TWI393574B - Water-based shampoo - Google Patents

Description

Water-based hair cleanser

The present invention relates to an aqueous hair cleansing agent which has excellent foaming and slippery quality at the time of shampooing and a slippery feel at the time of rinsing, and imparts luster and concentration to the processed hair and has excellent stability.

In the hair cleansing agent, a water-soluble cationic polymer is widely used for the purpose of imparting a conditioning effect to hair, but the effect of hair damaged by chemical treatment such as a hair dye and a permanent wave agent cannot be said to be sufficient. As a means for solving this problem, Patent Document 1 discloses a hair cleansing agent containing a high molecular weight amine-based modified polyfluorene oxide and an ammonium modified polyxylene. However, the amine-based modified polyfluorene or the like described in Patent Document 1 has a structure in which a side chain of a polyoxyalkylene has an alkylamine or an alkylammonium salt, and the water repellency is high, resulting in a hair detergent. In the case of lack of solubility and dispersibility, there is a problem in stability, and there is a problem that the foaming of the hair detergent is lowered, and it becomes hard and sticky during washing.

Further, Patent Document 2 proposes a hair cleansing agent comprising a copolymer of an amine-modified organic polyoxyalkylene chain and a block chain of a polyoxyalkylene chain. However, although the block copolymer has improved dispersibility in the hair cleansing agent, the stability cannot be said to be sufficient, and it still has a problem of becoming hard and sticky when washed.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-85918 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2002-326914

The present invention provides an aqueous hair purifying agent which has good foaming and slippery quality when shampooing, has a slippery feel upon rinsing, imparts luster and concentration to processed hair, and has excellent stability. .

The present inventors have discovered the use of block copolymers containing an anionic surfactant, an amine-modified organic polyoxyalkylene chain and a polyoxyalkylene chain, a water-soluble cationic polymer, and a pearlizing agent containing a specific component. In this case, a hair cleansing agent that satisfies the above requirements is obtained.

That is, the present invention provides an aqueous hair cleansing agent containing the following components (A), (B), (C) and (D).

(A) 1 to 30% by mass of an anionic surfactant, (B) 0.01 to 10% by mass of a copolymer having an amine-modified organic polyoxyalkylene chain and a block chain of a polyoxyalkylene chain, ( C) 0.01 to 5% by mass of a molecular weight of 100,000 to 1.9 million, a cationic charge density of 0.6 to 4 meq/g of a water-soluble cationic polymer, and (D) 0.1 to 10% by mass of a monomer selected from ethylene glycol monoalkyl esters, A pearlescent agent of at least one of a glycol dialkyl ester, an ethylene glycol monoalkyl ether, and an ethylene glycol dialkyl ether.

The hair cleansing agent of the present invention has good foaming and slippery foam quality at the time of shampooing, and has a slippery feel upon rinsing, and imparts luster and concentration to the processed hair.

The anionic surfactant of the component (A) of the present invention is preferably a sulfate-based, sulfonate-based or carboxylate-based one, and examples thereof include an alkyl sulfate, a polyoxyalkylene alkyl sulfate, and a polyoxygen. An alkyl alkenyl ether sulfate, an alkyl sulfosuccinate salt, an alkyl alkyl phenyl ether sulfate sulfonate, an alkane sulfonate, a higher fatty acid salt, an alkyl ether carboxylic acid or a salt thereof, Among them, polyoxyalkylene alkyl ether sulfates and alkyl sulfates are preferred, and those of the following general formula (2) or (3) are particularly preferred.

R'O(CH ₂ CH ₂ O) _n SO ₃ M (2) R'OSO ₃ M (3) wherein R' represents an alkyl or alkenyl group having 8 to 18 carbon atoms, and M represents a base Metal, alkaline earth metal, ammonium, n is the average weight of 1 to 5]

In particular, in the general formula (2), R' is an alkyl group having 12 to 14 carbon atoms, and n is a weight average of 1, and M is a combination of extremely fast foaming and good foaming feeling. It is preferably a polyoxyethylene alkyl ether sulfate of ammonium or sodium.

The component (A) may be used singly or in combination of two or more kinds, and the content thereof is 1% in the detergent composition of the present invention from the viewpoints of foaming, liquidity at the time of use, and detergency. 30% by mass, more preferably 5 to 25% by mass, particularly preferably 8 to 20% by mass.

