JP4728282B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention relates to an aqueous hair cleansing agent.

  For hair cleaning agents, water-soluble cationized polymers such as cationized cellulose and cationized guar gum are widely used for the purpose of imparting a conditioning effect to the hair. It is believed that the cationized polymer in the hair cleaning agent forms a water-insoluble complex with an anionic surfactant when diluted with water, and thus tends to remain on the hair surface and imparts a conditioning effect. However, the effect on hair damaged by chemical treatments such as hair coloring agents and permanent agents is not sufficient, and the phenomenon of entanglement and squeaking remains when rinsing the hair cleaning agent. . Therefore, as a means for enhancing the conditioning effect, cationized tara gum obtained by cationizing a polysaccharide obtained from the endosperm of a seed of a legume plant (Caesal pinia Spinosa) is applied to a hair cleanser (Patent Document 1). In addition, it has been proposed to use cationized tara gum and cationized guar gum in a hair cleansing agent (Patent Document 2). However, the conditioning effect on damaged hair is still not sufficient.

  In addition, amino-modified silicone may be used for the hair cleaning agent for the purpose of enhancing the conditioning effect. Patent Document 3 describes a hair cleanser containing a high molecular weight amino-modified silicone and an ammonium-modified silicone. However, the amino-modified silicone described in Patent Document 3 has a structure having a simple alkyleneamine or alkyleneammonium salt in the side chain of the polysiloxane skeleton, and thus has a high hydrophobicity, resulting in solubility in a hair cleanser. However, the dispersibility is poor and there are problems in stability, and there is a problem that the foaming of the hair cleaning agent is lowered, and it becomes sticky and sticky at the time of rinsing.

JP 2004-203801 A JP 2005-272658 A Japanese Patent Laid-Open No. 5-85918

  Even when used on hair damaged by chemical treatment, the present invention has quick foaming and slippery foam quality when shampooed, has a smooth feel when rinsed, and is glossy on the finished hair. An object of the present invention is to provide an aqueous hair cleanser with excellent storage stability.

  The present inventor uses an anionic surfactant, cationized tara gum, and an amino-modified silicone having a specific structure, so that it has excellent foam performance, feel and finish even on damaged hair, and is stable in storage. It has been found that an aqueous hair cleanser having excellent properties can be obtained.

That is, the present invention provides an aqueous hair cleanser containing the following components (A), (B) and (C).
(A) Anionic surfactant
(B) Cationized tara gum
(C) Amino-modified silicone represented by general formula (1) or (4)

[In the formula, each R ¹ independently represents a monovalent hydrocarbon group, a hydroxy group or an alkoxy group,
Each R ² independently represents a monovalent hydrocarbon group;
R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ represents the formula (2) or (3)

(Y represents a hydrogen atom or a group —CH ₂ —CH (OH) —R ³ —OH (R ³ is the same as above), R ⁵ represents a hydrogen atom or a group —R ³ NY ₂ (Y and R ³ are However, not all Y are hydrogen atoms.), A represents a number from 25 to 1000, and b represents a number from 1 to 200. ]

[Wherein, R ⁶ independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁷ represents either R ⁶ or E, and E represents —R ⁸ —Z. (Wherein R ⁸ 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). X is a divalent group, c is a number of 2 or more, d is a number of 1 or more, n is a number of 2 to 10, e is a number of 4 or more, and f is a number of 2 or more. ]

  Even when used on hair damaged by chemical treatment, the aqueous hair cleanser of the present invention has quick foaming and slippery foam quality when shampooed, has a smooth feel when rinsed, and has a smooth feel. Give gloss and unity. The aqueous hair cleanser of the present invention is excellent in storage stability.

  As the component (A) anionic surfactant, sulfuric acid type, sulfonic acid type and carboxylic acid type can be used. For example, alkyl sulfate, alkenyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl ester salt, alkane sulfonate, higher fatty acid salt, alkyl Ether carboxylates, and the like. Among them, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, alkyl sulfates, and alkenyl sulfates are preferable, and the following general formula (5) or (6) The thing represented by these is preferable.

R ⁹ O (CH ₂ CH ₂ O) _m SO ₃ M (5)
R ⁹ OSO ₃ M (6)

[In the formula, R ⁹ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, M represents a cation derived from an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid, and m represents a mass average. The number of 1-5 is shown. ]

Among these, R ⁹ in the general formula (5) is an alkyl group having 12 to 14 carbon atoms, m is a number of 1 on a mass average, and M is a number from the viewpoint of achieving both quick foaming and good foam feel. Polyoxyethylene alkyl ether sulfates in which is ammonium or sodium are preferred.

