JP4955959B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention relates to an aqueous hair cleansing agent that has good foaming at the time of shampooing, a foam quality with good slippage and a smooth feel at the time of rinsing, gives gloss to the finished hair, and is excellent in stability.

  A water-soluble cationic polymer is widely used as a hair cleaning agent for the purpose of imparting a conditioning effect to the hair, but it is suitable for hair damaged by chemical treatment such as a hair coloring agent or a permanent agent. The effect was not sufficient. As means for solving this, Patent Document 1 describes a hair cleanser containing a high molecular weight amino-modified silicone and an ammonium-modified silicone. However, since the amino-modified silicone described in Patent Document 1 has a structure such as having an alkyleneamine or alkyleneammonium salt in the side chain of polysiloxane, it is highly hydrophobic, resulting in solubility and dispersion in a hair cleanser. Due to its poor nature, there were problems with stability, and there was a problem that foaming of the hair washing agent was reduced and it became sticky and sticky at the time of rinsing.

  Patent Document 2 proposes a hair cleanser containing a copolymer having a block chain of an amino-modified organopolysiloxane chain and a polyoxyalkylene chain. However, although this block copolymer has improved dispersibility in the hair washing agent, it cannot be said that the stability is sufficient, and still has the problem of wrinkles and stickiness during rinsing.

JP-A-5-85918 JP 2002-326914 A

  The present invention provides an aqueous hair cleanser that has good foaming and slippery foam quality when shampooed, has a smooth feel when rinsed, gives gloss to the finished hair, and has excellent stability. For the purpose.

  The present inventor made the above request when using an anionic surfactant, a block copolymer having an amino-modified organopolysiloxane chain and a polyoxyalkylene chain, a water-soluble cationic polymer and a pearling agent containing a specific component. It has been found that a hair cleanser that satisfies the requirements can be obtained.

That is, the present invention provides the following components (A), (B), (C) and (D)
(A) 1-30% by mass of an anionic surfactant,
(B) 0.01 to 10% by mass of a copolymer having a block chain of an amino-modified organopolysiloxane chain and a polyoxyalkylene chain;
(C) 0.01 to 5% by mass of a water-soluble cationic polymer having a molecular weight of 100,000 to 1,900,000 and a cationic charge density of 0.6 to 4 meq / g,
(D) 0.1 to 10% by mass of a pearlizing agent containing at least one selected from ethylene glycol monoalkyl ester, ethylene glycol dialkyl ester, ethylene glycol monoalkyl ether, and ethylene glycol dialkyl ether,
An aqueous hair cleanser containing

  The hair cleanser of the present invention has good foaming and slippery foam quality at the time of shampooing, has a smooth feel at the time of rinsing, and gives gloss to the finished hair.

The anionic surfactant of the component (A) of the present invention is preferably a sulfate, sulfonate, or carboxylate, for example, alkyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl. Examples include ether sulfates, sulfosuccinic acid alkyl ester salts, sulfosuccinic acid alkylene alkyl phenyl ether sulfates, alkane sulfonates, higher fatty acid salts, alkyl ether carboxylic acids or salts thereof, among them polyoxyalkylene alkyl ether sulfates. Alkyl sulfates, particularly those represented by the following general formula (2) or (3) are preferred.
_{R'O (CH 2 CH 2 O)} n SO 3 M (2)
R'OSO ₃ M (3)
[Wherein, R ′ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, M represents an alkali metal, an alkaline earth metal, or ammonium, and n represents a number of 1 to 5 on a weight average basis. ]
Among these, from the viewpoint of achieving both quick foaming and good foam feel, R ′ in the general formula (2) is an alkyl group having 12 to 14 carbon atoms, n is a weight average of 1, and M is Polyoxyethylene alkyl ether sulfates that are ammonium or sodium are preferred.

  The component (A) may be used alone or in combination of two or more thereof, and the content thereof is 1 in the cleaning composition of the present invention from the viewpoint of foaming, liquid properties during use and detergency. It is -30 mass%, Furthermore, 5-25 mass% is preferable, and 8-20 mass% is especially preferable.

  Component (B) of the present invention is a copolymer having a block chain of an amino-modified organopolysiloxane chain and a polyoxyalkylene chain, and a copolymer represented by the general formula (1) is preferable.