The component (B) of the present invention is a copolymer having a block chain of an amine-modified organic polyoxyalkylene chain and a polyoxyalkylene chain, and is preferably a copolymer represented by the general formula (1).

In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² represents either R ¹ or E. E is represented by -R ³ -Z (wherein R ³ is a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z is a 1 to 3 amino group or an ammonium group) base. Y represents a divalent group. a is a number indicating 2 or more, b is a number of 1 or more, n is a number of 2 to 10, c is a number of 4 or more, and d is a number of 2 or more. In addition, the plurality of R ¹ , R ² and E may be the same or different. ]

In the general formula (1), R ^{1 is} preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or an ethyl group, particularly preferably a methyl group.

R ³ is preferably a linear or branched alkyl chain having 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylidene group, a trimethylene group, a propyl group, a tetramethylene group, etc., more preferably Trimethylene or propyl.

Z is preferably an amine group-containing or ammonium group-containing group represented by the general formula (4) or (5).

[wherein R ⁴ is a representation R ⁵ and R ⁶ are a hydrocarbon group which represents a hydrogen atom or a monovalent carbon number of 1 to 3, and each of R ⁵ and R ⁶ may be the same or different. e and f are integers representing 0 to 6, respectively. T ^- represents a halogen ion or an organic anion. ]

Preferred E groups in the general formula (1) are -(CH ₂ ) ₃ -NH ₂ , -(CH ₂ ) ₃ -N(CH ₃ ) ₂ , -(CH ₂ ) ₃ -NH-(CH ₂ ) ₂ -NH ₂ -(CH ₂ ) ₂ -NH-(CH ₂ ) ₂ -N(CH ₃ ) ₂ , -(CH ₂ ) ₃ -N ⁺ -(CH ₃ ) ₃ Cl ^- , more preferably -(CH ₂ ) ₃ -NH-(CH ₂ ) ₂ -NH ₂ . Specific examples of T ^- include halogen ions such as chlorine, iodine, and bromine; and organic anions such as dimethyl sulfate, diethyl sulfate, dimethyl phosphate, and diethyl phosphate.

In the general formula (1), preferred embodiments shown in the _divalent organic group of Y is an alkylene group or an arylene group, particularly preferred embodiment of stretch ethyl, propyl stretch, trimethylene, n-butyl or isobutyl extending extension Butyl, most preferably n-butyl or isobutylene.

In the general formula (1), a is a number from 2 to 1000, b is a number from 1 to 50, c is a number from 4 to 200, and d is preferably from 2 to 100.

In the block copolymer represented by the general formula (1), the proportion of the oxyalkylene block is preferably from 25 to 97% by mass, more preferably from 35 to 90% by mass, particularly preferably from 50 to 80% by mass based on the total amount of the copolymer. %, the block copolymer preferably has an average molecular weight of at least 1200. Further, the average molecular weights in the present specification are all values measured by a conventional method using GPC, chloroform as a solution, and polystyrene as a standard substance.

The term "oxynetane block" as used herein refers to a decane having 2 R ¹ groups represented by -[Si(R ¹ ) ₂ -O]-, and the ratio of the so-called oxane block is referred to as argon. The ratio of the molecular weight of the alkane block to the molecular weight of the block copolymer (1) is expressed by mass%. When it is in the above range, the block copolymer (1) is excellent in solubility or dispersibility in the hair cleansing agent, and is excellent in residualness to hair.

More preferably, it is an amine-modified polyoxyalkylene-polyoxyalkylene block copolymer having a polymerization unit represented by the general formula (6).

[wherein, a, b and d are synonymous with the above. g is a number indicating 4 or more. h is the number from 0 to 30]. In the general formula (6), a is preferably a number from 2 to 1,000, b is from 1 to 50, g is from 4 to 200, and d is from 2 to 100. Further, -0(C ₂ H ₄ O) _g (C ₃ H ₆ O) _h - is either a block copolymer or a random copolymer. Examples of this can be cited Dongli. Dowconing. Silicone's FZ-3789, polyoxynium SS-3588.

The dynamic viscosity used in the present invention, component (B) is having two or more of 10mm ² / s viscosity preferably, and to 100mm ² / s or more is more preferred to 1,000mm ² / s or more is particularly preferred to 5,000mm ² / Above s is the best. Further, it is preferably 1,000,000 mm ² /s or less, and more preferably 100,000 mm ² /s or less. Within this range, the component (B) is excellent in solubility or dispersibility in the hair cleansing agent, and is excellent in residualness to hair.

