JP5607311B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention relates to an aqueous hair cleansing agent.

  The main purpose of the hair cleaning agent is to remove dirt on the hair and scalp, to prevent dandruff and itching of the scalp, and to keep it 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. Further, as one means for preventing dandruff, it is generally known that it is effective to sterilize resident bacteria of the scalp, and an antibacterial agent is often added to a hair cleaning agent.

  As an example in which an alkyl ether sulfate is included as a main cleaning component and an antibacterial agent is used in combination, there is a hair cleaning agent as described in Patent Document 1. Although it has been reported that an anionic surfactant and an antibacterial agent are used in combination, excellent detergency and anti-dandruff properties can be obtained, but there is still room for improvement in terms of suppressing itching.

  There are 10 to 20 stratum corneum cells on the skin surface, not limited to the scalp, and these stratum corneum cells have an important role of retaining moisture inside the skin and protecting it from external stimuli. . The above-mentioned alkyl ether sulfate has a strong property of permeating into the stratum corneum to swell the cells and eluting natural moisturizing components such as amino acids and lipids originally present inside the cells. For this reason, repeated washing with a hair cleanser that contains these surfactants as the main ingredient reduces the moisture content of the scalp, so the skin becomes dry and surfactants and other irritating substances tend to enter the skin. As a result, the scalp may become itchy.

  An effective means for suppressing dandruff and itching is to use an amino acid anionic surfactant or an ether carboxylic acid anionic surfactant as the main washing component instead of the alkyl ether sulfate as in Patent Document 2, There is a cleaning composition using a bactericide. Amino acid-based anionic surfactants and ether carboxylic acid-based anionic surfactants have a property to suppress swelling of the stratum corneum compared to alkyl ether sulfates, but are effective in suppressing itching of the scalp, but on the other hand, they are poor in foaming. There was room for improvement in basic performance as a hair cleaning agent.

JP 2001-131593 A Japanese Patent Laid-Open No. 7-109204

  An object of the present invention is to provide a hair cleansing agent that has excellent foaming and anti-dandruff properties and suppresses irritation and itching to the scalp.

  The inventor of the present invention provides a sulfate-type anionic surfactant, specifically a hair cleansing agent containing an alkyl sulfate or an alkyl ether sulfate as a main cleaning agent, and an alkyl ether carboxylate having a specific structure and a specific antibacterial agent. Containing an aqueous hair cleanser that is superior in foaming, which is a basic performance as a cleansing agent, has excellent anti-dandruff properties, further suppresses swelling of the stratum corneum of the skin, has low irritation to the scalp, for example, has little itching It was found that it can be obtained.

That is, according to the present invention,
The following components (A), (B), (C):
(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, alkaline earth metal, ammonium, alkanolamine, or basic amino acid, n represents a number of 0 to 5 in terms of mass average.)
(B) an ether carboxylate type anionic surfactant represented by the following general formula (2) or (3),
R ² O (CH ₂ CH ₂ O) _m CH ₂ COOX (2)
R ² C (═O) NH (CH ₂ CH ₂ O) _m CH ₂ COOX (3)
(In the above general formulas (2) and (3), R ² represents an alkyl or alkenyl group having 10 to 18 carbon atoms, and X is derived from an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid. Represents a cation, and m represents a number of 0.5 to 10 in terms of mass average.)
(C) triclosan, triclocarban, piroctone auramine, zinc pyrithione, selenium disulfide, 3-methyl-4- (1-methylethyl) phenol, a benzalkonium salt or a benzethonium salt represented by the general formula (4) and An antibacterial agent selected from pyridinium salts represented by the general formula (6);

(In the general formula (4), R ⁵ represents an alkyl group having 8 to 14 carbon atoms or a group represented by the following formula (5), and Z ⁻ represents a halogen ion.)

(In the above general formula (6), R ⁶ represents a linear or branched alkyl group having 6 to 18 carbon atoms, and Z ⁻ represents a halogen ion.)
And an aqueous hair cleanser containing water.

  ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding foaming and anti-dandruff property, the aqueous hair washing agent which suppresses the irritation | stimulation and itching to a scalp is implement | achieved.

It is a schematic block diagram of the apparatus used for evaluation regarding the speed of foaming. It is a figure which shows the evaluation result of the stratum corneum swelling rate in an Example.

The aqueous hair cleansing agent of the present invention contains the following components (A), (B), (C) and water. Hereinafter, each component will be specifically described.
(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, alkaline earth metal, ammonium, alkanolamine, or basic amino acid, n represents a number of 0 to 5 in terms of mass average.)
(B) an ether carboxylate type anionic surfactant represented by the following general formula (2) or (3),
R ² O (CH ₂ CH ₂ O) _m CH ₂ COOX (2)
R ² C (═O) NH (CH ₂ CH ₂ O) _m CH ₂ COOX (3)
(In the above general formulas (2) and (3), R ² represents an alkyl or alkenyl group having 10 to 18 carbon atoms, and X is derived from an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid. Represents a cation, and m represents a number of 0.5 to 10 in terms of mass average.)
(C) triclosan, triclocarban, piroctone auramine, zinc pyrithione, selenium disulfide, 3-methyl-4- (1-methylethyl) phenol, a benzalkonium salt or a benzethonium salt represented by the general formula (4) and An antibacterial agent selected from pyridinium salts represented by the general formula (6).

(In the general formula (4), R ⁵ represents an alkyl group having 8 to 14 carbon atoms or a group represented by the following formula (5), and Z ⁻ represents a halogen ion.)

(In the above general formula (6), R ⁶ represents a linear or branched alkyl group having 6 to 18 carbon atoms, and Z ⁻ represents a halogen ion.)

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 represented by the general formula (1).

From the viewpoint of stably obtaining excellent foaming, in the general formula (1), R ¹ is preferably 12 to 14 carbon atoms, and n is preferably 1 to 2 in terms of mass average. , M are preferably ammonium or sodium.
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, and n represents a number of 1 to 2 in terms of mass average. And polyoxyethylene alkyl ether sulfates in which M is ammonium or sodium are preferred.

A component (A) may be used individually by 1 type, or may use 2 or more types together. From the viewpoint of further improving foaming, the content of the component (A) can be, for example, 1% by mass or more, preferably 5% by mass or more, and preferably 8% by mass or more with respect to the entire aqueous hair cleansing agent. More preferably. Further, from the viewpoint of low skin irritation, the content of the component (A) with respect to the entire aqueous hair cleansing agent can be, for example, 25% by mass or less, preferably 23% by mass or less, and preferably 20% by mass. More preferably, it is as follows.
Moreover, content of a component (A) is 1-25 mass% with respect to the whole aqueous hair cleaning agent in this invention from the point which improves the balance of foaming, the liquid property at the time of use, and the fingering property at the time of a rinse. Is more preferable, 5 to 23% by mass, and 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) ether carboxylate surfactant is a group of compounds having a hydrophobic group and a carboxyl group via a polyoxyethylene chain, and an alkyl ether carboxylate. And alkyl amide ether carboxylates. They are represented by the above general formulas (2) and (3), respectively.

In the general formulas (2) and (3), R ² is particularly preferably an alkyl group having 12 to 16 carbon atoms from the viewpoint of foaming and suppression of stratum corneum swelling.

  Moreover, in said general formula (2) and (3), although the average added mole number m of ethylene oxide is 0.5-10, it is preferable that it is 1-6 especially from a foaming viewpoint.

In the general formulas (2) and (3), X as a counter ion is an alkali metal such as sodium or potassium;
Alkaline earth metals such as calcium and magnesium;
Ammonium;
Ammonium derived from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine;
And cations derived from basic amino acids such as arginine and lysine.