[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² represents either R ¹ or E. E represents —R ³ —Z (wherein R ³ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z represents a primary to tertiary amino group-containing group or an ammonium group-containing group. ) Is represented. Y represents a divalent group. a is a number of 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. A plurality of R ¹ , R ² and E may be the same or different. ]

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

R ³ is preferably a linear or branched alkylene chain having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and more preferably a trimethylene group or a propylene group. is there.

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

[Wherein R ⁴ is

R ⁵ and R ^{6 each} represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and each R ⁵ and R ⁶ may be the same or different. e and f each represent an integer of 0-6. T ⁻ represents a halogen ion or an organic anion. ]

Preferred E groups in the general formula _{(1), - (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 - and is, more preferably, - a _{(CH 2) 3 -NH- (CH} 2) 2 -NH 2. T ^- Specific examples of chlorine, iodine, halogen ion such as bromine; methosulfate, ethosulfate, methemoglobin phosphate, and organic anions such as ethoxy phosphate.

  In the general formula (1), preferred examples of the divalent group represented by Y are an alkylene group or an arylene group, and particularly preferred examples are an ethylene group, a propylene group, a trimethylene group, an n-butylene group, or i-. A butylene group, most preferably an n-butylene group or an i-butylene group.

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

  The ratio of the siloxane block in the block copolymer represented by the general formula (1) is preferably 25 to 97% by mass, more preferably 35 to 90% by mass, and particularly preferably 50 to 80% by mass of the entire copolymer. It is preferred that the block copolymer has an average molecular weight of at least 1200. In addition, all the average molecular weights in this specification are values measured by an ordinary method using GPC, using chloroform as an eluent and polystyrene as a standard substance.

Here, the siloxane block refers to a siloxane having two R ¹ groups represented by — [Si (R ¹ ) ₂ —O] —, and the ratio of the siloxane block refers to the molecular weight of the siloxane block, The ratio to the molecular weight of the block copolymer (1) is expressed in mass%. If it is in the said range, the solubility or dispersibility in the hair cleaning agent of block copolymer (1) is good, and the persistence to hair is also high and preferable.

  A further preferred example is an amino-modified polysiloxane-polyoxyalkylene block copolymer having a polymer unit represented by the general formula (6).

[Wherein, a, b and d have the same meaning as described above. g represents a number of 4 or more. h shows the number of 0-30. In general formula (6), preferably, a is a number from 2 to 1000, b is a number from 1 to 50, g is a number from 4 to 200, and d is a number from 2 to 100. _{Further, -O (C 2 H 4 O} ) g (C 3 H 6 O) h - may be either a block copolymer or a random copolymer. Examples thereof include Toray Dow Corning Silicone FZ-3789 and Silicone SS-3588.

Kinematic viscosity of the component (B) used in the present invention preferably has a viscosity of more than 10 mm ² / s, more preferably not less than 100 mm ² / s, particularly preferably not less than 1,000mm ² / s, 5,000 mm ² / s or more is most preferable. Moreover, 1 million mm < ² > / s or less is preferable and 100,000 mm < ² > / s or less is still more preferable. Within this range, the solubility or dispersibility of the component (B) in the hair cleaning agent is good, and the residual property on the hair is also high and preferable.
The viscosity was measured with a B-type viscometer using a rotor No. 2 was measured at 6 rpm / min.

The amine equivalent of the component (B) used in the present invention is preferably 300 g / mol or more, and 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. Within this range, the component (B) is preferably dissolved or dispersible in the hair cleansing agent, and the squeaky feeling of the hair during rinsing is reduced and the softness is improved.
The amine equivalent (g / mol) can be determined by titrating an ethanol solution of the block copolymer with hydrochloric acid having a known concentration.

These components (B) can 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 squeaky feeling of the hair during rinsing. Especially preferably, it is 0.03 to 2 mass%.
In addition, (B) component used by this invention can be manufactured by the method of Unexamined-Japanese-Patent No. 9-183854, for example.

  The cationic polymer of component (C) of the present invention is a water-soluble polymer having a molecular weight of 100,000 to 1,900,000 and a cationic charge density of 0.6 to 4 meq / g. In particular, the molecular weight is preferably 200,000 to 1,800,000, particularly preferably 300,000 to 1,700,000, and the cationic charge density is 0.6 to 3.8 meq / g from the viewpoint of slipping during foaming and smoothness during rinsing. In particular, it is preferably 0.7 to 3.5 meq / g. The charge density of the water-soluble cationized polymer can be measured, for example, by a colloid titration method using potassium polyvinyl sulfate as a titration solution.