  Component (A) can be used alone or in combination of two or more thereof, and its content is in the aqueous hair cleansing agent of the present invention in terms of foaming, liquid properties during use, and cleanability. 1-30 mass% is preferable, Furthermore, 5-25 mass%, Furthermore, 8-20 mass% is preferable.

  Component (B) of the present invention is a cationized tara gum. Tara gum, which is derived from cationized tara gum, is a mannose in which galactose is bound as a side chain to the main chain of mannose, which is obtained from the endosperm of seeds of the cod legume (Caesal pinia Spinosa). Is a galactomannan polysaccharide with a composition ratio of 3 to 1 of galactose.

  The cationized tara gum used in the present invention has a structure in which a part of the hydroxyl group contained in the galactomannan in the tara gum is substituted with a quaternary nitrogen-containing group. Specifically, it can be produced by reacting tara gum with a compound having a quaternary nitrogen-containing group such as glycidyltrialkylammonium salt or 3-halogeno-2-hydroxypropyltrialkylammonium salt. In this case, the reaction is carried out in the presence of an alkali in a suitable solvent, preferably a hydrous alcohol. Such a quaternary nitrogen-containing group can be introduced according to a conventionally known method.

  The degree of cationization of the cationized tara gum, that is, the average number of moles of quaternary nitrogen-containing groups added per monosaccharide is not particularly limited, but is preferably 0.1 to 0.5. If it is less than 0.1, the amount of hair adsorbed becomes insufficient, and a sufficient conditioning effect is not recognized. On the other hand, if it exceeds 0.5, a sticky feeling is produced at the time of use, and the foamability is deteriorated.

  Examples of commercially available products include “Catinal CTR-100” and “Catinal CTR-200” (toho chemical industry).

  These components (B) can be used alone or in combination of two or more. The content of the component (B) in the aqueous hair cleansing agent of the present invention is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and further 0.03 to 0% from the viewpoint of reducing the squeaky feeling of the hair during rinsing. 2% by mass is preferred.

  Component (C) is an amino-modified silicone represented by the general formula (1) or (4).

[In the formula, each R ¹ independently represents a monovalent hydrocarbon group, a hydroxy group or an alkoxy group,
Each R ² independently represents a monovalent hydrocarbon group;
R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ represents the formula (2) or (3)

(Y represents a hydrogen atom or a group —CH ₂ —CH (OH) —R ³ —OH (R ³ is the same as above), R ⁵ represents a hydrogen atom or a group —R ³ NY ₂ (Y and R ³ are However, not all Y are hydrogen atoms.), A represents a number from 25 to 1000, and b represents a number from 1 to 200. ]

[Wherein R ⁶ independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁷ represents either R ⁶ or E, and E represents —R ⁸ —Z. (Wherein R ⁸ 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). X is a divalent group, c is a number of 2 or more, d is a number of 1 or more, n is a number of 2 to 10, e is a number of 4 or more, and f is a number of 2 or more. ]

  The amino-modified silicone represented by the general formula (1) is an amino-modified silicone having a specific amino functional group in the side chain.

In the general formula (1), examples of the monovalent hydrocarbon group in R ¹ include an alkyl group and an aryl group. R ¹ is preferably an alkyl group having 1 to 3 carbon atoms (particularly a methyl group) and an alkoxy group having 1 to 15 carbon atoms, more preferably 10 to 15 carbon atoms.

Examples of the monovalent hydrocarbon group represented by R ² include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, and a xylyl group. An aryl group having 6 to 10 carbon atoms; an aralkyl group having 6 to 10 carbon atoms such as a benzyl group and a phenethyl group. Of these, an alkyl group and further a methyl group are preferable.

The divalent hydrocarbon group having 1 to 10 carbon atoms as R ³ is methylene group; alkylene such as ethylene group, trimethylene group, propylene group, tetramethylene group, methyltrimethylene group, ethylethylene group, dimethylethylene group, etc. Group: an alkylene-arylene group represented by the formula — (CH ₂ ) ₂ —C ₆ H ₄ —. Of these, an alkylene group having 2 to 4 carbon atoms is preferable.

Of Y, the group —CH ₂ —CH (OH) —R ³ —OH is preferably a 2,3-dihydroxypropyl group.

R ⁴ is preferably a group represented by the formula (3), and R ^{5 in} the formula (3) is a 2-N- (2,3-dihydroxypropyl) aminoethyl group or 2-N, N-bis. A (2,3-dihydroxypropyl) aminoethyl group is preferred.

  In formula (1), a is preferably a number from 50 to 400, and b is preferably a number from 1 to 20.

