example, in the case of a cationic polymer formulation, the pH is in the range of 4-6, and in the case of anionic polymer formulation, the pH is in the range of 5.5-8.

  Although the form which the hair cosmetics of this invention can take is not specifically limited, It is preferable to take the form of cosmetics for hair finishes, such as a hair styling agent, a hair wax, and a hair cream. In particular, hair wax is preferable, and a remarkable effect is exhibited in hair wax.

  Hereinafter, the present invention will be specifically described with reference to examples. A compounding quantity is the mass%. Prior to the description of the examples, the viscosity measurement method and effect test method used in the present invention will be described.

1. Viscosity measurement

  Using a Brookfield (BL) viscometer (DIGITAL VISMETRON VDH: manufactured by Shibaura System Co., Ltd.), the viscosity (mPa · s) at 30 ° C. was measured using a No. 6 spindle at a rotation speed of 10 rpm.

2. Usage test A usage test is conducted by a panel of 20 people, and each evaluation item for the stringiness, elasticity, finger throat, hair styling, natural hair styling, and hair style keeping power is based on the following criteria. And evaluated. Subsequently, the evaluation points given by each person were totaled and evaluated based on the following evaluation criteria.

(Evaluation criteria)
5 points: Excellent.
4 points: Excellent.
3 points: Normal.
2 points: Inferior.
1 point: Very inferior.

(Evaluation criteria)
A: The total score is 80 or more.
A: The total score is 60 points or more and less than 80 points.
Δ: The total score is 40 points or more and less than 60 points.
X: The total score is less than 40 points.

3. Stability test After the sample was stored in a thermostat at 50 ° C. for 1 month, the appearance of the sample was visually observed and judged according to the following evaluation criteria.

(Evaluation criteria)
○: No change such as separation or creaming of the liquid phase (oil phase or water phase) was observed.
X: Some change such as separation of the liquid phase (oil phase or water phase) and creaming occurred.

[Examples 1-8, Comparative Examples 1-8]
Hair waxes having the ingredients and blending amounts shown in Tables 1 to 4 (total blending amount: 100% by mass) were prepared by the following method.

(Preparation method)
(Parts A) A small amount of (7) to (10) was added to the stirring (14) and stirred for a whole day and night. (Parts B) and (6) were added to 70 ° C. water, dissolved by stirring, and cooled after standing to confirm uniformity. (Parts C) After mixing (1) to (4), the mixture was heated to 80 ° C. and dissolved to confirm uniformity. Next, (Part A) and (Part B) were mixed and heated to 70 ° C. to dissolve uniformly. Subsequently, (Part C) kept at 80 ° C. was added and emulsified using an Ajihomo mixer (manufactured by Tokushu Kika). Next, (12) and (13) were added to increase the viscosity, and then (5) and (11) were added.

In Tables 1-4,
(Note 1) Adecanol GT-700 (Asahi Denka Co., Ltd.)
(Note 2) Shintalen L (manufactured by Sigma)
(Note 3) Pemulen TR-1 (manufactured by Noveon)
(Note 4) Koskat GA467 (Osaka Organic Industry Co., Ltd.)
(Note 5) Yuka Former R205 (Mitsubishi Chemical Corporation)
(Note 6) Amphoteric urethane resin carrying polysiloxane compound of Production Example 8

  The hair cosmetics of Examples 1 to 8 and Comparative Examples 1 to 8 were subjected to viscosity measurement and effect test, and the results are shown in Tables 1 to 4.

  As can be seen from Tables 1 and 2, all the hair waxes of Examples 1 to 8 containing the essential components of the present invention had excellent effects. Further, the hair waxes of Examples 5 to 8 further blended with a polysiloxane compound-carrying amphoteric urethane resin were further improved in the effects of stringiness and elasticity. On the other hand, as can be seen from Tables 3 and 4, the hair wax of Comparative Example 1 containing no ionic vinyl polymer, ethanol, the hair wax of Comparative Example 2 containing no ionic vinyl polymer, and hydrophobic modification Any of the hair waxes of Comparative Examples 3 to 6 in which no polyether urethane was blended could not exhibit the effects of the present invention. Further, none of the hair waxes of Comparative Examples 7 and 8 in which the viscosity of the hair wax is out of the range of 20,000 to 100,000 mPa · s cannot exhibit the effects of the present invention.

  Hereinafter, examples of the hair cosmetic composition of the present invention will be described. In addition, manufacture was performed according to the method of Examples 1-8. Each of the obtained hair cosmetics had a viscosity in the range of 20,000 to 100,000 mPa · s. Moreover, when the effect test was done with respect to these, the outstanding result was obtained in all.