A component (B) may be used individually by 1 type, or may use 2 or more types together.
Content of a component (B) can be 0.5 mass% or more with respect to the whole aqueous hair cleaning agent from a viewpoint of stratum corneum swelling suppression, and it is preferable to set it as 1 mass% or more, and is 2 mass. % Or more is more preferable. Further, from the viewpoint of further improving foaming, the content of the component (B) with respect to the entire aqueous hair cleansing agent can be, for example, 10% by mass or less, preferably 8% by mass or less, and preferably 6% by mass or less. More preferably.
The content of the component (B) is preferably 0.5 to 10% by mass with respect to the entire aqueous hair cleanser of the present invention, from the viewpoint of further improving the stratum corneum swelling suppression, foaming, and finger balance during rinsing. Further, 1 to 8% by mass, particularly 2 to 6% by mass is preferable.

  From the viewpoint of excellent foaming, the components (A) and (B) may have a mass ratio represented by (B) / ((A) + (B)) × 100 (%) of 50% or less. Among these, 40% or less, particularly 30% or less is preferable. Further, from the viewpoint of mildness with respect to the scalp, the mass ratio represented by (B) / ((A) + (B)) × 100 (%) is, for example, 5% or more, preferably 10% or more. Good.

Next, the component (C) will be described. Examples of the antibacterial agent (C) of the present invention include triclosan, triclocarban, piroctone auramine, zinc pyrithione, selenium disulfide, 3-methyl-4- (1-methylethyl) phenol, the above general formula (4) Benzalkonium salt or benzethonium salt represented by general formula (6) and a pyridinium salt represented by general formula (6).
Among these, piroctone auramine, zinc pyrithione, and benzalkonium salt are preferable, and zinc pyrithione is particularly preferable.

The content of component (C) can be, for example, 0.1% by mass or more, and preferably 0.4% by mass or more, based on the entire aqueous hair cleansing agent, from the viewpoint of anti-dandruff properties. Further, from the viewpoint of product stability, the content of the component (C) with respect to the entire aqueous hair cleaning agent can be, for example, 4% by mass or less, and is preferably 3% by mass or less.
Further, from the viewpoint of obtaining sufficient antibacterial properties, the component (C) is preferably contained in the aqueous hair cleansing agent in an amount of 0.1 to 4% by mass, particularly 0.4 to 3% by mass.

In the present invention, a hair cleansing agent containing a specific alkyl sulfate or alkyl ether sulfate type anionic surfactant as a main cleaning agent contains a specific alkyl ether carboxylate type anionic surfactant and a specific antibacterial agent. As a result, the foaming and anti-dandruff properties are excellent, and the stratum corneum swelling of the skin is suppressed, for example, itching is small.
Here, the reason why the balance of foaming, anti-dandruff property, and low irritation to the scalp is improved by including the component (A), the component (B) and the component (C) as essential components is not necessarily clear, Component (B) is effectively adsorbed on the surface of the scalp stratum corneum to form a protective film, thereby effectively suppressing swelling of the stratum corneum while maintaining the functions of component (A) and component (C) It is guessed.

  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 ester, polyoxyalkylene sorbit fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene ether Examples include alkylene (hardened) castor oil, sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, fatty acid alkanolamide, alkyl glycoside, monoalkyl or monoalkenyl glyceryl ether, and the like.

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 nonionic surfactants, 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, such as oleic acid diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide. Coconut oil fatty acid monoethanolamide, lauric acid isopropanolamide, lauric acid monoethanolamide, and the like.

  Monoalkyl glyceryl ether or monoalkenyl glyceryl ether is also a suitable nonionic surfactant, and the alkyl group or alkenyl group may be a linear or branched alkyl group having 4 to 10 carbon atoms, particularly 8 to 10 carbon atoms. 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 -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 ), (B), and fatty acid amide propyl betaine, fatty acid alkanolamide, and monoalkyl glyceryl ether are particularly preferable because not only foaming power is improved but also appropriate liquidity 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. Furthermore, the range of 0.5-8 mass%, especially 1-6 mass% is preferable.