  The amino-modified silicone represented by the general formula (1) can be synthesized, for example, by reacting an amino-modified silicone with an epoxy functional compound such as glycidol as described in EP0399706A2. Examples of the amino-modified silicone represented by the general formula (1) include compounds represented by the following formula. Moreover, as a commercial item, "8500 Conditioning Agent" (CAS No.237753-63-8) of Dow Corning is mentioned.

[In the formula, R ¹⁰ represents an alkyl group having 13 to 15 carbon atoms, 70 to 80% of Y ′ is a group —CH ₂ CH (OH) CH ₂ OH, and the remaining 30 to 20% is a hydrogen atom. Indicates. ]

  The amino-modified silicone represented by the general formula (4) is a block copolymer composed of an amino-modified polysiloxane block having an amino functional group in the side chain and a polyoxyalkylene block.

In the general formula (4), as R ⁶ , independently of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in R ⁸ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a decylene group, and an octadecylene group. More preferred are a methylene group, an ethylene group, and a propylene group.

  Z is preferably an amino group-containing group or an ammonium group-containing group represented by the general formula (7) or (8).

[Wherein R ¹¹ is

R ¹² represents a hydrogen atom or a monovalent hydrocarbon group, and each R ¹² may be the same or different. g and h each represent an integer of 0-6. T ⁻ represents a halide ion or an organic anion. ]

Examples of the monovalent hydrocarbon group represented by R ¹² in the general formulas (7) and (8) include a methyl group, an ethyl group, and a propyl group. T ^- Specific examples of the chloride ion, iodide ion, halide ions such as bromide ion, methosulfate, ethosulfate, methemoglobin phosphate, and organic anions such as ethoxy phosphate.

Preferred E groups in the general formula (4) 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 - and is, more preferably, - (CH ₂₎ a _{3 -NH- (CH 2) 2 -NH} 2.

  In the general formula (4), a preferable example of the divalent group represented by X is an alkylene group or an arylene group, specifically, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, or an isobutylene group. And a tetramethylene group and an isobutylene group are more preferable.

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

  In the block copolymer represented by the general formula (4), the proportion of the siloxane block is preferably 25 to 97% by mass, more preferably 35 to 90% by mass, and still more 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 ⁶ groups represented by — [Si (R ⁶ ) ₂ —O] —, and the ratio of the siloxane block refers to the molecular weight of the siloxane block. The ratio with respect to the molecular weight of a block copolymer (4) is represented with the mass%. If it is in the said range, the solubility or dispersibility of the block copolymer (4) in the aqueous hair cleansing agent will be good, and the residual property to hair is also high and preferable.

  Of the amino-modified silicones represented by the general formula (4), a more preferred example is an amino-modified polysiloxane-polyoxyalkylene block copolymer having a polymer unit represented by the general formula (9).

[Wherein, c, d and f have the same meaning as described above, i represents a number of 4 or more, and j represents a number of 0 to 30. ]

In the general formula (9), preferably, c is a number from 2 to 1000, d is a number from 1 to 50, i is a number from 4 to 200, and f is a number from 2 to 100. The unit of —O (C ₂ H ₄ O) _i (C ₃ H ₆ O) _j — may be either block or random in polyoxyethylene and polyoxypropylene.

  Examples thereof include Toray Dow Corning FZ-3789, DOW CORNING TORAY SS-3588, and DOW CORNING TORAY SILSTYLE104.

  These components (C) can be used alone or in combination of two or more. The content of the component (C) in the aqueous hair cleansing agent of the present invention is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and further 0.03 to 0% from the viewpoint of reducing the squeaky feeling of the hair during rinsing. It is preferable that it is 2 mass%.

  Furthermore, the mass ratio of the component (B) / (C) is preferably in the range of 1/10 to 10/1, more preferably 1/5 to 5 / from the viewpoint of smoothness during foaming and rinsing. 1 is preferred.

  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 oils, sucrose fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, fatty acid alkanolamides, alkyl glycosides, monoalkyl glyceryl ethers, monoalkenyl glyceryl ethers And the like.

Among these, polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan fatty acid ester, polyoxyalkylene fatty acid esters such as polyoxyalkylene (C ₈ -C ₂₀ ) fatty acid ester, polyoxyethylene hydrogenated castor oil and other poly Oxyalkylene (hardened) castor oils and alkyl glycosides are preferred.

  Fatty acid alkanolamides are also suitable, and may be either monoalkanolamides or dialkanolamides, and those having an acyl group having 8 to 18 carbon atoms and more preferably 10 to 16 carbon atoms are preferred. Further, those having a hydroxyalkyl group having 2 to 3 carbon atoms are preferred, for example, 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.