  Specific examples of water-soluble cationic polymers include cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, diallyl quaternary ammonium salts / acrylamide copolymers, vinyl imidazolium trichloride / vinyl pyrrolidone copolymers, hydroxyethyl cellulose / Dimethyldiallylammonium chloride copolymer, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer, vinylpyrrolidone / methacrylamide Propyltrimethylammonium chloride copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / poly Tylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (Sandos Corp., Cartaletin), cation described in JP-A-53-139734, JP-A-60-36407 And a cationic polymer derivative, a cationized guar gum derivative, and a diallyl quaternary ammonium salt / acrylamide copolymer are particularly preferable.

  Further, for example, Marquat 550 (NALCO, copolymer of acrylamide and diallyldimethylammonium salt; CTFA name polyquaternium-7), rubiquat FC370 (BASF, 1-vinyl-2-pyrrolidone and 1-vinyl-3- Copolymer of methylimidazolium salt; CTFA name polyquaternium-16), Gafquat 755N (ISP, copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate; CTFA name polyquaternium-11), Ucare polymer JR and the same LR series (Amercol, a salt of a reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name polyquaternium-10), Poise C-60H, Poise C-80M, Poise C-150L Kao Corporation, salts of reaction product between trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name polyquaternium -10), Jaguar series (Rhodia, commercially available products may be used, such as guar hydroxypropyltrimonium chloride).

  Component (C) may be used alone or in combination of two or more thereof, and its content is 0.01 to 5% by mass in the cleaning composition of the present invention, but from the time of washing the hair to the time of rinsing. From the point of smoothness, 0.05-2 mass% is preferable, and 0.1-1 mass% is especially preferable.

  Component (D) of the present invention is a pearling agent containing at least one selected from 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 monobehenyl ester. Examples of the ethylene glycol dialkyl ester include ethylene glycol distearyl ester and ethylene glycol dibehenyl ester. 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. Two or more of these may be used in combination, and the content thereof is 0.1% in the aqueous hair cleanser of the present invention from the viewpoint of improving the stability of the cleanser and improving smoothness during foaming and rinsing. It is 10 mass%, Furthermore, 0.5-5 mass% is preferable, and 1-4 mass% is especially preferable.

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

Nonionic surfactants include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbite fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl. Phenyl ethers, polyoxyalkylene (hardened) castor oil, sucrose fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, fatty acid alkanolamides, alkyl glycosides, monoalkyl glyceryl ethers, monoalkenyl glyceryl And ethers. Among these, alkyl glycosides, polyoxyalkylene (C ₈ -C ₂₀ ) fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamides, monoalkyl glyceryl ethers, monoalkenyl Glyceryl ethers are preferred.
The fatty acid alkanolamides may be monoalkanolamides or dialkanolamides, and those having an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms are preferred. In particular, those having a hydroxyalkyl group having 2 to 3 carbon atoms are preferable, such as oleic acid diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide. Coconut oil fatty acid monoethanolamide, lauric acid isopropanolamide, lauric acid monoethanolamide, and the like.
The alkyl group or alkenyl group in the monoalkyl glyceryl ethers or monoalkenyl glyceryl ethers is preferably a linear or branched alkyl group having 4 to 10 carbon atoms, particularly 8 to 10 carbon atoms. Specifically, 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, n -A decyl group, an isodecyl group, etc. are mentioned, 2-ethylhexyl group and an isodecyl group are especially preferable.

  Examples of amphoteric surfactants include betaine surfactants. Of these, betaine surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, and alkylhydroxysulfobetaine are more preferred, and fatty acid amidopropyl betaine is particularly preferred. The fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and in particular, lauric acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine and the like. preferable.

  These nonionic or amphoteric surfactants can be used alone or in combination of two or more in the aqueous hair cleanser. However, when the aqueous hair cleanser of the present invention is in the form of an aqueous liquid cleanser. It is particularly preferable to use fatty acid amidopropyl betaine, fatty acid alkanolamide, or monoalkyl glyceryl ether together with component (A) because not only foaming power is improved, but also an appropriate liquid property is obtained.

  The content of the nonionic or amphoteric surfactant is preferably 0.1 to 15% by mass, more preferably 0.5 to 8% by mass, particularly 1 to 6% by mass in the hair cleansing agent of the present invention. It is preferable because a good foam increasing effect can be obtained.