Further, the viscosity was measured by a Brookfield viscometer at 25 ° C under Rotor No. 2 at 6 rpm / min.

The component (B) used in the present invention preferably has an amine equivalent of 300 g/mol or more, more preferably 600 g/mol or more. Further, it is preferably 10,000 g/mol or less, more preferably 5,000 g/mol or less, and particularly preferably 2,500 g/mol or less. In this range, the component (B) is excellent in solubility or dispersibility in the hair cleansing agent, and it is preferable to reduce the hairiness of the hair during rinsing and to improve the softness.

Further, the amine equivalent (g/mol) can be determined by titrating a known concentration of hydrochloric acid with an ethanol solution of the block copolymer.

These (B) components may be used alone or in combination of two or more. The content of the component (B) in the hair cleansing agent of the present invention is in the range of 0.01 to 10% by mass, preferably 0.02 to 5% by mass, from the viewpoint of reducing the feeling of hairiness during hair washing. Good is 0.03~2% by mass.

Further, the component (B) used in the present invention is produced, for example, by the method described in JP-A-9-183854.

The cationic polymer of the component (C) of the present invention is a polymer having a molecular weight of from 100,000 to 1.9 million and a cationic charge density of from 0.6 to 4 meq/g. In particular, in terms of slippage during blistering and slippage during rinsing, it is preferably a molecular weight of 200,000 to 1.8 million, particularly a molecular weight of 300,000 to 1.7 million, and a cationic charge density of 0.6 to 3.8 meq/g. Especially 0.7~3.5meq/g is preferred. The charge density of the water-soluble cationized polymer can be measured, for example, by a colloidal dissolution method using polyvinyl potassium sulfate as a titration solution.

Specific examples of the water-soluble cationic polymer include a cationized cellulose derivative, a cationic starch, a cationized guaia rubber derivative, a diallyl quaternary ammonium salt/acrylamide copolymer, and a trichloroethylene. Imidazolium/vinylpyrrolidone copolymer, hydroxyethylcellulose/dimethyldiallyl ammonium chloride copolymer, vinylpyrrolidone/quaternary dimethylamine ethyl methacrylate copolymer, polyethylene a pyrrolidone/alkylamino acrylate copolymer, a polyvinylpyrrolidone/alkylamino acrylate/vinylcaprolactone copolymer, a vinylpyrrolidone/methacrylamide propylamine trimethylammonium chloride copolymer, Alkyl acrylamide/acrylate/alkylaminoalkyl acrylamide/polyethylene glycol methacrylate copolymer, adipic acid/dimethylamino hydroxypropyl ethylene monoamine copolymer (Sundose, USA) The cationic polymer described in Japanese Laid-Open Patent Publication No. SHO-63-139734, and the cationized cellulose derivative and the cationized guaia rubber. Derivatives, diallyl quaternary ammonium salts/acrylamide copolymers are preferred.

Further, for example, Macoat 550 (NALCO Corporation, a copolymer of acrylamide and diallyldimethylammonium salt; CTFA name Polyquatanium-7), Rubiquat FC370 (BASF Corporation, 1-vinyl-2-pyrrolidone) can be used. Copolymer with 1-vinyl-3-methylimidazolium salt; CTFA name Polyquatanium-16), Gafuquat 755N (ISP company, copolymerization of 1-vinyl-2-pyrrolidone and dimethylamine ethyl methacrylate) Fit; CTFA name Polyquatanium-11), Ucare Polymer JR and LR series (Amerchol, a salt of a reaction of trimethylammonium substituted epoxide with hydroxyethyl cellulose; CTFA name Polyquatanium-10), Poise C- 60H, Poise C-80M, Poise C-150L (Kao Corporation, salt of the reaction of trimethylammonium substituted epoxide with hydroxyethyl cellulose; CTFA name Polyquatanium-10), Jaguar series (Rohdia, chlorination) Commercial products such as guaiahydroxypropyltrimonium).

The component (C) may be used alone or in combination of two or more kinds, and the content thereof is preferably from 0.01 to 5% by mass in the detergent composition of the present invention, and from the viewpoint of slipperiness from the time of shampooing to the time of rinsing It is more preferably 0.05 to 2% by mass, and particularly preferably 0.1 to 1% by mass.