  Furthermore, the component (D) monoalkyl glyceryl ether and monoalkenyl glyceryl ether are also suitable, and the alkyl group or alkenyl group is a linear or branched alkyl having 4 to 10 carbon atoms, and further having 8 to 10 carbon atoms. A group or an alkenyl group is preferred. 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 -Decyl group, isodecyl group and the like can be mentioned, and 2-ethylhexyl group and isodecyl group are more preferable.

  Examples of amphoteric surfactants include betaine surfactants. Of these, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, alkylhydroxysulfobetaine and the like are more preferred, and fatty acid amidopropyl betaine is more preferred. The fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and more preferably amidopropyl betaine laurate, palm kernel fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine. Etc. are preferred.

  These nonionic surfactants or amphoteric surfactants can be used alone or in combination of two or more in the aqueous hair cleanser, but the aqueous hair cleanser of the present invention is in the form of an aqueous liquid cleanser. In the case of using the fatty acid amide propyl betaine, fatty acid alkanolamide or monoalkyl glyceryl ether together with the component (A), not only the foaming power becomes better, but also an appropriate liquid property can be obtained. Is preferable.

  The content of the nonionic surfactant or amphoteric surfactant is preferably 0.1 to 15% by mass in the aqueous hair cleansing agent of the present invention, and a good foam increasing effect is obtained. From the above points, 0.5 to 8% by mass, further 1 to 6% by mass is more preferable.

  In order to improve the finish after drying, the aqueous hair cleansing agent of the present invention may further contain a cationic surfactant, a cationic polymer other than component (B), and silicones other than component (C). it can.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, alkoxytrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylamines and salts thereof, alkoxydimethylamines and salts thereof, alkylamidodimethylamines and salts thereof, and the like.

(i) Examples of the alkyltrimethylammonium salt include those represented by the following general formula.
R ¹³ −N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein, R ¹³ represents an alkyl group having 12 to 22 carbon atoms, and X ⁻ represents a halide ion such as a chloride ion or a bromide ion. ]
Specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride.

(ii) Examples of the alkoxytrimethylammonium salt include those represented by the following general formula.
R ¹⁴ —O—R ¹⁵ —N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms, R ¹⁵ represents an ethylene group or a propylene group optionally substituted by a hydroxy group, and X ⁻ is the same as above. ]
Specific examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride, and the like.

(iii) Examples of the dialkyldimethylammonium salt include those represented by the following general formula.
(R ¹⁶ ) ₂ N ⁺ (CH ₃ ) ₂ X ⁻
[Wherein, R ¹⁶ independently represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and X ⁻ is the same as described above. ]
Specifically, distearyl dimethyl ammonium chloride etc. are mentioned.

(iv) Examples of alkyldimethylamine and salts thereof include those represented by the following general formula and salts thereof.
R ¹⁷ —N (CH ₃ ) ₂
[Wherein, R ¹⁷ represents an alkyl group having 12 to 22 carbon atoms. ]
Specific examples include behenyl dimethylamine, stearyl dimethylamine and organic acid salts thereof.

(v) Examples of alkoxydimethylamine and salts thereof include those represented by the following general formula and salts thereof.
R ¹⁸ —O—R ¹⁹ —N (CH ₃ ) ₂
[Wherein, R ¹⁸ represents an alkyl group having 12 to 22 carbon atoms, and R ¹⁹ represents an ethylene group or a propylene group. ]

(vi) Examples of the alkylamidodimethylamine and salts thereof include those represented by the following general formula and salts thereof.
R ²⁰ —C (═O) NH—R ²¹ —N (CH ₃ ) ₂
[Wherein, R ²⁰ represents an alkyl group having 11 to 21 carbon atoms, and R ²¹ represents an ethylene group or a propylene group. ]

Examples of cationic surfactants other than the above (i) to (vi) include ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, ethyl sulfate lanolin fatty acid aminoethyltriethylammonium, ethyl sulfate lanolin fatty acid aminopropyltriethylammonium, methyl sulfate lanolin fatty acid amino. trimethyl ammonium, methyl sulfate lanolin fatty acid aminopropyl ethyl dimethyl ammonium ethyl sulfate isoalkanes acid (C ₁₄ ~C ₂₀₎ aminopropyl dimethylammonium ethyl sulfate isoalkanes acid (C ₁₈ ~C ₂₂₎ aminopropyl dimethylammonium ethyl sulfate Aminopropylethyldimethylammonium isostearate, aminopropylethyldimethylammonium ethylsulfate isononanoate and alkyl Examples include limethylammonium saccharin.