  In the aqueous hair cleansing agent of the present invention, a silicone as represented by the general formula (7) can be blended for improving the finish after drying.

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 size of the dispersed silicone particles is preferably less than 100 μm, more preferably 50 μm or less, particularly 4 μm or less, and further preferably 2 μm or less. The average particle size is preferably 0.1 μm or more from the viewpoint of the feeling of use and the conditioning effect.

  As such silicone oil, for example, Toray Dow Corning Silicone Co., Ltd., which contains 60% by mass of dimethylpolysiloxane oil having an m of 300 to 6,500 in the formula (7) and has an average particle size of 0.8 μm, Use of “silicone CF2450” or “silicone CF2460” of Toray Dow Corning Silicone Co., which contains 50% by mass of dimethylpolysiloxane oil with m of 300-6,500 and an average particle size of 50 μm can do.

  Such a silicone oil is preferably contained in the aqueous hair cleansing agent of the present invention in an amount of 0.01 to 10% by mass from the viewpoints of foam feel at the time of shampooing, feel after drying and improvement of gloss. 0.05 to 6 mass%, particularly 0.3 to 3 mass%, particularly 0.5 to 2 mass% is preferable.

  In the aqueous hair cleansing agent of the present invention, a cationic surfactant and a modified silicone other than the component (B) can be further blended in order to improve the finish after drying.

As the cationic surfactant, for example, those shown in the following (i) to (vi) are preferably used.
(I) Alkyltrimethylammonium salt Examples include those represented by the following general formula.
R ¹¹ −N ⁺ (Me) ₃ X ⁻
[Wherein R ¹¹ 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) Alkoxytrimethylammonium salt Examples include those represented by the following general formula.
R ¹² —O—R ¹³ —N (Me) ₃ X ⁻
[Wherein R ¹² represents an alkyl group having 12 to 22 carbon atoms, R ¹³ represents an ethylene group or a propylene group, Me represents a methyl group, and X ⁻ is the same as described above. ]

(Iii) Dialkyldimethylammonium salt Examples include those represented by the following general formula.
R ¹⁴ ₂ −N ⁺ (Me) ₂ X ⁻
[Wherein, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, Me represents a methyl group, and X ⁻ is the same as above. ]

(Iv) Alkyldimethylamine and its salt Examples thereof include those represented by the following general formula.
R ¹⁵ -N (Me) ₂
[Wherein, R ¹⁵ represents an alkyl group having 12 to 22 carbon atoms, and Me represents a methyl group. ]

(V) Alkoxydimethylamine and salts thereof Examples thereof include those represented by the following general formula.
R ¹⁶ —O—R ¹⁷ —N (Me) ₂
[Wherein R ¹⁶ represents an alkyl group having 12 to 22 carbon atoms, R ¹⁷ represents an ethylene group or a propylene group, and Me represents a methyl group]

(vi) Alkylamidodimethylamine and salts thereof Examples thereof include those represented by the following general formula.
R ¹⁸ —C (═O) NH—R ¹⁹ —N (Me) ₂
[Wherein, R ¹⁸ represents an alkyl group having 11 to 21 carbon atoms, R ¹⁹ represents an ethylene group or a propylene group, and Me represents a methyl group. ]

Examples of cationic surfactants other than the above (i) to (vi) include ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium (alkanoylaminopropyl dimethylethylammonium ethyl sulfate, alkanoyl group derived from lanolin), ethyl sulfate lanolin fatty acid amino Ethyl triethyl ammonium, ethyl lanolin sulfate fatty acid aminopropyl triethyl ammonium, methyl sulfate lanolin fatty acid amino ethyl trimethyl ammonium, methyl sulfate lanolin fatty acid aminopropyl ethyl dimethyl ammonium, ethyl sulfate isoalkanoic acid (C ₁₄ -C ₂₀ ) aminopropyl ethyl dimethyl ammonium, ethyl sulfuric isoalkanes acid (C ₁₈ ~C ₂₂₎ aminopropyl dimethylammonium, aminopropyl ethylsulfate isostearate Dimethylammonium, ethyl sulfate, isononanoic acid aminopropyl ethyl dimethyl ammonium and alkyl trimethylammonium saccharin.