The component (D) of the present invention is a pearlizing agent containing at least one selected from the group consisting of ethylene glycol monoalkyl ester, ethylene glycol dialkyl ester, ethylene glycol monoalkyl ether, and ethylene glycol dialkyl ether. Examples of the ethylene glycol monoalkyl ester include ethylene glycol monostearyl ester and ethylene glycol monoprene ester. Further, examples of the ethylene glycol dialkyl ester include ethylene glycol distearyl ester and ethylene glycol disorbent. Examples of the ethylene glycol monoalkyl ether include ethylene glycol monostearyl ether, and examples of the ethylene glycol dialkyl ether include ethylene glycol distearyl ether. Further, it may be used in combination of two or more kinds, and the content thereof is 0.1 to 10 by mass in the aqueous hair detergent of the present invention from the viewpoint of improving the stability of the detergent and improving the slipperiness at the time of foaming and rinsing. % is preferable, and it is preferably 0.5 to 5% by mass, particularly preferably 1 to 4% by mass.

In the aqueous hair cleansing agent of the present invention, a nonionic surfactant or an amphoteric surfactant may be contained in order to further improve the cleaning performance.

Examples of the nonionic surfactant include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycerol fatty acid esters, and polyoxyalkylene fatty acids. Esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene (hardened) castor oils, sucrose fatty acid esters, polyglyceryl ethers, polyglycerol fatty acid esters And fatty acid alkanolamines, alkyl glycosides, monoalkyl glyceryl ethers, monoalkenyl glyceryl ethers, and the like. Among them, alkyl glycosides, polyoxyalkylene (C ₈ ~C _{2 0} ) fatty acid esters, polyoxyethylene ethyl sorbitan fatty acid esters, polyoxyethylene hardened castor oil, fatty acid alkanols Amines, monoalkyl glyceryl ethers, and monoalkenyl glyceryl ethers are preferred.

The fatty acid alkanolamine may be any of a monoalkanolamine or a dialkylolamine, and has a mercapto group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms. good. In particular, a hydroxyalkyl group having 2 to 3 carbon atoms is preferred, and examples thereof include oleic acid diethanolamine, palm kernel oil fatty acid diethanolamine, coconut oil fatty acid diethanolamine, and lauric acid diethanolamine. Polyoxyethylene coconut oil fatty acid monoethanol decylamine, coconut oil fatty acid monoethanol decylamine, lauric acid isopropanol decylamine, lauric acid monoethanol decylamine and the like.

The alkyl group or the alkenyl group in the monoalkyl glyceryl ether or monoalkenyl glyceryl ether is preferably a linear or branched alkyl group having 4 to 10 carbon atoms, particularly 8 to 10 carbon atoms. Specific examples thereof include n-butyl group, isobutyl group, n-pentyl group, 2-methylbutyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, and A mercapto group, an isodecyl group or the like, and particularly preferably a 2-ethylhexyl group or an isodecyl group.

As an amphoteric surfactant, beet It is a surfactant and the like. Alkyl dimethylaminoacetate beet Fatty acid amidinopropyl beet Alkyl hydroxy sulfo beet Beet Surfactant is preferred, and the fatty acid amidoxib is used. It is especially good. Fatty acid amidoxib It is preferably a fluorenyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and particularly a guanamine propyl laurate Palm kernel oil fatty acid amidoxib beet Coconut oil fatty acid amidoxib beet It is better.

These nonionic or amphoteric surfactants may be used in the form of an aqueous liquid detergent in the form of an aqueous liquid detergent in one or a combination of two or more of the aqueous hair cleansing agents. (A), as well as the fatty acid amidinopropyl beet The fatty acid alkanolamine or monoalkyl glyceryl ether is particularly preferable because not only the foaming power is further improved, but also moderate liquidity can be obtained.

The content of the nonionic or amphoteric surfactant is preferably from 0.1 to 15% by mass in the hair detergent of the present invention, and more preferably from 0.5 to 8% by mass, particularly from 1 to 6% by mass. The bubble effect is good.

In the aqueous hair cleansing agent of the present invention, in order to improve the processability after drying, polyfluorene oxygen as shown in the general formula (7) may be blended.