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

  Next, as the cationized polymer other than the component (B), cationized cellulose, cationized starch, cationized guar gum, cationized locust bean gum, diallyldialkylammonium salt / acrylamide copolymer, vinyl imidazolium chloride / vinyl pyrrolidone Copolymer, hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, vinylpyrrolidone / alkylaminoacrylate copolymer, vinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer Polymer, vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer, alkylacrylamide / alkyl acrylate / alkylamino It is described in alkyl acrylamide / polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (US Sands Co., Cartaletin), JP-A-53-139734, JP-A-60-36407. And cationic polymers such as cationized cellulose, cationized guar gum, and diallyldialkylammonium salt / acrylamide copolymer are preferred.

  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 LR series (Amercor, salt of reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name Polyquaternium-10), Poise C-60H, Poise C-80M, Poise C-150L (above , Kao Corporation, salt of reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name polyquaternium-10 Jaguar series (Rhodia, guar hydroxypropyl trimethyl ammonium chloride), Catinal CLB-100 (Toho Chemical Industry Co., locust bean hydroxypropyltrimonium chloride) can be used commercially available products.

  Two or more cationized polymers other than these components (B) may be used in combination, and from the viewpoint of smoothness from the time of shampooing to the time of rinsing, the content thereof is 0.01% in the aqueous hair cleansing agent of the present invention. -3 mass% is preferable, 0.05-2 mass% is further preferable, and 0.1-0.5 mass% is further preferable.

The aqueous hair cleansing agent of the present invention preferably contains, as component (E), dimethylpolysiloxane represented by the following formula as dispersed oil droplets.
R ²³ (CH ₃ ) ₂ SiO — [(CH ₃ ) ₂ SiO] _k —Si (CH ₃ ) ₂ R ²³
[Wherein, R ²³ represents a methyl group or a hydroxy group, and k represents a number of 1 to 20,000. ]

  Dimethylpolysiloxane is dispersed in the aqueous hair cleansing agent of the present invention, and the average particle size of the dispersed particles is preferably less than 100 μm, more preferably 50 μm or less, further 4 μm or less, and further preferably 2 μm or less. In addition, 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 dimethylpolysiloxane, for example, “Silicone CF2450” manufactured by Toray Dow Corning Co., which contains 60% by mass of dimethylpolysiloxane oil having a k of 300 to 6,500 in the formula and has an average particle diameter of 0.8 μm, or Commercially available “Silicone CF2460” manufactured by Toray Dow Corning Co., which contains 50% by mass of dimethylpolysiloxane oil having a k of 300 to 6,500 and an average particle size of 20 μm can be used.

  Furthermore, silicones other than components (C) and (E) may be contained. Examples of such silicones include amino-modified silicones other than component (C), polyether-modified silicones, methylphenylpolysiloxanes, fatty acid-modified silicones, alcohol-modified silicones, alkoxy-modified silicones, epoxy-modified silicones, fluorine-modified silicones, and cyclic silicones. And alkyl-modified silicone.

  Silicones other than these components (C) and (E) may be used in combination of two or more, and from the viewpoint of smoothness from the time of shampooing to the time of rinsing, the content thereof is the aqueous hair cleansing agent of the present invention The content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and further preferably 0.1 to 2% by mass.

  The aqueous hair cleansing agent of the present invention may further contain a pearling agent such as ethylene glycol monofatty acid ester, ethylene glycol difatty acid ester, ethylene glycol monoalkyl ether or ethylene glycol dialkyl ether.

  Examples of the ethylene glycol monofatty acid ester include ethylene glycol monostearate and ethylene glycol monobehenate, and examples of the ethylene glycol difatty acid ester include ethylene glycol distearate and ethylene glycol dibehenate. 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 in the aqueous hair cleansing agent of the present invention from the viewpoint of improving the storage stability of the aqueous hair cleansing agent and improving smoothness during foaming and rinsing. 0.1 to 10% by mass, preferably 0.5 to 5% by mass, and more preferably 1 to 4% by mass.

  In addition, the aqueous hair cleansing agent of the present invention can contain an oil as another conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin; oils and fats such as castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, coconut oil; beeswax, whale wax, Waxes such as lanolin and carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, myristyl alcohol, behenyl alcohol, cetostearyl alcohol; isopropyl palmitate, isopropyl myristate, myristine Octyldodecyl acid, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, Esters such as tridecyl isononanoate; higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearic acid, isopalmitic acid; other isostearyl glyceryl ethers And polyoxypropylene butyl ether. Among these, higher alcohols or fats and oils are preferable, and myristyl alcohol, cetyl alcohol, stearyl alcohol, sunflower oil, and coconut oil are more preferable. These oil agents can be used alone or in combination of two or more thereof, and the content thereof is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass in the aqueous hair cleansing agent of the present invention. Furthermore, 0.3-1 mass% is preferable.

