JP5426212B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention relates to an aqueous hair cleansing agent.

  The main purpose of the hair cleanser is to remove dirt on the hair and scalp and keep them clean. In order to obtain a hair cleanser with high detergency, an anionic surfactant having the same charge as the hair and scalp, particularly a strong acid anionic surfactant such as a sulfate group or a sulfonate group in the anion portion, is used as the main cleaning agent. It is preferable to use it from the viewpoint of preventing reattachment of dirt. Among them, alkyl sulfates and alkyl ether sulfates are most commonly used as main ingredients of hair cleansing agents because of their abundant foam amount and excellent stain removal properties.

  On the other hand, alkyl sulfates and alkyl ether sulfates have problems in terms of mildness to the scalp. The stratum corneum cells, which are present in 10 to 20 layers on the skin surface, have an important role of keeping moisture inside the skin and protecting external stimuli. The above-mentioned alkyl sulfates and alkyl ether sulfates are It has a strong property of permeating into the stratum corneum to swell cells and eluting natural moisturizing components such as amino acids and lipids originally present inside the cells. Therefore, repeated washing with a hair cleansing agent containing these surfactants as the main ingredient reduces the moisture content of the scalp, causing the skin to become dry, and surfactants and external irritants are likely to enter the skin. Therefore, the scalp tends to be itchy.

  As a means for imparting mildness to the scalp, there is a method of preparing a hair cleanser with an amino acid anionic surfactant as the main ingredient instead of the alkyl ether sulfate. In general, amino acid-based surfactants are difficult to swell the stratum corneum and have mild properties on the skin, but on the other hand, the anionic part is often a weak acid such as a carboxylic acid, so that foaming and dirt removal properties are reduced. It was not sufficient and was insufficient to satisfy the basic performance as a hair cleanser. Therefore, in order to solve this problem, as described in Patent Document 1, a detergent composition based on an alkyloylalkyltaurine salt type anionic surfactant whose anion portion is a sulfonic acid group has been proposed. Yes. However, compared with alkyl sulfates and alkyl ether sulfates, foaming and foam amount are still insufficient, and it is difficult to satisfy the basic performance as a hair cleanser.

  In addition, as an attempt to achieve both mildness and foaming, as described in Patent Document 2, the alcohol moiety has an alkyl group having 8 to 16 carbon atoms with respect to an anionic surfactant such as alkyl ether sulfate. A shampoo composition is proposed in which a nonionic surfactant such as polyethoxylated alcohol having 10 to 45 ethoxy groups per molecule is used in combination, and the pH of the composition is 6.0 to 8.0. Yes. Further, as a similar attempt, as described in Patent Document 3, there is a shampoo composition using a nonionic surfactant having an HLB of at least 8 in combination with an anionic surfactant such as alkyl ether sulfate. Proposed.

  In general, nonionic surfactants are known to have a stratum corneum swelling property and mild skin properties, but it is difficult to obtain an abundant amount of foam suitable for a hair cleanser. In Patent Document 2, the nonionic surfactant is used in the composition at least 38% by weight, and in Patent Document 3, the nonionic surfactant is used in the composition at least 29% by weight. When a relatively large amount of nonionic surfactant was blended in this way, the amount of foam necessary as a hair cleansing agent could not be obtained, and both mildness and foaming could not be achieved.

JP-A-61-272295 JP 49-099104 A Japanese Patent Laid-Open No. 04-225909

  An object of the present invention is to provide an aqueous hair cleanser that is excellent in foaming, smoothness of foam, and fingering during rinsing, and that is mild and less itchy on the scalp.

  The present inventor is a water-based hair cleansing agent comprising an alkyl sulfate or alkyl ether sulfate as a main cleaning component, by mixing a small amount of a polyoxyethylene alkyl ether type nonionic surfactant having an alkyl group having a specific chain length, It has been found that a hair cleanser that suppresses swelling of the stratum corneum and has both mildness to the scalp and excellent foaming can be obtained.

That is, according to the present invention, the following components (A) and (B):
(A) a sulfate-type anionic surfactant represented by the following general formula (1):
R ¹ O (CH ₂ CH ₂ O) _n SO ₃ M (1)
(In the general formula (1), 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, n is a mass average and represents a number from 0 to 5);
(B) a polyoxyethylene alkyl ether type nonionic surfactant represented by the following general formula (2),
R ² O (CH ₂ CH ₂ O) _m H (2)
(In the general formula (2), R ² represents a linear or branched alkyl group or alkenyl group having 16 to 22 carbon atoms, and m represents a number of 5 to 30 on a mass average basis);
And an aqueous hair cleanser containing (B) / ((A) + (B)) in a mass ratio of 1/100 to 25/100.