R(CH ₃ ) ₂ SiO-[(CH ₃ ) ₂ SiO] _m -Si(CH ₃ ) ₂ R (7) [wherein R represents a methyl group or a hydroxyl group, and m represents a number of 1 to 20,000]

The average particle diameter of the dispersed particles of polyoxymethylene is preferably less than 100 μm, more preferably 50 μm or less, particularly preferably 4 μm or less, more preferably 2 μm or less. Further, when the average particle diameter is 0.1 μm or more, the feeling of use and the conditioning effect are preferred.

As such a polyoxygenated oil, for example, 60% by mass of a dimethylpolysiloxane having a formula (7) of 300 to 6,500 may be used, and Toray with an average particle diameter of 0.8 μm may be used. Dowconing Silicone's "Silicone CF2450" or m is 300~6,500 dimethyl polysiloxane oil 50% by mass, and the average particle size is 50 μm. Dowconing Silicone is a "Silicone CF2460" type marketer.

The polyoxygenated oil is preferably contained in the aqueous hair cleansing agent of the present invention in an amount of 0.01 to 10% by mass, more preferably 0.05, in terms of improving the feeling of the bubble upon shampooing, the touch and the feeling after drying. It is preferably 6% by mass, particularly 0.3 to 3% by mass, particularly preferably 0.5 to 2% by mass.

In the aqueous hair cleansing agent of the present invention, in order to improve the processing after drying, the cationic surfactant and the modified polyfluorene oxygen other than the component (B) may be further blended.

As the cationic surfactant, for example, those shown in the following (i) to (vi) are suitably used.

(i) The alkyltrimethylammonium salt can be, for example, the following general formula.

R ^{1 1} -N ⁺ (Me) ₃ X ^- wherein R ^{1 1} represents an alkyl group having 12 to 22 carbon atoms, Me represents a methyl group, and X ^- represents a halogen (chlorine or bromine) ion. ]

(ii) The alkoxytrimethylammonium salt may, for example, be represented by the following general formula.

R ^{1 2} -O-R ^{1 3} -N(Me) ₃ X ^- wherein R ^{1 2} represents an alkyl group having 12 to 22 carbon atoms, and R ^{1 3} represents an exoethyl or propyl group, Me To represent a methyl group, X ^- is the same as above]

(iii) The dialkyldimethylammonium salt may, for example, be represented by the following general formula.

R ^{1 4} ₂ -N ⁺ (Me) ₂ X ^- wherein R ^{1 4} represents an alkyl group or a benzyl group having 12 to 22 carbon atoms, Me represents a methyl group, and X ^- is the same as described above]

(iv) The alkyldimethylamine and the salt thereof may, for example, be represented by the following general formula.

R ^{1 5} -N(Me) ₂ [wherein R ^{1 5} represents an alkyl group having 12 to 22 carbon atoms, and Me represents a methyl group]

(v) Alkoxydimethylamine and a salt thereof are, for example, those represented by the following general formula.

R ^{1 6} -O-R ^{1 7} -N(Me) ₂ [wherein R ^{1 6} represents an alkyl group having 12 to 22 carbon atoms, R ^{1 7} represents an exoethyl group or a propyl group, and Me represents methyl]

(vi) The alkylguanamine dimethylamine and the salt thereof may, for example, be represented by the following general formula.

R ^{1 8} -C(=O)NH-R ^{1 9} -N(Me) ₂ [wherein, R ^{1 8} represents an alkyl group having 11 to 21 carbon atoms, and R ^{1 9} represents an ethyl group or a stretching group. Base, Me is methyl

Examples of the cationic surfactant other than the above (i) to (vi) include ethyl sulphate aqueous lanolin fatty acid amine propyl ethyl dimethyl ammonium (alkyl sulfonium propyl dimethyl ethyl ammonium ethyl sulphate) Salt, alkyl hydrazide is derived from aqueous lanolin), ethyl sulphate aqueous lanolin fatty acid amine ethyl triethyl ammonium, ethyl sulfuric acid aqueous lanolin fatty acid amine propyl triethyl ammonium, methyl sulfuric acid aqueous lanolin fatty acid amine Ethyltrimethylammonium, methylsulfate-containing lanolin fatty acid amine propylethyldimethylammonium, ethylsulfate isoalkanoic acid (C _{1 4} ~C _{2 0} )amine propylethyldimethylammonium, Ethyl isobutyl acid (C _{1 8} ~ C _{2 2} ), amine propyl ethyl dimethyl ammonium, ethyl sulforamate, propyl propyl dimethyl ammonium, ethyl sulfonate Propyl ethyl dimethyl ammonium and alkyl trimethyl ammonium saccharin.