[Example 9] Hair wax component content (mass%)
Water Residual ethanol 10.0
1,3-butylene glycol 5.0
Oligosuccinic acid PEG-3-PPG-20 3.0
Glycerin 3.0
EDTA · 2Na-2H2O 0.2
Phenoxyethanol 0.5
Talc 2.0
Polymethyl methacrylate 1.0
Candelilla Row 5.0
Paraffin wax 3.0
Mineral oil 5.0
Hydrogenated isopolybutene 3.0
Trioctanoin 3.0
Dimethicone 1.0
Amodimethicone 1.0
Stearic acid 2.0
PEG-60 hydrogenated castor oil 2.0
Glyceryl stearate 0.5
Hydrophobically modified polyether urethane of Production Example 1 1.0
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 3.0
Carbomer (Note 1) 0.15
L-Arginine 0.5
Sodium L-glutamate 0.5
Total 100.0

(Note 1) Shintalen K (manufactured by Sigma)

Viscosity: 48,000 mPa · s, pH: 7.20

[Example 10] Hair wax component content (mass%)
Water Residual ethanol 5.0
Propylene glycol 10.0
PEG / PPG-14 / 7 dimethyl ether 1.0
Sodium hexametaphosphate 0.1
Methylparaben 0.2
Silica 1.0
Carnauba wax 2.0
Microcrystalline wax 5.0
Mineral oil 5.0
Pentaerythrityl tetraoctanoate 5.0
Phenyltrimethicone 2.0
Sodium cocoamphoacetate 2.0
Isostearic acid 1.0
Polysorbate-60 2.0
Alkyl-modified carboxyvinyl polymer (Note 1) 0.5
Hydrophobically modified polyether urethane of Production Example 2 0.8
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 10 1.0
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 19 1.0
Triethanolamine 0.05
Soy lecithin 1.0
Total 100.0

(Note 1) Pemulen TR-2 (manufactured by Noveon)

Viscosity: 68,000 mPa · s, pH: 6.90

[Example 11] Hair wax component content (mass%)
Water Residual ethanol 8.0
Propylene glycol 5.0
PEG-90M 0.05
Penteto acid 5Na 0.1
Methylparaben 0.05
Kaolin 1.0
Bentonite 1.0
Beeswax 5.0
Polyethylene wax 2.0
Vaseline 5.0
Cetyl octanoate 5.0
PEG-5-PPG-65 pentaerythrityl 2.0
Aminopropyl methicone 1.0
Ores-20 3.0
Cationic vinyl polymer (Note 1) 0.25
Cationic vinyl polymer of Production Example 6 0.25
Hydrophobic modified polyether urethane of Production Example 3 1.5
Amphoteric urethane resin carrying polysiloxane compound of Production Example 0.5 0.5
Amphoteric urethane resin carrying polysiloxane compound of Production Example 18 0.5
Lactic acid 0.2
(Acrylates / stearyl acrylate / ethylamine oxide methacrylate) copolymer (Note 2) 1.0
Total 100.0

(Note 1) Koscut GA467 (Osaka Organic Industry Co., Ltd.)
(Note 2) Diaformer Z-772 (Mitsubishi Chemical Corporation)

Viscosity: 52,400 mPa · s, pH: 5.10

[Example 12] Hair wax component content (mass%)
Water Residual ethanol 15.0
Maltose 1.0
Sorbitol 1.0
EDTA · 2Na-2H2O 0.2
Mowl 3.0
Vaseline 8.0
Mineral oil 3.0
Dimethicone 1.0
Aminopropyl dimethicone 1.0
Stearic acid 2.0
Ores-20 2.0
Glyceryl stearate 0.5
Hydrophobically modified polyether urethane of Production Example 4 1.0
(Dimethylacrylamide / acryloyldimethyltaurine sodium) crosspolymer (Note 1) 0.2
Amphoteric urethane resin carrying polysiloxane compound of Production Example 5.0 5.0
L-carnitine 0.5
Total 100.0

(Note 1) SU-GEL (Toho Chemical Co., Ltd.)