  The aqueous hair cleansing agent of the present invention is excellent in foaming, smoothness of foam, and fingering at the time of rinsing, and is mild and less itchy on the scalp.

It is a schematic block diagram of the apparatus used for evaluation regarding the speed of foaming.

  The aqueous hair cleansing agent of the present invention contains the above components (A), (B) and water. Hereinafter, each component will be specifically described.

First, the component (A) will be described.
In the aqueous hair cleansing agent of the present invention, the component (A) is an alkyl sulfate or alkyl ether sulfate sulfate type anionic surfactant represented by the general formula (1).

(A) Sulfate-type anionic surfactant represented by the following general formula (1)
R ¹ O (CH ₂ CH ₂ O) _n SO ₃ M (1)
(In the general formula (1), R ¹ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, M represents an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid, and n represents mass. Shows an average number of 0-5.)

Among these, from the viewpoint of having quick foaming and high detergency, R ¹ in the general formula (1) is an alkyl group having 12 to 14 carbon atoms, n is a mass average of 1 to 2 and M is Polyoxyethylene alkyl ether sulfates that are ammonium or sodium are preferred.

  Component (A) may be used singly or in combination of two or more, and the content thereof is that of foaming, liquid properties at the time of use, and fingering properties at the time of rinsing. 1 to 25% by mass in the aqueous hair cleansing agent is preferable, 5 to 23% by mass, particularly 8 to 20% by mass is preferable.

Next, the component (B) will be described.
In the aqueous hair cleansing agent of the present invention, the component (B) is a polyoxyethylene alkyl ether type nonionic surfactant represented by the general formula (2).

(B) Polyoxyethylene alkyl ether type nonionic surfactant represented by the following general formula (2)
R ² O (CH ₂ CH ₂ O) _m H (2)
(In the above general formula (2), R ² represents a linear or branched alkyl group or alkenyl group having 16 to 22 carbon atoms, and m represents a number of 5 to 30 in terms of mass average.)

  Typical commercial products corresponding to such component (B) include Emalex 606 (polyoxyethylene (6) stearyl ether, molecular weight 518, manufactured by Nippon Emulsion), Emulgen 306P (polyoxyethylene (6) stearyl ether). , Molecular weight 518, manufactured by Kao Corporation), Emulgen 320P (polyoxyethylene (13) stearyl ether, molecular weight 827, manufactured by Kao Corporation), Emulgen 210 (polyoxyethylene (7) cetyl ether, molecular weight 534, manufactured by Kao Corporation), Emulgen Polyoxyethylene alkyl ether type surfactants such as 409P (polyoxyethylene (9) oleyl ether, molecular weight 648, manufactured by Kao Corporation), Emulgen 430 (polyoxyethylene (30) oleyl ether, molecular weight 1132, manufactured by Kao Corporation) Can be mentioned.

  The nonionic surfactant that is the component (B) of the present invention is considered to form a protective film on the surface of the stratum corneum, and as a result, has the effect of suppressing the penetration of the anionic surfactant that is the component (A) into the stratum corneum. Have. In order to express such an effect, it is preferable that the nonionic surfactant as the component (B) is efficiently adsorbed on the surface of the stratum corneum and does not permeate itself into the stratum corneum.

In order for the component (B) to be efficiently adsorbed to the stratum corneum surface, the component (B) preferably has a critical micelle concentration (CMC) of about 1 × 10 ⁻⁶ M or less. The CMC value decreases as the alkyl chain length increases. From this point of view, R ² in the above formula (2) is a straight chain or branched alkyl group or alkenyl group having 16 to 22 carbon atoms, and in particular, the viewpoint of achieving both the adsorptivity to the stratum corneum and the foaming of the hair cleaning agent Therefore, polyoxyethylene stearyl ether in which R ² in the formula (2) is 18 is particularly preferable.

  Moreover, in order that a component (B) does not osmose | permeate the inside of a stratum corneum, it is preferable that the molecular weight of a component (B) is 500 or more. From that point of view, m in the above formula (2) is 5 to 30, but in particular, m is preferably 5 to 20 from the viewpoint of achieving both stratum corneum swelling and foaming, and particularly m is 6 to 10. It is preferable.