  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, and 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, and more preferably 0.05 to 4 mass%, Furthermore, 0.1-3 mass% is preferable.

  In addition to the above-mentioned components, the components used in ordinary aqueous hair cleansing agents can be appropriately blended in the aqueous hair cleansing agent of the present invention depending on the purpose. Such components include, for example, anti-dandruff agents; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; humectants such as glycerin, sorbitol, and panthenol; colorants such as dyes and pigments; Solvent extract, protein obtained from shell or pearl with pearl layer or hydrolyzate thereof, honey, royal jelly, protein obtained from silk or hydrolyzate thereof, protein-containing extract obtained from legume seed, ginseng Extracts, rice germ extract, hibermata extract, aloe extract, moon peach leaf extract, chlorella extract and other extracts; pearling agents such as titanium oxide; fragrances; UV absorbers; antioxidants; Ingredients listed in pediatric shampoo INGREDIENTS (MICELLE PRESS)

  The aqueous hair cleansing agent of the present invention preferably has a pH (diluted 20 mass times with water, 25 ° C.) of 2 to 6 when applied to hair from the viewpoint of improving the gloss and unity of the hair, It is preferably 3 to 5, more preferably 3.5 to 4.5. As the pH adjuster, it is preferable to use an organic acid, and further 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% by mass in the aqueous hair cleansing agent of the present invention in terms of foam quality and improvement in hair flexibility during hair washing. More preferably, it is 0.1 to 3% by mass, and further preferably 0.3 to 2% by mass. Moreover, you may use bases, such as sodium hydroxide, potassium hydroxide, ammonium chloride, together with these organic acids as another pH adjuster.

  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 or a lower alcohol, particularly water, as a solvent is preferable.

Examples 1-4 and Comparative Examples 1-4
Hair cleaning agents shown in Table 1 were prepared and evaluated by the following evaluation methods. The results are also shown in Table 1. In addition, pH is a value at 25 ° C. after 20-fold dilution with water.

Evaluation method (1) Speed of foaming The speed of foaming was evaluated using the apparatus shown in FIG.
The apparatus of FIG. 1 has a drainage port (not shown) on the bottom surface, a transparent plastic cylindrical container 10 (diameter 160 mm, height 55 mm) with an open top surface, a transparent plastic lid 20 and a motor 30. It has a built-in control unit 40, measuring instrument 50, and torque detector 60. In this container 10, a disk 11 (approximately 160 mm in diameter) in which hair 1 (90 mm, 30 g in total) is implanted in a plurality of flock holes P shown in FIG. The container 10 is rotated by the motor 30 in the direction of the arrow x, whereby the hair 1 in the container 10 is also rotated.

  On the back surface of the lid 20, there are a first protrusion 21 corresponding to a human finger (3 columnar protrusions having a diameter of 15 mm and a height of 12 mm) and a second protrusion 22 corresponding to a brush (vertical 10 mm). 9 projections each having a width of 2 mm and a height of 12 mm are provided so as to come into contact with the hair 1 when the lid 20 is placed on the upper surface of the container 10 as indicated by an arrow y. The lid 20 is provided with a funnel-shaped injection hole 25 for injecting the cleaning agent. When the lid 20 is put on the container 10, it is not fixed to the container 10 and is supported on the support column 41 via the torque detector 60 and the measuring instrument 50. Therefore, when the container 10 is covered with the lid 20 and the container 10 is rotated, the hair 1 and the protrusions 21 and 22 in the container 10 slide. Therefore, when a cleaning agent is applied to the hair 1 from the injection hole 25, the cleaning agent can be foamed in a state close to that of actual hair.

First, the hair was wetted with 30 g of water, 0.3 mL of model sebum composed of lanolin was added, and then 1.5 mL of the evaluation sample was applied. Next, the container 10 is rotated at 70 revolutions per minute to slide the hair 1 and the protrusions 21 and 22 and the generated foam is collected in the measuring instrument 50. Depending on the time until the foam amount reaches 25 mL, Evaluation was made according to the following criteria.
◎: Less than 100 seconds ○: More than 100 seconds and less than 200 seconds △: More than 200 seconds and less than 300 seconds ×: More than 300 seconds

(2) Slippery feeling when foaming After rinsing a hair bundle of 25cm in length, 5.5cm in width and 10g in weight with warm water at 40 ℃, remove excess water and use 0.5g of hair cleanser Foamed well for about 30 seconds. At that time, the sense of slip 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) Slippery feeling when rinsing After rinsing a human hair bundle 25cm in length, 5.5cm in width and 10g in weight with warm water at 40 ° C, remove excess water and use 0.5g of hair cleanser Foamed well 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