  Two or more kinds of cationic surfactants may be used in combination, and from the viewpoint of smoothness from the time of shampooing to the time of rinsing, the content is 0.01 to 10% by mass in the aqueous hair cleaning agent of the present invention. Further, 0.05 to 6% by mass, particularly 0.3 to 3% by mass, and particularly 0.5 to 2% by mass are preferable.

Examples of the modified silicones other than the component (B) include those shown below.
(A) Amino-modified silicone Various amino-modified silicones can be used, but in particular, in the third edition of the CTFA Dictionary (US, Cosmetic Ingredient Dictionary) under the name of Amodimethicone having an average molecular weight of about 3,000 to 100,000. Are preferred. Examples of commercially available products include SM 8704C (Toray Dow Corning Silicone), DC 929 (Dow Corning), KT 1989 (GE Toshiba Silicone), 8500 Conditioning Agent (Toray Dow Corning Silicone). It is done.

(B) Other silicones Other than the above, polyether modified silicone, methylphenyl polysiloxane, fatty acid modified silicone, alcohol modified silicone, alkoxy modified silicone, epoxy modified silicone, fluorine modified silicone, cyclic silicone, alkyl modified silicone, etc. It is done.

  These silicones may be used in combination of two or more, and from the point of smoothness from the time of shampooing to the time of rinsing, the content thereof is 0.01 to 10% by mass in the aqueous hair cleaning agent of the present invention. Further, 0.05 to 6% by mass, particularly 0.3 to 3% by mass, and particularly 0.5 to 2% by mass are preferable.

  Moreover, an oil agent can be contained as another conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin; glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; beeswax, whale wax, lanolin, carnauba wax, etc. Waxes; alcohols such as myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, glycerin, etc .; isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate , Esters such as propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate; Higher fatty acids such as acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; other isostearyl glyceryl ethers, polyoxypropylene butyl ethers, etc. It is done. Of these, higher alcohols are preferable, and myristyl alcohol, cetyl alcohol, and stearyl alcohol are particularly preferable. These oil agents can be used alone or in combination of two or more, and the content thereof is preferably 0.2 to 2% by mass, more preferably 0.3 to 1.8% by mass in the aqueous hair cleansing agent of the present invention. %, Particularly 0.5 to 1.5% by mass is preferred.

  The aqueous hair cleansing agent of the present invention may contain a viscosity modifier, and as the viscosity modifier, hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, isoprene glycol, ethanol, benzyl alcohol Benzyloxyethanol, phenoxyethanol, clay minerals, salts (sodium chloride, ammonium chloride, sodium citrate, etc.), among which benzyl alcohol, ethanol, polypropylene glycol, sodium chloride, sodium citrate are preferred. Two or more types of viscosity modifiers may be used in combination, and the amount used thereof is preferably 0.01 to 5% by mass in the aqueous hair cleansing agent of the present invention, from the viewpoint of the amount of foam and foam quality. 0.05-4 mass%, especially 0.1-3 mass% are preferable.

  In addition to the above-described components, the aqueous hair cleansing agent of the present invention can be appropriately blended with components used in ordinary hair cleansing agents depending on the purpose. Such components include, for example, anti-dandruff agents; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; moisturizers such as sorbitol and panthenol; colorants such as dyes and pigments; Products, proteins obtained from pearl shells or pearls or hydrolysates thereof, proteins obtained from silk or hydrolysates thereof, protein-containing extracts obtained from legume seeds, ginseng extract, rice germ extract , Hibamata extract, Aloe extract, Moon peach leaf extract, Chlorella extract, etc .; Pearling agent such as titanium oxide; Fragrance; Dye; Ultraviolet absorber; Antioxidant; Other encyclopedia of Ingredients and the like described in shampoos and ingredients (ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS)).

  The aqueous hair cleansing agent of the present invention preferably has a pH (diluted by 20 times by weight at 25 ° C.) of 2 to 6 when applied to hair from the viewpoint of improving the gloss and unity of the hair, The pH is preferably 3 to 5, particularly preferably 3.5 to 4.5. As the pH adjuster, it is preferable to use an organic acid, particularly α-hydroxy acid, and specifically, malic acid, citric acid, lactic acid, and glycolic acid are preferable. Two or more of these organic acids may be used in combination, and the amount used is 0.01 to 5 mass in the aqueous hair cleansing agent of the present invention in terms of foam quality and improvement in hair flexibility during hair washing. % Is preferable, further 0.1 to 3% by mass, particularly 0.3 to 2% by mass is preferable. Further, as other pH adjusting agents, bases such as sodium hydroxide, potassium hydroxide, 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 liquid form and gel form, but a liquid form using water and / or a lower alcohol, particularly water, as a solvent is preferable.