The cationic surfactant may be used in combination of two or more kinds, and from the viewpoint of slipperiness from the time of shampooing to the time of rinsing, the content is preferably 0.01 to 10% by mass in the aqueous hair detergent of the present invention, and more preferably It is preferably 0.05 to 6% by mass, particularly 0.3 to 3% by mass, particularly preferably 0.5 to 2% by mass.

Examples of the modified polyfluorenes other than the component (B) include those shown below.

(a) Amine-based modified polyoxyl can be modified with various amine groups, especially at an average molecular weight of about 3,000 to 100,000, as described by the Amodimethicone name in the CTFA dictionary (US, Cosmetic Ingredient Dictionary, 3rd edition). It is better. Commercially available products include SM 8704C (Dollying Silicone Co., Ltd.), DC 929 (Dowconing Co., Ltd.), KT 1989 (GE Toshiba Silicone Co., Ltd.), and 8500 Conditioning Agent (Dongli. Dowconing Silicone Co., Ltd.).

(b) Other polyoxyl oxides, in addition to the above, polyether modified polyfluorene oxide, methylphenyl polyoxyalkylene, fatty acid modified polyfluorene, alcohol modified polyoxyl, alkoxy modification Polyfluorene oxide, epoxy modified polyfluorene oxide, fluorine modified polyfluorene oxide, cyclic polyfluorene oxide, alkyl modified polyoxane and the like.

These polysiloxanes may be used in combination of two or more kinds, and the content is preferably from 0.01 to 10% by mass in the aqueous hair cleansing agent of the present invention, in terms of slipperiness from the time of shampooing to washing. Further, it is preferably 0.05 to 6% by mass, particularly 0.3 to 3% by mass, particularly preferably 0.5 to 2% by mass.

Further, as another conditioning agent, an oil agent may be contained. Examples of the oil agent include hydrocarbons such as squalene, squalane, flowing petroleum wax, flowing isoparaffin, and cycloalkane; glycerides such as castor oil, cocoa butter, eucalyptus oil, avocado oil, and olive oil; Waxes such as beeswax, cetyl wax, water-containing lanolin, carnauba wax, etc.; myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, glycerin, etc. Alcohols; isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleic acid ester, 2-B Esters of cetyl myristate, isodecyl isononanoate, tridecyl isononate, etc.; tannic acid, lauric acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid , higher fatty acids such as coconut oil fatty acid, isostearic acid, isopalmitic acid, etc.; other isostearyl glyceryl ether, polyoxypropylene butyl ether and the like. Among them, higher alcohols are preferred, and especially myristyl alcohol, cetyl alcohol, and stearyl alcohol are preferred. These oil agents may be used alone or in combination of two or more kinds, and the content thereof is preferably 0.2 to 2% by mass, more preferably 0.3 to 1.8% by mass, particularly 0.5 to 1.5% by mass of the aqueous hair detergent of the present invention. % is better.

The aqueous hair cleansing agent of the present invention may further contain a viscosity adjusting agent, and examples of the viscosity adjusting agent include hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, and the like. Pentadiene diol, ethanol, benzyl alcohol, benzyloxyethanol, phenoxyethanol, clay minerals, salts (sodium chloride, ammonium chloride, sodium citrate, etc.), among others, benzyl alcohol, ethanol, Polypropylene glycol, sodium chloride, and sodium citrate are preferred. The viscosity modifier may be used in combination of two or more kinds, and the amount of use thereof is preferably from 0.01 to 5% by mass, more preferably from 0.05% by weight, based on the amount of the foam and the foam. 4% by mass, particularly 0.1 to 3% by mass, is preferred.

In the aqueous hair cleansing agent of the present invention, in addition to the above components, the components used in the usual hair cleansing agent may be appropriately blended according to the purpose. As such a component, for example, an anti-dandruff agent; a vitamin agent; a bactericide; an anti-inflammatory agent; a preservative; a chimeric agent; a humectant such as sorbitol or panthenol; a coloring agent such as a dye or a pigment; Solvent extract, protein obtained by shell or pearl of true bead layer or hydrolyzate thereof, protein obtained from silk or hydrolyzate thereof, protein-containing extract obtained from seeds of leguminous plant, human extract, rice germ extract , extracts of Japanese Luohanbai extract, spice extract, moon leaf extract, chlorella extract, etc.; pearlescent agents such as titanium oxide; perfume; pigment; ultraviolet absorber; antioxidant; other ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS)] The ingredients and the like.

