JP4728283B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention relates to an aqueous hair cleansing agent.

  Dimethylpolysiloxane is widely used as a hair cleanser for the purpose of imparting a conditioning effect to the hair. Although dimethylpolysiloxane is effective in improving the smoothness of the detergent when foamed, it has a low persistence to the hair when rinsed, and it is difficult to impart smoothness by itself. As a method for efficiently remaining dimethylpolysiloxane on the hair, a method in which cationized guar gum and dimethylpolysiloxane having an average particle size of less than 2 μm are used in combination as in Patent Document 1 has been proposed. However, since the average particle size of dimethylpolysiloxane is as small as 2 μm and is relatively stably dispersed in water, the residual property on hair is not sufficient, and the cationized guar gum is not smooth enough during rinsing. The problem of hair getting tangled during rinsing remained. Therefore, as a means for enhancing the conditioning effect, a cationized tara gum obtained by cationizing a polysaccharide obtained from the endosperm of a seed of the legume cod (Caesal pinia Spinosa) is applied to a hair cleanser (Patent Document 2). In addition, it has been proposed to use cationized tara gum and cationized guar gum in a hair cleansing agent (Patent Document 3). In these, there is an example in which an aqueous emulsion of dimethylpolysiloxane is used, but any dimethylpolysiloxane has an average particle size of less than 1 μm, has poor persistence on hair, and has the problem that hair is entangled during rinsing. I still had it.

Japanese Unexamined Patent Publication No. 4-234309 JP 2004-203801 A JP 2005-272658 A

  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 inventor is excellent in foam performance, feel and finish even for damaged hair by using an anionic surfactant, cationized tara gum, and dimethylpolysiloxane having a particle size of a certain size or more. It has been found that an aqueous hair cleanser with excellent storage stability 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) Dimethylpolysiloxane present as dispersed particles having an average particle diameter of 2 to 100 μm

  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 (1) or (2) The thing represented by these is preferable.

R ¹ O (CH ₂ CH ₂ O) _m SO ₃ M (1)
R ¹ OSO ₃ M (2)

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

Among these, R ¹ in the general formula (1) 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. It is preferable that it is 2 mass%.

Component (C) is dimethylpolysiloxane present as dispersed particles having an average particle diameter of 2 to 100 μm. Examples of dimethylpolysiloxane include those represented by the following general formula (3).
R ² (CH ₃ ) ₂ SiO — [(CH ₃ ) ₂ SiO] _n —Si (CH ₃ ) ₂ R ² (3)
[Wherein, R ² independently represents a methyl group or a hydroxy group, and n represents a number of 1 to 20,000. ]

The dimethylpolysiloxane of component (C) preferably has a kinematic viscosity at 25 ° C. of 10 to 30,000,000 mm ² / s in terms of smoothness during foaming and rinsing, and no stickiness after drying, Furthermore 1,000~20,000,000mm ² / s, more preferably a 10,000~10,000,000mm ² / s. Commercially available products include KF-96A-5cs, KF-96A-10cs, KF-96A-100cs, KF-96A-1000cs, KF-96A-5000cs, KF-96H-10,000cs, KF-96H-50,000cs , KF-96H-100,000 cs, KF-96H-1,000,000 cs (above, Shin-Etsu Silicone). These dimethylpolysiloxanes can be used alone or in combination of two or more. Moreover, you may use what is marketed as a mixture with liquid cyclic silicones, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

  The component (C) dimethylpolysiloxane is preferably used in the form of an aqueous emulsion formed mechanically in advance. In preparing the aqueous emulsion, it is preferable to contain at least one emulsifier from the viewpoint of stabilizing the emulsion.

  Examples of the emulsifier used here include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl fatty acid ester, polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid ester, Nonionic surfactants such as glycerin fatty acid ester, sucrose fatty acid ester, polyether-modified silicone; cations such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylamine salt, alkoxydimethylamine salt, alkylamidodimethylamine salt Surfactant: Sodium dodecylbenzenesulfonate, sodium alkyl sulfate, ammonium alkyl sulfate, polyoxyethylene Sodium alkyl ether sulfate, polyoxyethylene alkyl ether sulfate, potassium coconut oil fatty acid, anionic surfactants such as coconut oil fatty acid methyl taurine sodium and the like.