Evaluation Method (1) Speed of Foaming Using the apparatus shown in FIG. 1 (the apparatus disclosed in Japanese Patent Laid-Open No. 10-73584) and the following method, the amount of foaming is 1.5 mL of the evaluation sample and 0.3 mL of model sebum. Was measured, and the time until the amount of foam reached 25 mL was evaluated.
In the apparatus shown in FIG. 1 and FIG. 2, a hair 1 in which 30 g of 90 mm hair was implanted in a disk 11 having a diameter of about 160 mm was used. The container 10 has a cylindrical shape having a diameter of 160 mm and a height of 220 mm, and the lid 20 includes three columnar projections having a diameter of 15 mm and a height of 12 mm as the first projection 21. As the projection 22, a projection having 9 projections 10 mm long, 2 mm wide and 12 mm high was used. Moreover, the rotation speed of the container 10 by the motor was set to 70 rotations per minute.
In the foaming evaluation method using this apparatus, first, wet the hair with 30 g of water, add model sebum, apply the evaluation sample, then slide the hair 1 and the protrusions 21 and 22; Bubbles were collected in the meter 50. In this case, the amount of collected bubbles was recorded every 50 seconds immediately after the start of sliding. The evaluation criteria are as follows.
<Evaluation criteria>
◎: Less than 100 seconds ○: More than 100 and less than 200 seconds △: More than 200 and less than 300 seconds ×: More than 300 seconds

(2) Slip feeling when rinsing After rinsing a human hair bundle of 25 cm in length, 5.5 cm in width and 10 g in weight with warm water of 40 ° C, excess water is removed and 0.5 g of hair washing agent is added. Used and whipped for about 30 seconds. After that, the hair feeling with bubbles was rinsed with 40 ° C. hot water at a flow rate of 2 L / min, and the slip feeling was sensory evaluated. The evaluation was performed by five people, and the total value of the evaluation was shown. The evaluation criteria are as follows.
4: Slip well 3: Slightly slide 2: Not slippery 1: Not slippery

(3) Glossiness after drying The hair bundle treated in the same manner as the slip evaluation was rinsed with running water (2 L / min) at 40 ° C., and then the moisture was sufficiently wiped off with a towel and dried naturally. After drying, the gloss and unity were evaluated visually. The evaluation was performed by five people, and the total value of the evaluation was shown.
4: Good 3: Slightly good 2: Not very good 1: Not good

(4) Stability The hair washing agent was filled in 100 ml in a 110 ml standard bottle and evaluated after being stored at 50 ° C. for 1 month.
○: No change due to storage Δ: Slight change due to storage (within tolerance)
×: Apparently changed by storage (outside tolerance)

Examples 1-6 and Comparative Examples 1-4
Hair cleaning agents shown in Table 1 were prepared and evaluated by the above evaluation methods. The pH is a value at 25 ° C. diluted 20 times by weight with water.

* 1 Lauryl ether (1) ammonium sulfate; ethylene oxide weight average addition mole number 1
* 2 Block copolymer of amino-modified organopolysiloxane and polyoxyalkylene chain; “Silicone SS-3588”, Toray Dow Corning Silicone (kinematic viscosity 65,000 mm ² / s, amine equivalent 1250 g / mol)
* 3 Amino-modified silicone; "Silicone KT1989", GE Toshiba Silicone Corp. * 4 Cationized hydroxyethyl cellulose; "Poise M-80", Kao Corporation, molecular weight 800,000, cationic charge density 1.0 meq / g
* 5 Diallyldimethylammonium chloride / acrylamide copolymer; “Mercoat 550”, NALCO, molecular weight of 1.5 million, cationic charge density of 3.1 meq / g, polymer effective content of 8.5%
* 6 Cationized hydroxyethyl cellulose; “Kachinal HC-200”, Toho Chemical Industry Co., Ltd., molecular weight 2 million, cation charge density 0.8 meq / g
* 7 Dimethyldiallylammonium chloride copolymer; “Mercoat 100”, NALCO), molecular weight 50,000, cationic charge density 6.2 meq / g, polymer effective content 40.0%
* 8 Dimethicone 1; viscosity 10,000 cs / 10 cs = 95/5 mixture, average particle size 0.5 μm
* 9 Dimethicone 2: Silicone CF2460, Toray Dow Corning Silicone, average particle size 50 μm