  Component (B) may be used singly or in combination of two or more. The content thereof is mild to the scalp, foams, and the point of fingering at the time of rinsing, the aqueous composition of the present invention. 0.1-10 mass% in a hair cleaning agent is preferable, Furthermore, 0.5-7 mass%, Especially 1-5 mass% is preferable.

  Moreover, from the viewpoint of achieving both mildness to the scalp and excellent foaming, the mass ratio of (B) / ((A) + (B)) is 1/100 to 25/100 in the components (A) and (B). In particular, 3/100 to 23/100 is preferable, and 5/100 to 20/100 is particularly preferable.

  The aqueous hair cleansing agent of the present invention may further contain an organic carboxylic acid or an anti-inflammatory agent in order to further improve the inhibitory effect of scalp dandruff, itching, pimples, bulkiness, and the like.

As the organic carboxylic acid, those having 2 to 6 carbon atoms are preferable, and among them, dicarboxylic acid (which may have a hydroxy group) and hydroxymonocarboxylic acid are more preferable. Specifically, examples of the dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, and oxalic acid. Examples of the dicarboxylic acid having a hydroxy group include malic acid and tartaric acid. Examples of the hydroxy monocarboxylic acid include glycolic acid, lactic acid, hydroxyacrylic acid, oxybutyric acid, glyceric acid, and gluconic acid.
Among these organic carboxylic acids, glycolic acid, lactic acid, malonic acid, maleic acid, and malic acid are preferable. Examples of the salts of these organic carboxylic acids include salts with alkali metals, alkaline earth metals, ammonia, and organic amine compounds.

  The organic carboxylic acid or a salt thereof may be used alone or in combination of two or more, and the content thereof is 0.1% in the aqueous hair cleanser from the viewpoint of providing a sufficient scalp improving effect. -5% by mass is preferable, 0.2-3% by mass, more preferably 0.5-2% by mass.

The aqueous hair cleansing agent of the present invention has a pH of 1 to 5 at 25 ° C. when diluted 20 times with water, in order to maximize the scalp symptom improving effect of the organic carboxylic acid, A pH of 2 to 4.5 is preferable, and a pH of 3 to 4.5 is particularly preferable.
In order to adjust the pH of the composition to such a preferable range, an organic or inorganic acid or alkali agent can be appropriately combined and used in an appropriate amount. Examples of the organic acid include citric acid and glutamic acid in addition to the above organic carboxylic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Examples of the alkali include sodium hydroxide and potassium hydroxide.

  The aqueous hair cleansing agent of the present invention is excellent in foaming, foam smoothness and rinsing smoothness regardless of the pH value, and has the effect of suppressing stratum corneum swelling and itching. Furthermore, when an organic carboxylic acid or a salt thereof is contained and the pH at the time of 20-fold dilution is acidified to 1 to 5, an anti-dandruff effect that cannot be obtained neutrally can be newly obtained.

  Anti-inflammatory agents include anti-inflammatory agents such as glycyrrhetinic acid, glycyrrhizic acid and derivatives thereof, as well as components having an anti-inflammatory function, such as ε-aminocaproic acid, allantoin, sodium guaiazulenesulfonate, d-camphor, l-menthol, Examples include urea, pyridoxine dipalmitate, glycyrrhetinyl stearate, tranexamic acid, vitamin A oil, hydrocortisone, prednisolone, pyridoxine hydrochloride, photosensitizer 301, zinc oxide, hydrocortisone acetate, and the like. Examples of the derivatives of glycyrrhetinic acid or glycyrrhizic acid include alkali metal salts such as sodium salt and potassium salt, salts such as ammonium, and esters such as glycerin ester and stearyl ester. Specific examples include dipotassium glycyrrhizinate, disodium glycyrrhizinate, trisodium glycyrrhizinate, monoammonium glycyrrhizinate, glyceryl glycyrrhetinate, and stearyl glycyrrhetinate.

  The anti-inflammatory agent may be used alone or in combination of two or more, and the content thereof is preferably 0.001 to 10% by mass, particularly 0.005 to 5% by mass, and particularly preferably 0.00. It is preferable to contain 01-1 mass%.

  In order to further improve the cleaning performance, the aqueous hair cleansing agent of the present invention may contain an anionic surfactant other than component (A), a nonionic surfactant other than component (B) or an amphoteric surfactant. Good.