Viscosity: 36,000 mPa · s, pH: 6.80

[Example 13] Hair wax component content (mass%)
Water Residual ethanol 5.0
Dipropylene glycol 5.0
Diglycerin 2.0
EDTA · 2Na-2H2O 0.2
Phenoxyethanol 0.5
Carnauba wax 2.0
Beeswax 2.0
Mineral oil 5.0
Cetyl octanoate 5.0
Behenic acid 2.0
Setes-20 2.0
Glyceryl stearate 0.5
Hydrophobic modified polyether urethane (Note 1) 1.0
Acrylic acid / methacrylic acid steareth-20 copolymer (Note 2) 0.5
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 13 2.5
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 16 2.5
Creatine 0.5
Total 100.0

(Note 1) Adecanol GT-700 (Asahi Denka Co., Ltd.)
(Note 2) Acrine-22 (Rohm & Haas)

Viscosity: 66,000 mPa · s, pH: 6.90

[Example 14] Hair wax component content (mass%)
Water Residual ethanol 8.0
Urea 1.0
Trimethylglycine 1.0
Isoprene glycol 8.0
EDTA · 2Na-2H2O 0.2
Cetanol 5.0
Beeswax 2.0
Mineral oil 5.0
Dioctyl succinate 5.0
Myristic acid 2.0
Polysorbate-80 0.5
Hydrophobic modified polyether urethane (Note 1) 2.0
Polyquaternium-39 (Note 2) 1.0
Amphoteric urethane resin carrying polysiloxane compound of Production Example 2.0 2.0
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 17 2.0
Creatine 0.5
Total 100.0

(Note 1) Adecanol GT-700 (Asahi Denka Co., Ltd.)
(Note 2) Marcote Plus 3300 (Calgon)

Viscosity: 71,000 mPa · s, pH: 6.20

[Example 15] Hair wax component content (mass%)
Water Residual ethanol 8.0
Propylene glycol 5.0
PEG-90M 0.05
Penteto acid 5Na 0.1
Methylparaben 0.05
Kaolin 1.0
Bentonite 1.0
Beeswax 5.0
Polyethylene wax 2.0
Vaseline 5.0
Cetyl octanoate 5.0
PEG-5-PPG-65 pentaerythrityl 2.0
Aminopropyl methicone 1.0
Ores-20 3.0
Cationic vinyl polymer of Production Example 5 0.05
Cationic vinyl polymer of Production Example 7 0.05
Hydrophobic modified polyether urethane (Note 1) 1.5
Polysiloxane compound-carrying amphoteric urethane resin of Production Example 15 2.0
Lactic acid 0.2
Total 100.0

(Note 1) Adecanol GT-700 (Asahi Denka Co., Ltd.)

Viscosity: 53,000 mPa · s, pH: 5.20

Claims (9)

(A) 0.01-30 mass% of wax, (b) the following general formula (1)

(In General Formula (1), R ¹ represents a hydrocarbon group, R ² and R ⁴ each independently represent an alkylene group having 2 to 4 carbon atoms , and R ³ may be a hydrocarbon having a urethane bond. represents a group, R ⁵ represents a hydrocarbon group having minute岐鎖, m is a number of 2 or more, h is a number of 1 or more, the number of each k and n are independently 0 to 1000 range However, both k and n are not 0.) 0.1 to 10% by mass of the hydrophobically modified polyether urethane represented by (c) 0.001 to 5% by mass of the ionic vinyl polymer And (d) 0.1 to 30% by mass of alcohol, and the viscosity is 30,750 to 100,000 mPa · s. In the hydrophobically modified polyether urethane represented by the general formula (1) according to claim 1, R ¹ and R ² are each independently an ethylene group or a propylene group , R ³ is an alkylene group or a tolylene group having 4 to 8 carbon atoms, R ⁴ is an ethylene group, R ⁵ is a branched alkyl group having 8 to 36 carbon atoms, m is 2, h is 1, k is a number in the range of 67 to 1000 , and n is in the range of 10 to 35 . The hair cosmetic composition according to claim 1, which is a number.   (C) The hair cosmetic composition according to claim 1 or 2, wherein the ionic vinyl polymer is an anionic vinyl polymer, a cationic vinyl polymer or an amphoteric vinyl polymer.   The hair cosmetic composition according to claim 3, wherein the anionic vinyl polymer is a carbomer and / or an alkyl-modified carboxyvinyl polymer. The hair cosmetic according to claim 3, wherein the cationic vinyl polymer is an amine-containing (meth) acrylate monomer copolymer . The hair cosmetic according to claim 3, wherein the amphoteric vinyl polymer is a (meth) acrylic unit-containing amphoteric polymer .   Furthermore, (e) polysiloxane compound carrying | support amphoteric urethane resin is contained, The hair cosmetics as described in any one of the Claims 1 thru | or 6 characterized by the above-mentioned.   (E) The hair cosmetic composition according to claim 7, wherein the content of the polysiloxane compound-carrying amphoteric urethane resin is 0.01 to 10% by mass in the total amount of the hair cosmetic composition.   The hair cosmetic composition according to any one of claims 1 to 8, wherein the hair cosmetic composition is a hair wax.