(4) Glossy unit 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. The evaluation criteria are as follows.
4: Good 3: Somewhat good 2: Not very good 1: Not good

(5) Stability The hair cleansing agent was filled in 100 mL in a 110 mL standard bottle and stored at 50 ° C. for 1 month for evaluation. The evaluation criteria are as follows.
○: No change due to storage △: Slight change due to storage (within tolerance)
×: Apparently changed by storage (outside tolerance)

* 1: Polyoxyethylene (1) ammonium lauryl ether sulfate; ethylene oxide mass average addition mole number 1
* 2: Cationized tara gum; Kachinal CTR-100 (Toho Chemical Industries)
* 3: Cationized hydroxyethyl cellulose; Poise C-80M (Kao Corporation)
* 4: Cationized guar gum; Jaguar C-13S (Rhodia)
* 5: Amino-modified silicone; 8500 Conditioning Agent (Toray Dow Corning)
* 6: Amino-modified silicone; DOW CORNING TORAY SS-3588 (Toray Dow Corning)
* 7: Amino-modified silicone; Silicone KT-1989 (GE Toshiba Silicones)
* 8: Isodecyl glyceryl ether; derived from alcohol obtained by converting propylene trimer by oxo method (hereinafter the same)
* 9: Dimethylpolysiloxane emulsion; Viscosity (10000 mm ² / s) / (10 mm ² / s) = 95/5, average particle size 4.0 μm, dimethylpolysiloxane 60% by mass)

Example 5 Conditioning Shampoo
(mass%)
Polyoxyethylene (1) ammonium lauryl ether sulfate (average number of moles of ethylene oxide added) 13.0
Cationized tara gum (Catinal CTR-100, Toho Chemical Industries) 0.2
Amino-modified silicone (8500 Conditioning Agent, Toray Dow Corning) 0.3
Cationized cellulose (Poise C-80M, Kao) 0.3
Diallyldimethylammonium chloride / acrylamide copolymer (Mercoat 550, Ondeo Narco, effective content 8.5% by mass) 1.7
Dimethylpolysiloxane emulsion (silicone viscosity 10,000mm ² / s, average particle size 4μm, effective content 60% by mass) 1.7
Ethylene glycol distearate 2.0
Isodecyl glyceryl ether 0.5
Lauroylamidopropylbetaine 1.0
Myristyl alcohol 0.4
Cetyl alcohol 0.1
Cocoyl monoethanolamide 0.5
Polyoxyethylene (16) lauryl ether 0.7
Polypropylene glycol (mass average molecular weight 400) 0.5
Benzyl alcohol 0.3
Ethanol 3.0
Camellia oil 0.01
Panthenol 0.05
Royal Jelly 0.01
Refined honey 0.01
Silk extract 0.05
Sodium chloride 0.2
Perfume Appropriate amount Malic acid 0.5
pH adjuster (lactic acid) Amount to reach pH 3.9 Ion exchange water Balance

Example 6 Conditioning Shampoo
(mass%)
Polyoxyethylene (2) sodium lauryl ether sulfate (ethylene oxide average addition mole number 2) 13.0
Cationized tara gum (Catinal CTR-200, Toho Chemical Industry Co., Ltd.) 0.5
Amino-modified silicone (SS-3588, Toray Dow Corning) 0.1
Cationized guar gum (Jaguar C-17, Rhodia) 0.1
Diallyldimethylammonium chloride homopolymer (Mercoat 100, Ondeo Narco, effective 40% by mass) 0.8
Highly polymerized dimethylpolysiloxane emulsion (silicone CF2450, Toray Dow Corning, particle size 0.2-0.8μm,
Effective mass 60% by mass) 2.0
Ethylene glycol distearate 3.0
Isodecyl glyceryl ether 0.7
Lauroylamidopropylbetaine 2.0
Cocoyl monoethanolamide 0.5
Myristyl alcohol 0.5
Cetyl alcohol 0.5
Polyoxyethylene (16) lauryl ether 1.0
Benzyl alcohol 1.0
Polypropylene glycol (mass average molecular weight 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
pH adjuster (sodium hydroxide) Amount to reach pH 3.9 Ion-exchanged water Balance