  As the anionic surfactant other than the component (A), sulfuric acid-based, sulfonic acid-based and carboxylic acid-based ones can be used. Examples include sulfosuccinic acid alkylene alkyl phenyl ether sulfates, sulfosuccinic acid alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonates, higher fatty acid salts, alkyl ether carboxylic acids or salts thereof, among them alkyl ethers. Carboxylic acid or a salt thereof is preferred.

  Nonionic surfactants other than component (B) include polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene sorbite fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene Examples include alkyl phenyl ether, polyoxyalkylene (hardened) castor oil, sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, fatty acid alkanolamide, alkyl glycoside, monoalkyl or monoalkenyl glyceryl ether.

Among these, polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters such as polyoxyalkylene (C ₈ -C ₂₀ ) fatty acid esters, and polyoxyalkylenes such as polyoxyethylene hydrogenated castor oil (Hardened) castor oil and alkyl glycoside are preferred.

  Fatty acid alkanolamides are also suitable, which may be either monoalkanolamides or dialkanolamides, and those having an acyl group having 8 to 18 carbon atoms, particularly 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.

  Monoalkyl glyceryl ether or monoalkenyl glyceryl ether is also suitable, and the alkyl group or alkenyl group 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, 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 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, the component (A) It is particularly preferable to use fatty acid amidopropyl betaine, fatty acid alkanolamide, and monoalkyl glyceryl ether together with (B) because not only foaming power is improved but also an appropriate liquid property is obtained.

  The content of these surfactants is preferably from 0.1 to 15% by mass in the 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, particularly 1 to 6% by mass is more preferable.

In the aqueous hair cleansing agent of the present invention, a cationic surfactant, a cationized polymer and silicones can be further blended in order to improve the finish after fingering and after drying.
Examples of the cationic surfactant include alkyl trimethyl ammonium salts, alkoxy trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl amine salts, alkoxy dimethyl amine salts, alkyl amide dimethyl amine salts, and the like.

(I) Alkyltrimethylammonium salt For example, what is represented by the following general formula is mentioned.
R ¹¹ −N ⁺ (CH ₃ ) ₃ X
(In the above formula, R ¹¹ represents an alkyl group having 12 to 22 carbon atoms, and X represents a halogen (chlorine or bromine) ion.)
Specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride.

(Ii) Alkoxytrimethylammonium salt Examples include those represented by the following general formula.
R ¹² —O—R ¹³ —N (CH ₃ ) ₃ X
(In the above formula, R ¹² represents an alkyl group having 12 to 22 carbon atoms, R ¹³ represents an ethylene group or a propylene group, and X is the same as above.)
Specific examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride, and the like.

(Iii) Dialkyldimethylammonium salt For example, what is represented by the following general formula is mentioned.
R ¹⁴ ₂ -N ⁺ (CH ₃ ) ₂ X
(In the above formula, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and X is the same as above.)
Specifically, distearyl dimethyl ammonium chloride etc. are mentioned.

(Iv) Alkyldimethylamine salt For example, what is represented by the following general formula is mentioned.
R ¹⁵ -N _(CH 3) ₂
(In the above formula, R ¹⁵ represents an alkyl group having 12 to 22 carbon atoms.)
Specific examples include organic acid salts of behenyl dimethylamine and stearyl dimethylamine.

(V) Alkoxydimethylamine salt For example, what is represented by the following general formula is mentioned.
R ¹⁶ —O—R ¹⁷ —N (CH ₃ ) ₂
(In the above formula, R ¹⁶ represents an alkyl group having 12 to 22 carbon atoms, and R ¹⁷ represents an ethylene group or a propylene group.)

(Vi) Alkylamidodimethylamine salt Examples include those represented by the following general formula.
R ¹⁸ —C (═O) NH—R ¹⁹ —N (CH ₃ ) ₂
(In the above formula, R ¹⁸ represents an alkyl group having 11 to 21 carbon atoms, and R ¹⁹ 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 aminopropylethyl dimethyl ammonium, ethyl sulfate lanolin fatty acid aminoethyl triethyl ammonium, ethyl sulfate lanolin fatty acid aminopropyl triethyl ammonium, 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 isononate Examples include rualkyltrimethylammonium 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 thereof is 0.01 to 10% by mass in the aqueous hair cleaning agent of the present invention. More preferably, it is 0.05 to 5% by mass, particularly 0.1 to 2% by mass.