Example 7 Conditioning Shampoo (mass%)
Lauryl ether (1) Ammonium sulfate 12.0
(Ethylene oxide average addition mole number 1)
Amino-modified polysiloxane-polyoxyalkylene copolymer (SS-3587, Toray Dow Corning Silicone) 0.1
Cationized human hydroxyethyl cellulose (Polymer JR-400, Amerchol)
0.3
Cationized guar gum (Jaguar C-13S, Rhodia) 0.3
Dimethyldiallylammonium / acrylamido copolymer (Marcote 550, NALCO) 1.2
Ethylene glycol distearyl ester 2.0
2-Ethylhexyl glyceryl ether 0.5
Laurylamidopropylbetaine 1.0
Myristyl alcohol 0.3
Cetyl alcohol 0.3
Cocoyl monoethanolamide 0.8
Polyoxyethylene (16) lauryl ether 0.7
Methyl polysiloxane emulsion 1.0
(Silicone viscosity 10,000cs, particle size 0.2-0.8μm)
Amino-modified silicone (8500 Conditioning Agent, Toray Dow Corning Silicone) 0.3
Polypropylene glycol (Mw = 400) 0.5
Benzyl alcohol 0.3
Ethanol 3.0
Panthenol 0.05
Silk extract 0.05
Sodium chloride 1.0
Perfume Appropriate amount Malic acid 0.5
Lactic acid pH 3.9 Amount of ion-exchanged water Balance

Example 8 Conditioning Shampoo (mass%)
Lauryl ether (2) Sodium sulfate 13.0
(Ethylene oxide average addition mole number 2)
Amino-modified polysiloxane-polyoxyalkylene copolymer (FZ-3789, Toray Dow Corning Silicone) 0.8
Cationized hydroxyethyl cellulose (Poise C-80M, Kao) 0.5
Sialyl quaternary ammonium salt / acrylamid copolymer (Mercoat 550, NALCO)
2.5
Ethylene glycol distearyl ester 3.0
Isodecyl glyceryl ether 0.7
Laurylamidopropylbetaine 2.0
Cocoyl monoethanolamide 0.5
Myristyl alcohol 1.5
Polyoxyethylene (16) lauryl ether 1.0
Amino-modified silicone (SM 8704C, Toray Dow Corning Silicone)
1.2
Highly polymerized methylpolysiloxane emulsion 1.0
(Silicone CF2450, particle size 0.2-0.8μm, Toray Dow Corning Silicone)
Benzyl alcohol 1.0
Polypropylene glycol (Mw = 400) 0.2
Sodium chloride 1.0
Hydrolyzed conchiolin solution (dry matter 3% by mass) 0.05
Panax ginseng extract (dry matter 3% by weight) 0.05
Soybean extract (0.4% by weight of dry matter) 0.05
Eucalyptus extract (dry matter 0.2% by mass) 0.05
Rice germ oil 0.05
Glycolic acid 1.0
Perfume Appropriate amount Sodium hydroxide Amount of pH 3.9 Deionized water Balance

Example 9 Conditioning Shampoo (mass%)
Lauryl ether (1) Sodium sulfate 16.0
(Ethylene oxide average addition mole number 1)
Amino-modified polysiloxane-polyoxyalkylene copolymer 1.0
(Silicone SS-3588, Toray Dow Corning Silicone)
Cationized human hydroxyethyl cellulose (Polymer JR-30M, Amerchol)) 0.5
Ethylene glycol distearyl ether 3.0
Isodecyl glyceryl ether 0.3
Cocoyl monoethanolamide 0.5
Stearyl alcohol 1.0
Glycerin 1.0
Highly polymerized methylpolysiloxane emulsion 0.5
(Silicone CF2460, particle size 20-80μm, Toray Dow Corning Silicone)
Sodium chloride 0.2
Benzyloxyethanol 0.5
Malic acid 0.7
Perfume Appropriate amount of lactic acid 0.1
Amount of citric acid to reach pH 5.5 Ion exchange water Balance