Example 7 Conditioning Shampoo
(mass%)
Polyoxyethylene (1) sodium lauryl ether sulfate (ethylene oxide average addition mole number 1) 16.0
Cationized tara gum (Catinal CTR-100, Toho Chemical Industries) 0.7
Amino-modified silicone (8500 Conditioning Agent, Toray Dow Corning) 0.5
Highly polymerized dimethylpolysiloxane emulsion (Silicone CF2460, Toray Dow Corning, particle size 20μm,
Effective mass 75% by mass) 3.0
Ethylene glycol distearate 3.0
2-Ethylhexyl glyceryl ether 0.3
Cocoyl monoethanolamide 0.5
Stearyl alcohol 1.0
Glycerin 1.0
Sodium chloride 0.2
Benzyloxyethanol 0.5
Malic acid 0.7
Perfume Appropriate amount of lactic acid 0.1
pH adjuster (citric acid) Amount to reach pH 5.5 Ion-exchanged water Balance

Example 8 Conditioning Shampoo
(mass%)
Polyoxyethylene (2.5) sodium lauryl ether sulfate (ethylene oxide average addition mole number 2.5) 15.0
Cationized tara gum (Catinal CTR-200, Toho Chemical Co., Ltd.) 0.2
Amino-modified silicone (SILSTYLE 104, Toray Dow Corning) 1.0
Cationized locust bean gum (Catinal CLB-100, Toho Chemical Industry Co., Ltd.) 0.2
Methyl polysiloxane emulsion (silicone viscosity 5,000mm ² / s, particle size 0.2-0.8μm, effective content 65% by mass) 2.0
Ethylene glycol distearate 2.0
Lauroylamidopropylbetaine 3.0
Cocoyl monoethanolamide 0.8
Polyoxyethylene (16) lauryl ether 2.0
Sodium cocoamphoacetate 1.0
Stearoxypropyldimethylamine malate 0.5
Polypropylene glycol (mass average molecular weight 400) 0.5
Sodium chloride 1.0
Malic acid 0.8
Citric acid 0.75
pH adjuster (sodium hydroxide) Amount to reach pH 3.5 Ion exchange water Balance

  The hair cleaners of Examples 5 to 8 had quick foaming and good slipping at the time of foaming and rinsing, had good gloss and cohesiveness of the finished hair, and were excellent in storage stability.

It is a whole figure of the apparatus used for evaluation of the speed of foaming. (a) A top view of a disk for planting hair, and (b) a cross-sectional view of a disk for planting hair.

Explanation of symbols

1 Hair
10 containers
11 disc
20 lids
21 First protrusion
22 Second protrusion
23 Foam induction wall
24 Hair prevention pin
25 Injection hole
30 motor
40 Control unit
41 Prop
50 Weighing scale
51 Water injection hole
60 Torque detector P Flocking hole

Claims (6)

An aqueous hair cleanser containing the following components (A), (B) and (C).
(A) Anionic surfactant
(B) Cationized tara gum
(C) Amino-modified silicone represented by general formula (1) or (4)

[In the formula, each R ¹ independently represents a monovalent hydrocarbon group, a hydroxy group or an alkoxy group,
Each R ² independently represents a monovalent hydrocarbon group;
R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ is the formula (3)

(Y represents a hydrogen atom or a group —CH ₂ —CH (OH) —R ³ —OH (R ³ is the same as above), R ⁵ represents a hydrogen atom or a group —R ³ NY ₂ (Y and R ³ are However, not all Y are hydrogen atoms.), A represents a number from 25 to 1000, and b represents a number from 1 to 200. ]

[Wherein R ⁶ independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁷ represents R ⁶ or E, and E represents —R ⁸ —Z (where R ⁸ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, Z represents a primary to tertiary amino group-containing group or an ammonium group-containing group. Represents a divalent group, c is a number of 2 or more, d is a number of 1 or more, n is a number of 2 to 10, e is a number of 4 or more, and f is a number of 2 or more. ]   The aqueous hair cleanser according to claim 1, comprising 1 to 30% by mass of component (A), 0.01 to 10% by mass of component (B), and 0.01 to 10% by mass of component (C).   The aqueous hair cleansing agent according to claim 1 or 2, wherein the mass ratio of the component (B) / (C) is 1/110 to 10/1.   The component (D) further contains a glyceryl ether selected from monoalkyl glyceryl ethers having 4 to 10 carbon atoms in the alkyl group and monoalkenyl glyceryl ethers having 4 to 10 carbon atoms in the alkenyl group. The aqueous hair cleansing agent according to any one of the above.   The aqueous hair cleanser according to any one of claims 1 to 4, further comprising a component (E) dimethylpolysiloxane.   The aqueous hair cleanser according to any one of claims 1 to 5, having a pH of 2 to 6 at 25 ° C when diluted 20 times by weight with water.

Images