  Next, as the cationized polymer, cationized cellulose, cationized starch, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, cationized xanthan gum, diallyl quaternary ammonium salt / acrylamide copolymer , Vinyl imidazolium trichloride / vinyl pyrrolidone copolymer, hydroxyethyl cellulose / dimethyldiallylammonium chloride copolymer, vinyl pyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinyl pyrrolidone / alkylamino acrylate copolymer, polyvinyl pyrrolidone / Alkylamino acrylate / vinyl caprolactam copolymer, vinyl pyrrolidone / methacrylamidopropyl trimethylammonium chloride Polymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (Sandos Co., Cartaletin), JP-A-53-139734, Examples thereof include cationic polymers described in JP-A-60-36407, and in particular, cationized cellulose, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, diallyl quaternary ammonium salt / Acrylamide copolymers 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 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, salt of reaction product of trimethylammonium substituted epoxide and hydroxyethylcellulose; CTFA name polyquaternium-10), Jaguar series (Rhodia Co., Ltd., salt of reaction product of trimethylammonium substituted epoxide and guar gum), kachinal CF-100 (Toho Chemical Industry Co., Ltd., salt of the reaction product of trimethylammonium substituted epoxide and fenugreek gum), Katchinal CTR-100 (Toho Chemical Industry Co., Ltd., salt of the reaction product of trimethylammonium substituted epoxide and tara gum), Kachinal CLB-100 ( Commercial products such as Toho Chemical Industry Co., Ltd., a salt of a reaction product of trimethylammonium substituted epoxide and locust bean gum) can be used.

  These cationized polymers 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 3% by mass in the aqueous hair cleaning agent of the present invention. Further, 0.05 to 2% by mass, particularly 0.1 to 1% by mass is preferable.

  Examples of silicones include the following.

(1) Dimethylpolysiloxane Examples include those represented by the following general formula (3).
_{(CH 3) 3 Si - [} (CH 3) 2 SiO] d -Si (CH 3) 3 (3)
(In the above formula, d represents a number of 3 to 2 × 10 ^4. )

  Dimethylpolysiloxane exists as dispersed particles in the aqueous hair cleanser, but the average particle size of the dispersed particles is preferably 0.1 to 100 μm from the viewpoint of the finish after drying and the storage stability of the hair cleanser, It is preferably 0.1 to 50 μm, particularly preferably 0.1 to 4 μm, and more preferably 0.1 to 2 μm.

  The average particle diameter of the polydimethylsiloxane emulsion is a median diameter measured by a laser light scattering method, and is measured using, for example, a Coulter LS-130 with a general particle diameter measuring apparatus using laser light scattering. Can do.

  As such a dimethylpolysiloxane, for example, “Toray Dow Corning Co., Ltd.” containing 60% by mass of a dimethylpolysiloxane oil having a d of 300 to 6,500 in the formula (3) and an average particle diameter of 0.8 μm is used. It is possible to use “silicone CF2450” or “Silicon CF2460” commercially available from Toray Dow Corning, which contains 75% by mass of dimethylpolysiloxane oil having d of 300 to 6,500 and an average particle size of 20 μm. it can.

  Such dimethylpolysiloxane 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 viewpoint of foam feeling during hair washing, feel after drying and improvement of gloss, 0.05-6 mass%, especially 0.3-3 mass%, especially 0.5-2 mass% are preferred.

(2) Amino-modified silicone Various amino-modified silicones can be used. In particular, the CTFA Dictionary (USA, Cosmetic Ingredient Dictionary), 9th edition, 2002 under the name of Amodimethicone having an average molecular weight of about 3000 to 100,000. , Volume 1, p107 are preferred. Commercially available products include SM 8704C (Toray Dow Corning), DC 929 (Dow Corning), KT 1989 (Momentive Performance Materials), 8500 Conditioning Agent, DOW CORNING TORAY SS-3588, DOW CORNING TORAY. SILSTLE 104 (Toray Dow Corning) etc. are mentioned.

(3) Other silicones Other than 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 and the like It is done.

  These amino-modified silicones and other silicones may be used in combination of two or more. 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. -5 mass% is preferable, Furthermore, 0.05-2 mass%, Furthermore, 0.1-1 mass% is preferable.

The aqueous hair cleansing agent of the present invention may further contain a pearling agent containing 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 monostearic acid ester and ethylene glycol monobehenic acid ester. Examples of the ethylene glycol difatty acid 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 from the viewpoint of improving the storage stability of the hair cleaning agent and improving the smoothness during rinsing and rinsing, and improving the stability of the hair cleaning agent. 0.1-10 mass% is preferable in the aqueous hair cleansing agent of this invention, Furthermore, 0.5-5 mass%, Especially 1-4 mass% is preferable.