  As a method for preparing the above-mentioned aqueous emulsion, after mixing dimethylpolysiloxane and an emulsifier, water is slowly added with stirring, and a high shear mixer is used for phase inversion from the W / O emulsion to the O / W emulsion. And mixing at a high speed, then adding the remaining water, and mixing again at a high speed with a high shear mixer.

  The average particle size of the aqueous emulsion can be arbitrarily changed by changing the type and amount of the emulsifier to be used and the stirring rotation speed of the high shear mixer.

  In the present invention, the average particle size of the emulsion is 2 to 100 μm, but from the viewpoint of persistence to hair, 3 to 50 μm, more preferably 4 to 30 μm is preferable. The average particle size of the aqueous emulsion is synonymous with the average particle size of dimethylpolysiloxane as component (C) in the aqueous hair cleansing agent.

  The average particle diameter of the dimethylpolysiloxane emulsion can be measured by a particle diameter measuring apparatus using laser light scattering, for example, using a Coulter LS-130.

Such dimethylpolysiloxane emulsion, for example, after a kinematic viscosity at 25 ° C. were mixed dimethylpolysiloxane is 8,000,000mm ² / s and 5,000 mm ² / s at 1 to 1 ratio, cetyltrimethylammonium chloride What is marketed as “Silicone CF2460” manufactured by Toray Dow Corning Co., Ltd., having an average particle size of 20 μm, emulsified with the above can be used.

  The content of component (C), dimethylpolysiloxane, is preferably 0.01 to 10% by mass in the aqueous hair cleansing agent of the present invention, and is smooth from the time of shampooing to rinsing and not sticky after drying. Therefore, 0.1 to 5% by mass is more preferable, and 0.5 to 2% by mass is more 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 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 foaming power is improved, but also an appropriate liquid property is obtained. preferable.

  The content of the nonionic surfactant or the amphoteric surfactant is preferably 0.1 to 15% by mass in the aqueous hair cleansing agent of the present invention because a good foam increasing effect is obtained. From the above points, the range of 0.5 to 8% by mass, and more preferably 1 to 6% by mass is 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 ³ −N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein R ³ 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 ⁴ —O—R ⁵ —N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein, R ⁴ represents an alkyl group having 12 to 22 carbon atoms, R ⁵ represents an ethylene group or a propylene group which may be substituted with 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 ⁶ ) ₂ N ⁺ (CH ₃ ) ₂ X ⁻
[Wherein, R ⁶ 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 ⁷ -N (CH _{3) 2}
[Wherein, R ⁷ 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 ⁸ —O—R ⁹ —N (CH ₃ ) ₂
[Wherein R ⁸ represents an alkyl group having 12 to 22 carbon atoms, and R ⁹ 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 ¹⁰ —C (═O) NH—R ¹¹ —N (CH ₃ ) ₂
[Wherein, R ¹⁰ represents an alkyl group having 11 to 21 carbon atoms, and R ¹¹ 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.

Examples of silicones other than the component (C) include those shown below.
(1) Amino-modified silicone Various amino-modified silicones can be used, but are described in the third edition of the CTFA Dictionary (US, Cosmetic Ingredient Dictionary) under the name of Amodimethicone with an average molecular weight of about 3,000-100,000. Those are preferred. Commercially available products include SM 8704C (Toray Dow Corning), DC 929 (Dow Corning), KT 1989 (GE Toshiba Silicone), 8500 Conditioning Agent, DOW CORNING TORAY SS-3588, DOW CORNING TORAY SILSTYLE 104 ( Toray Dow Corning).

(2) Other silicones In addition to the above, polyether-modified silicone, methylphenylpolysiloxane, 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 is preferably 0.01 to 10% by mass in the aqueous hair cleaning agent of the present invention, Furthermore, 0.05-5 mass%, Furthermore, 0.1-2 mass% is preferable.

  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.