The aqueous hair cleansing agent of the present invention is preferably applied to the hair at a pH (20 times by weight of water, 25 ° C) of 2 to 6 and more preferably pH 3 from the viewpoint of improving the gloss and concentration of the hair. 5. It is especially preferred to have a pH of 3.5 to 4.5. The pH adjuster is preferably an organic acid, particularly an α-hydroxy acid, and specifically, malic acid, citric acid, lactic acid, or glycolic acid is preferred. These organic acids may be used in combination of two or more kinds, and the amount of use thereof is preferably from 0.01 to 5% by mass in the aqueous hair cleansing agent of the present invention in terms of improving the foaming property of the foam and the hair softening at the time of shampooing. Further, it is preferably 0.1 to 3% by mass, particularly preferably 0.3 to 2% by mass. Further, as another pH adjuster, a base such as sodium hydroxide, potassium hydroxide or ammonium chloride may be used in combination with these organic acids.

The form of the aqueous hair cleansing agent of the present invention can be appropriately selected from a liquid form, a gel form, and the like, and it is preferred that the solvent be water and/or a lower alcohol, particularly a liquid using water.

[Examples] <Evaluation method>

(1) The speed of foaming was measured by the apparatus shown in Fig. 1 (the apparatus disclosed in Japanese Patent Laid-Open No. Hei 10-73584) and the method shown below to evaluate the foaming of 1.5 ml of the sample and 0.3 ml of the model sebum. The amount was measured, and the time until the amount of bubbles was 25 ml was evaluated.

In the apparatus shown in Figs. 1 and 2, as the hair 1, 30 g of hair of 90 mm was used for planting on a circular plate 11 having a diameter of about 160 mm. The container 10 is a cylindrical shape having a diameter of 160 mm and a height of 220 mm, and the cover 20 is formed by using three cylindrical protrusions having a diameter of 15 mm and a height of 12 mm as the first protrusions 21, and having nine longitudinal 10 mm, a lateral width of 2 mm, and a height of 12 mm. The protrusions serve as the second protrusions 22. Further, the number of revolutions of the container 10 caused by the motor was set to 70 revolutions per minute.

In the foaming evaluation method using the device, first, the hair is moistened with 30 g of water, and after adding the model sebum, the sample is evaluated, and then the hair 1 and the projections 21 and 22 are slid and caught by the meter 50. Grab the collection of foam. In this case, the catch collection amount of the bubble is recorded every 50 seconds immediately after the start of the slide. The evaluation criteria are as follows.

<Evaluation criteria> ◎: less than 100 seconds ○: 100 or more less than 200 seconds △: 200 or more less than 300 seconds ×: 300 seconds or more

(2) Slipperiness during rinsing The human hair bundle with a length of 25 cm, a width of 5.5 cm and a weight of 10 g is gently washed with warm water of 40 ° C, and then excess water is taken out, and 0.5 g of hair detergent is used and about 30 Fully bubbling in seconds. Thereafter, the bundle of blistering hair was rinsed with warm water of 40 ° C at a flow rate of 2 liters/min, and the feeling of slipperiness was evaluated by the function. The evaluation was performed in 5 people, and the total value of the evaluation was shown. Moreover, the evaluation criteria are as follows.

4: Good slippery 3: Slightly slippery 2: quite slippery 1: not slippery

(3) Gloss and concentration after drying The hair bundles treated with the slip evaluation were washed with running water (2 liters/min) at 40 ° C, and the water was sufficiently wiped with a towel and naturally dried. After drying, the gloss and concentration were visually evaluated. The evaluation was performed in 5 people, and the total value of the evaluation was shown.

4: Good 3: slightly better 2: quite poor 1: poor

(4) Stability 100 ml of the hair cleansing agent was filled in a 110 ml size bottle and evaluated after storage at 50 ° C for 1 month.