In addition, the aqueous hair cleansing agent of the present invention can contain an oil as another conditioning agent. Oils include hydrocarbon oils such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin;
Glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, coconut oil;
Waxes such as beeswax, whale wax, lanolin, carnauba wax;
Higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, glycerin, myristyl alcohol, behenyl alcohol, cetostearyl alcohol;
Ester oils such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, 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, isostearyl acid, isopalmitic acid;
Other examples include isostearyl glyceryl ether and polyoxypropylene butyl ether. Of these, higher fatty acids, higher alcohols, and glycerides are preferable, and lauric acid, myristyl alcohol, cetyl alcohol, stearyl alcohol, sunflower oil, coconut oil, and the like are particularly preferable. These oil agents can be used alone or in combination of two or more, and the content thereof is preferably 0.1 to 2% by mass, more preferably 0.2 to 1 in the aqueous hair cleansing agent of the present invention. 0.5% by mass, particularly 0.3 to 1% by mass is preferable.

  The aqueous hair cleansing agent of the present invention may contain a viscosity modifier. Viscosity modifiers include hydroxyethylcellulose, methylcellulose, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, isoprene glycol, ethanol, benzyl alcohol, benzyloxyethanol, phenoxyethanol, clay minerals, salts (sodium chloride, ammonium chloride, citric acid) Sodium) and the like. Among them, benzyl alcohol, ethanol, polypropylene glycol, sodium chloride, and sodium citrate are preferable. 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 cleanser of the present invention from the viewpoint of the amount of foam and foam quality, and more preferably 0. 0.05 to 4% by mass, particularly 0.1 to 3% by mass is 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 ingredients include, for example, preservatives; chelating agents; moisturizers such as sorbitol and panthenol; colorants such as dyes and pigments; polar solvent extracts of eucalyptus, shells or nacres with nacre, Its hydrolyzate, honey, royal jelly, protein obtained from silk or hydrolyzate thereof, protein-containing extract obtained from legume seeds, ginseng extract, rice germ extract, hibamata extract, aloe extract, Extracts such as moon peach leaf extract and chlorella extract; pearlizing agent such as titanium oxide; fragrance; ultraviolet absorber; antioxidant; other ENCYCLOPDIA OF SHAMPOO INGREDIENTS (Hunting , Anthony L.L., 198 Year issued, components and the like that are described in MICELLE PRESS)).

  The form of the aqueous hair cleansing agent of the present invention can be appropriately selected from a liquid form, a gel form, etc., but a liquid form using water or a lower alcohol, particularly water, as a medium is preferable.

(Examples 1-9 and Comparative Examples 1-9)
Aqueous hair cleansing agents shown in Table 1 were prepared and evaluated by the following evaluation methods. The results are shown in Table 1. In addition, pH is a value in 25 degreeC at the time of diluting 20 mass times with water.

Evaluation method 1
(1) Speed of foaming Using the apparatus described in Japanese Patent Application Laid-Open No. 10-73584, evaluation was performed by the method described in Examples of the same publication.
That is, FIG. 1 shows a container 10 that houses an object (hair 1) to which a cleaning agent is applied, protrusions 21 and 22 that come into contact with the hair 1, a measuring instrument 50 that measures foam generated in the container 10, and a container 10 is a motor 30 that moves the container 10 so that the lid 20 that guides the foam generated in the container 10 to the measuring instrument 50 and the hair 1 accommodated in the container 10 and the projections 21 and 22 slide. Is a foaming performance evaluation apparatus equipped with Wet hair 1 with an equal amount of water, inject 1.5 mL of an evaluation sample and 0.3 mL of model sebum made of lanolin from the injection hole 25, measure the amount of foaming, and the time until the amount of foam reaches 250 mL It was evaluated by.

  In addition, as hair 1, hair obtained by implanting 30 g of hair having a length of 90 mm on a disk 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 20 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.