Production Example 1 Preparation of dimethylpolysiloxane emulsion (Inventive dimethylpolysiloxane emulsion 1, effective 60 mass%, average particle size 2 μm)
20 a kinematic viscosity of the dimethylpolysiloxane 6,000,000mm ² / s at 25 ℃, 500mm ² / s dimethylpolysiloxane 40 parts by mass of the homogeneously by HEIDON Co. Three-One with a motor BL600 200 rpm of the rotational speed of the Mix until. Next, while stirring at a rotation speed of 200 rpm, 3.5 parts by mass of polyoxyethylene (23) lauryl ether and 1.5 parts by mass of polyoxyethylene (4) lauryl ether were added and mixed for 10 minutes. Then, 25 parts by weight of water was added while stirring at a rotation speed of 200 rpm, and then at a rotation speed of 5,000 rpm using an Ajihomo mixer (f2 / 5 model, No. 023010) manufactured by Tokushu Kika Kogyo Co., Ltd. Stir for 5 minutes. Next, 10% by mass of water was added, and the mixture was stirred for 5 minutes at a rotational speed of 5000 rpm using the same Ajihomo mixer.
The average particle size of the emulsified particles of the silicone emulsion was 2.0 μm as measured by laser diffraction at an appropriate concentration using Coulter LS-130.

Production Example 2 Preparation of a dimethylpolysiloxane emulsion (this invention dimethylpolysiloxane emulsion 2, effective 60 mass%, average particle size 4 μm)
Example of production except that 55 parts by weight of dimethylpolysiloxane with a kinematic viscosity of 10,000 mm ² / s and 5 parts by weight of dimethylpolysiloxane with 10 mm ² / s were mixed and the rotational speed of the Ajihomo mixer was changed to 3000 rpm. In the same manner as in Example 1, a dimethylpolysiloxane emulsion was prepared.
When the average particle size of the emulsified particles was measured in the same manner as in Production Example 1, it was 4.0 μm.

Examples 1-2 and Comparative Examples 1-4
Using the dimethylpolysiloxane emulsion obtained in Production Examples 1 and 2, hair cleansing 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) Glossiness after drying The hair bundle treated in the same manner as in 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: Dimethylpolysiloxane emulsion; containing 25% by mass and 35% by mass of dimethylpolysiloxane with kinematic viscosities of 6,000,000mm ² / s and 500mm ² / s, respectively, with an average particle size of 0.7μm. What is marketed as silicone CF2450.

Example 3 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 Co., Ltd.) 0.3
Dimethylpolysiloxane emulsion (Invention product dimethylpolysiloxane emulsion 2, Production Example 2) 1.7
Isodecylglyceryl ether (Produced from alcohol obtained by converting propylene trimer by oxo method, the same shall apply hereinafter) 0.5
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
Ethylene glycol distearate 2.0
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-exchanged water Balance

Example 4 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 Industries) 0.4
Dimethylpolysiloxane emulsion (Silicone CF2460, Toray Dow Corning, average particle size 20μm,
Effective mass 75% by mass) 3.0
Isodecyl glyceryl ether 0.7
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
Ethylene glycol distearate 3.0
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 5 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) 0.8
Dimethylpolysiloxane emulsion (Invention dimethylpolysiloxane emulsion 1, Production Example 1) 3.0
2-Ethylhexyl glyceryl ether 0.3
Amino-modified silicone (8500 Conditioning Agent, Toray Dow Corning) 0.5
Ethylene glycol distearate 3.0
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 exchange water Balance

Example 6 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
Dimethylpolysiloxane emulsion (Invention dimethylpolysiloxane emulsion 2, Production Example 2) 2.0
2-Ethylhexyl glyceryl ether 1.5
Amino-modified silicone (SILSTYLE 104, Toray Dow Corning) 1.0
Cationized locust bean gum (Catinal CLB-100, Toho Chemical Industry Co., Ltd.) 0.2
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 cleansing agents of Examples 3 to 6 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 (4)

An aqueous hair cleanser containing the following components (A), (B) , (C) and (D) .
(A) Anionic surfactant
(B) Cationized tara gum
(C) Dimethylpolysiloxane present as dispersed particles having an average particle diameter of 2 to 100 μm
(D) 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 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 component (A) is represented by the following general formula (1) or (2).
R ¹ O (CH ₂ CH ₂ O) _m SO ₃ M (1)
R ¹ OSO ₃ M (2)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, M represents a cation derived from an alkali metal, an alkaline earth metal, ammonium, an alkanolamine or a basic amino acid, and m represents a mass average. The number of 1-5 is shown. ] The aqueous hair cleanser according to any one of claims 1 to 3 , which has a pH of 2 to 6 at 25 ° C when diluted 20 mass times with water.

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