○: No change caused by preservation was observed. △: Some slight changes were observed through storage (within the allowable range) ×: Seek significant changes through storage (outside the allowable range)

[Examples 1 to 6 and Comparative Examples 1 to 4]

The hair cleansing agent shown in Table 1 was prepared and evaluated by the above evaluation method. Further, the pH was 20 times by weight diluted with water and at 25 °C.

*1 lauryl ether (1) ammonium sulfate; ethylene oxide weight average addition molar number 1 * 2 amine modified organic polyoxane and polyoxyalkylene chain block copolymer; "polyoxyl SS-3588", Dong Li. Dowconing. Silicone (dynamic viscosity 65,000mm ² /s, amine equivalent 1250g / mol) * 3 amine-based modified polyoxo; "polyoxyn KT1989", GE Toshiba Silicone * 4 cationized hydroxyethyl cellulose; Poise M-80", Kao Corporation, molecular weight of 800,000, cationic charge density of 1.0 meq / g * 5 diallyl dimethyl dimethyl ammonium / acrylamide copolymer; "Macoat550", NALCO company, molecular weight is 1.5 million, cationic charge density 3.1 meq/g, polymer active ingredient 8.5% *6 cationized hydroxyethyl cellulose; "Catinol HC-200", Toho Chemical Industry Co., Ltd., molecular weight 2 million, cationic charge density 0.8 meq/ g *7 dimethyl diallyl ammonium chloride copolymer; "Macoat 100", NALCO company), molecular weight 50,000, cationic charge density 6.2 meq / g, polymer active ingredient 40.0% * 8 Dimethiconel; viscosity 10,000 cs /10cs=95/5 mixture, average particle size 0.5 μ m *9 Dimethicone2; polyfluorene CF2460, Toray. Dowconing. Silicone, with an average particle size of 50 μm

The hair cleansing agents of Examples 7 to 11 have excellent rapid foaming, good foaming and smoothness during rinsing, and the processed hair has good gloss and concentration, and is excellent in stability.

(industrial availability)

The aqueous hair cleansing agent of the present invention has good foaming and slippery foam quality during shampooing, has a slippery feel upon rinsing, and imparts luster and concentration to the processed hair.

1. . . Hair

10. . . container

11. . . Circular plate

20. . . cover

twenty one. . . First protrusion

twenty two. . . Second protrusion

twenty three. . . Bubble induced wall

twenty four. . . Prevent hair from getting caught in the plug

25. . . Injection hole

30. . . motor

50. . . Meter

51. . . Water injection hole

60. . . Torque detector

Fig. 1 is a view showing a detergent evaluation device.

Fig. 2 is a plan view (a) of a circular plate of hair implanted hair and a sectional view (b) of a circular plate of hair implanted hair.

Claims (3)

An aqueous hair cleansing agent characterized by containing the following components (A), (B), (C) and (D): (A) 1 to 30% by mass of an anionic surfactant; (B) 0.01 to 0.8 % by mass of a copolymer having an amine-modified organic polyoxyalkylene chain and a block chain of a polyoxyalkylene chain; (C) 0.01 to 5% by mass of a molecular weight of 100,000 to 1.9 million, and a cationic charge density of 0.6~ 4 meq/g of a water-soluble cationic polymer; and (D) 0.1 to 10% by mass of a mixture selected from the group consisting of ethylene glycol monoalkyl esters, ethylene glycol dialkyl esters, ethylene glycol monoalkyl ethers, and ethylene glycol dioxane A pearlescent agent of at least one substance of an ether. The aqueous hair cleansing agent of claim 1, wherein the component (B) is a copolymer represented by the general formula (1) Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R ² is any one of R ¹ or E; and E is —R ³ —Z (wherein R ³ is represented by Direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Z is a group represented by a 1 to 3 amino group or an ammonium group; Y is a divalent group; and a is 2 or more. The number b is 1 or more, n is 2 to 10, c is 4 or more, and d is 2 or more; and a plurality of R ¹ , R ^{2 ,} and E may be the same or different. The aqueous hair cleansing agent according to claim 1 or 2, wherein the (A) anionic surfactant is represented by the general formula (2) or (3); and R'O(CH ₂ CH ₂ O) _n SO ₃ M (2) R'OSO ₃ M (3) wherein R' represents an alkyl or alkenyl group having 8 to 18 carbon atoms, M represents an alkali metal, an alkaline earth metal, ammonium, and n is a weight. The average value is 1~5].