The evaluation criteria are as follows.
◎: 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 human hair bundle of 25 cm in length, 5.5 cm in width and 10 g in weight with warm water at 40 ° C, excess water is removed, and 0.5 g of hair cleanser is added. Used and whipped for about 30 seconds. At that time, the sense of slip was sensory-evaluated according to the following five-step criteria. The evaluation was performed by five people, and the average value was obtained. An average of 4.0 or more was shown as “◎”, 3.2 to 3.9 as “◯”, 2.5 to 3.1 as “Δ”, and 2.4 or less as “x”.
5: Glide well 4: Slightly glide 3: Feels normal 2: Does not slide very much 1: Does not slide

(3) Slippery 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. Thereafter, 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 subjected to sensory evaluation based on the following five-step criteria. The evaluation was performed by five people, and the average value was obtained. An average of 4.0 or more was shown as “◎”, 3.2 to 3.9 as “◯”, 2.5 to 3.1 as “Δ”, and 2.4 or less as “x”.
5: Glide well 4: Slightly glide 3: Feels normal 2: Does not slide very much 1: Does not slide

(4) Swelling property of stratum corneum After sterilizing the human buttocks with ethanol, the stratum corneum was scraped and sufficiently dried to prepare a stratum corneum powder. After putting 20 mg of this dried stratum corneum powder into a measurement tube for NMR having a diameter of 5 mm, 0.8 mL of a hair cleaning solution diluted 20 times by mass with ion-exchanged water is poured into the tube, and the height when standing for 2 hours is increased. Measured. The evaluation criteria are relative values with the height when 100 mL of ion-exchanged water is added to 20 mg of the stratum corneum powder, and indicate that the stratum corneum swells as the value increases. The evaluation criteria are as follows.
◎: Less than 110% ○: 110% or more and less than 120% △: 120% or more and less than 125% ×: 125% or more

(5) Itching inhibitory effect Ten male panelists were allowed to wash their hair once a day using each cleaning agent for one month. After 1 month of use, scalp itch after hair washing was evaluated on a five-point scale, with an average value of 10 or more being 4.0 or more on average, “◎”, 3.2 to 3.9 being “◯”, 2.5 -3.1 was shown as "△" and 2.4 or less was shown as "x".
5: Little itching 4: Little itching 3: Feeling the same as usual 2: Slight itching 1: Itching

* 1 Cationized cellulose; “Poise C-80M”, manufactured by Kao Corporation * 2 Used as a pH adjuster.
* 3 In the comparative example, calculation was performed using the value of component (A) or component (A ′), component (B) or component (B ′).

  From Table 1, in the composition of Examples 1-9, while being excellent in foaming, foam sliding, and sliding at the time of rinsing, the effect of suppressing stratum corneum swelling was high, and it had the effect of suppressing itching of the scalp. .

Evaluation method 2
Using the formulations of Example 2 and Comparative Example 6, “component (B) or component (B ′)” in “component (A) and component (B) or component (B ′)” for stratum corneum swellability Evaluation was made by varying the mass% value of (ie, (BorB ′) / ((A) + (BorB ′))).
After sterilizing the human buttocks with ethanol, the stratum corneum was scraped off, and a well-dried stratum corneum powder was prepared. After 20 mg of this dried stratum corneum powder was put into an NMR measuring tube with a diameter of 5 mm, 0.8 mL of a hair cleansing solution adjusted to a surfactant concentration of 30 mM with ion-exchanged water was poured and mixed for 2 hours. The height at the time of standing still was measured. The evaluation standard was a relative value when the height when 100 mL of ion-exchanged water was added to 0.2 mg of the stratum corneum powder was 100%. The evaluation results are shown below.

  According to Table 2, the amount of the polyoxyethylene alkyl ether type nonionic surfactant corresponding to the component (B) in the aqueous hair cleanser according to the formulation of Example 2 is larger than that in the formulation of Comparative Example 6. Even if it was less, it was possible to suppress stratum corneum swelling. From the results shown in Table 1, it can be seen that the smaller the amount of component (B), the better the foaming speed. Therefore, by using a specific polyoxyethylene alkyl ether type nonionic surfactant as used in the examples, Since the stratum corneum swelling is suppressed, the scalp is mild, and the amount of the component (B) can be reduced, so that it is possible to obtain an aqueous hair cleanser that is excellent in foaming.

(Examples 10 to 15)
Hair cleansing agents shown in Table 3 were prepared and evaluated by the following evaluation methods. The results are shown in Table 3. In addition, pH is a value in 25 degreeC at the time of diluting 20 mass times with water.

Evaluation methods (1) Speed of foaming, (2) Slip feeling during foaming, (3) Slip feeling during rinsing, (4) Swelling property of stratum corneum, (5) Itching suppression effect And it evaluated by the method similar to Comparative Examples 1-9 (Table 1). (6) The anti-dandruff property was evaluated by the following method.