Example 10 Conditioning Shampoo (mass%)
Lauryl ether (2.5) sodium sulfate 15.0
(Ethylene oxide average addition mole number 2.5)
Amino-modified polysiloxane-polyoxyalkylene copolymer 0.4
(Silicone SS-3588, Toray Dow Corning Silicone)
Cationized guar gum (Jaguar C-14S, Rhodia) 0.5
Ethylene glycol distearyl ester 2.0
Laurylamidopropylbetaine 3.0
Cocoyl monoethanolamide 0.8
Polyoxyethylene (16) lauryl ether 2.0
Stearoxypropyldimethylamine malate 0.5
Methyl polysiloxane emulsion 1.0
(Silicone viscosity 5,000cs, particle size 0.2-0.8μm)
Polypropylene glycol (Mw = 400) 0.5
Sodium chloride 1.0
Malic acid 0.8
Citric acid 0.75
Sodium hydroxide Amount to be pH 3.5 Ion-exchanged water Balance

Example 11 Conditioning Shampoo (mass%)
Lauryl ether (1) ammonium sulfate 14.0
(Ethylene oxide average addition mole number 1)
Amino-modified polysiloxane-polyoxyalkylene copolymer 0.5
(Silicone SS-3588, Toray Dow Corning Silicone)
Cationized human hydroxyethyl cellulose (Polymer JR-400, Amerchol)
0.4
Ethylene glycol distearyl ester 2.0
Isodecyl glyceryl ether 1.5
Cocoylamidopropylbetaine 1.0
Lauryl hydroxysulfobetaine 1.0
Lauric acid 0.5
Oleic acid 0.7
Cocoyl benzalkonium chloride 0.5
Ethanol 0.5
Hibamata extract 0.05
Malic acid 0.7
Perfume Appropriate amount Sodium hydroxide Amount to reach pH 5.5 Ion-exchanged water Balance

  The hair cleansing agents of Examples 7 to 11 had fast foaming and good slipping at the time of foaming and rinsing, had good gloss and cohesiveness of the finished hair, and were excellent in stability.

  The aqueous hair cleansing agent of the present invention has good foaming and slippery foam quality at the time of shampooing, has a smooth feel at the time of rinsing, and gives gloss to the finished hair.

It is a figure which shows a cleaning agent evaluation apparatus. It is a top view (a figure) of the disc which implants hair, and sectional drawing (b figure) of the disc which implanted hair.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hair 10 Container 20 Lid 21 1st protrusion 22 2nd protrusion 23 Foam guide wall 24 Hair entrapment prevention pin 25 Injection hole 30 Motor 50 Metering device 51 Water injection hole 60 Torque detector

Claims (3)

Next component (A), (B), (C), (D)
(A) 1-30% by mass of an anionic surfactant,
(B) a copolymer having a block chain of an amino-modified organopolysiloxane chain and a polyoxyalkylene chain, 0.01 to 0.3 % by mass,
(C) a water-soluble cationic polymer having a molecular weight of 100,000 to 1,900,000 and a cationic charge density of 0.6 to 4 meq / g, 0.01 to 5% by mass,
(D) 0.1 to 10% by mass of a pearlizing agent containing at least one selected from ethylene glycol monoalkyl ester, ethylene glycol dialkyl ester, ethylene glycol monoalkyl ether, and ethylene glycol dialkyl ether,
And at least one selected from the group consisting of fatty acid amide propyl betaine, fatty acid alkanolamide and monoalkyl glyceryl ether as a nonionic surfactant or amphoteric surfactant, 0.1 to 15% by mass,
A water-based hair cleansing agent comprising: a component (B) which is a copolymer represented by the following general formula (6).

[Wherein, a is a number of 2 to 1000, b is a number of 1 to 50, d is a number of 2 to 100, g is a number of 4 to 200, and h is a number of 0 to 30. _{Further, -O (C 2 H 4 O} ) g (C 3 H 6 O) h - is a block copolymer or random copolymer. ] Furthermore, the aqueous hair cleansing agent of Claim 1 containing 0.01-10 mass% of silicone shown by following General formula (7).
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. ] (A) The aqueous hair cleansing agent according to claim 1 or 2, wherein the anionic surfactant is a polyoxyalkylene alkyl ether sulfate or an alkyl sulfate represented by the general formula (2) or (3).
_{R'O (CH 2 CH 2 O)} n SO 3 M (2)
R'OSO ₃ M (3)
[Wherein, R ′ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, M represents an alkali metal, an alkaline earth metal, or ammonium, and n represents a number of 1 to 5 on a weight average basis. ]

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