(6) Anti-dandruff 10 male panelists were allowed to wash their hair once a day using each cleaning agent for 1 month. After the final shampooing, the shampoo was allowed to live for 2 days without being shampooed, and then again washed twice with 3 g of the same detergent composition, and the two shampoos were collected. The whole amount of the collected hair washing solution was filtered with 50 nylon mesh to remove unnecessary dust and hair. The total amount of the filtrate was filtered through a 255 nylon mesh (100 × 100 μm) whose weight was measured in advance. The nylon mesh was air-dried at room temperature for about 48 hours, and the weight increase was defined as the dandruff weight.

  From Table 3, the compositions of Examples 10 to 15 are excellent in foaming, foam and smoothness at the time of rinsing regardless of the presence or absence of organic carboxylic acid and pH, and suppress the swelling of the stratum corneum and itching of the scalp. It was confirmed that an anti-dandruff effect can be obtained by adding an organic carboxylic acid and adjusting the pH to 5 or less.

Below, the formulation example using the aqueous hair cleaning agent of this invention is shown.
(Example 16) Shampoo
(mass%)
Polyoxyethylene (2) sodium lauryl ether sulfate 12.5
Polyoxyethylene (6) stearyl ether 2.5
Lactic acid 1.0
Dipotassium glycyrrhizinate 0.1
Isodecyl glyceryl ether 2.0
Lauryl hydroxysulfobetaine 1.0
Cationized guar gum 0.2
("Jaguar C-13", Rhodia)
Cationized tara gum 0.2
("Kachinar CTR-100", Toho Chemical Co., Ltd.)
Diallyldimethylammonium chloride / acrylamide copolymer 1.2
("Marcote 550", Ondeonalco, effective content 8.5% by mass)
Dimethylpolysiloxane 2.0
(“Silicone CF2450”, Toray Dow Corning, 60% effective)
Ethylene glycol distearate 2.0
Myristyl alcohol 0.2
Lauric acid 0.1
Polyoxyethylene (16) lauryl ether 0.3
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 of pH adjuster (potassium hydroxide) Amount of pH 3.9 Deionized water Balance

(Example 17) Shampoo
(mass%)
Polyoxyethylene (1) Sodium lauryl ether sulfate 10.0
Polyoxyethylene (4) sodium lauryl ether acetate 4.0
Polyoxyethylene (5) behenyl ether 1.5
Glycolic acid 2.0
Dipotassium glycyrrhizinate 0.1
Palm oil fatty acid monoethanolamide 2.0
Lauroylamidopropylbetaine 2.5
Cationized locust bean gum 0.2
("Kachinar CLB-100", Toho Chemical Co., Ltd.)
Cationized fenugreek gum 0.2
("Kachinar CLB-100", Toho Chemical Co., Ltd.)
Dimethylpolysiloxane 3.0
(“Silicone CF2460”, Toray Dow Corning, 75% effective)
Aminopolyether modified silicone 0.2
(“Silicone SILSTLE 104”, Toray Dow Corning)
Ethylene glycol distearate 1.5
Dipropylene glycol 3.0
Benzyloxyethanol 0.5
l-Menthol 1.0
Sodium chloride 0.2
Perfume Appropriate amount pH adjuster (sodium hydroxide) Amount to reach pH 3.5 Ion exchange water Balance

  The hair cleansing agents of Examples 16 to 17 are excellent in quick foaming, foaming and fingering at the time of rinsing, have an effect of suppressing stratum corneum swelling, mild to the skin and suppressing itching of the scalp. It was. Furthermore, the anti-dandruff effect was also high.

Claims (3)

The following components (A) and (B):
(A) a sulfate-type anionic surfactant represented by the following structural formula (1),
R ¹ O (CH ₂ CH ₂ O) _n SO ₃ M (1)
(In the general formula (1), 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, n is a mass average and represents a number from 0 to 5);
(B) a polyoxyethylene alkyl ether type nonionic surfactant represented by the following structural formula (2),
R ² O (CH ₂ CH ₂ O) _m H (2)
(In the general formula (2), R ² represents a linear or branched alkyl group or alkenyl group having 16 to 22 carbon atoms, and m represents a number of 5 to 30 on a mass average basis);
And an aqueous hair cleanser containing (B) / ((A) + (B)) in a weight ratio of 1/100 to 25/100.   2. The aqueous hair cleanser according to claim 1, further comprising at least one organic carboxylic acid or a salt thereof and having a pH of 1 to 5 at 25 ° C. when diluted 20 times with water.   The aqueous hair cleanser according to claim 1 or 2, further comprising 0.001 to 10% by mass of at least one anti-inflammatory agent.

Images