The aqueous hair cleansing agent of the present invention may further contain a cationic surfactant, a cationized polymer and silicones 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 Q ⁻
(In the above general formula, R ¹¹ represents an alkyl group having 12 to 22 carbon atoms, and Q ⁻ 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 Q ⁻
(In the above general formula, R ¹² represents an alkyl group having 12 to 22 carbon atoms, R ¹³ represents an ethylene group, a propylene group or a hydroxypropylene group, and Q ⁻ 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 Q ⁻
(In the above general formula, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and Q ⁻ 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 Examples include those represented by the following general formula.
R ¹⁶ —O—R ¹⁷ —N (CH ₃ ) ₂
(In the above general 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 general 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 ethylsulfate isononanoate and Examples thereof include alkyltrimethylammonium 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, diallyldialkylammonium salt / acrylamide copolymer, Vinyl imidazolium trichloride / vinyl pyrrolidone copolymer, hydroxyethyl cellulose / dimethyl diallylammonium chloride copolymer, vinyl pyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinyl pyrrolidone / alkyl amino acrylate copolymer, polyvinyl pyrrolidone / Alkyl amino acrylate / vinyl caprolactam copolymer, vinyl pyrrolidone / methacrylamidopropyl trimethyl ammonium chloride Copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (US Sandos, Cartaletin), JP-A-53-139734 And cationic polymers described in JP-A-60-36407. Particularly preferred are cationized cellulose, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, and diallyldialkylammonium salt / acrylamide copolymer.

  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, salt of reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name polyquaternium-10), Poise C-60H, Poise C-80M, Poise C-15 L (Kao Corporation, a salt of a reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name polyquaternium-10), Jaguar series (Rhodia, a salt of a reaction product of trimethylammonium substituted epoxide and guar gum), Kachinal CF -100 (Toho Chemical Industry Co., Ltd., salt of reaction product of trimethylammonium substituted epoxide and fenugreek gum), Kachinal CTR-100 (Toho Kagaku Kogyo Co., Ltd., salt of reaction product of trimethylammonium substituted epoxide and tara gum), Katchinal CLB- Commercially available products such as 100 (Toho Chemical Industry Co., Ltd., salt of 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 those shown in the following (I) to (III).

(I) Dimethylpolysiloxane Examples include those represented by the following general formula (7).
_{(CH 3) 3 Si - [} (CH 3) 2 SiO] d -Si (CH 3) 3 (7)
(In the general formula (7), d represents a number of 3 to 20,000.)

  Dimethylpolysiloxane is present 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, Furthermore, it is preferable that it is 0.1-50 micrometers, especially 0.1-4 micrometers, especially 0.1-2 micrometers.

  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 by a general particle diameter measuring apparatus using laser light scattering. Can do.

  As such dimethylpolysiloxane, for example, Toray Dow Corning Co., Ltd., which contains 60% by mass of dimethylpolysiloxane oil having d of 300 to 6,500 in the above general formula (7) and has an average particle diameter of 0.8 μm "Silicone CF2450", which contains 75% by mass of dimethylpolysiloxane oil having a d of 300-6,500 and an average particle diameter of 20 µm, "Silicon CF2460" manufactured by Toray Dow Corning, Inc. can do.

  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, It is preferable to contain 0.05-6 mass%, especially 0.3-3 mass%, especially 0.5-2 mass%.

(II) Amino-modified silicone A variety of amino-modified silicones can be used. In particular, the CTFA Dictionary (US, Cosmetic Ingredient Dictionary), 9th edition, 2002 with an average molecular weight of about 3000 to 100,000 under the name of Amodimethicone. , Volume1, 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.

(III) 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, etc. 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% by mass is preferable, more preferably 0.05-2% by mass, and particularly preferably 0.1-1% by mass.

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 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.
These may be used in combination of two or more, 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 cleaning 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, 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, isostearic 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, glycerin, benzyl alcohol, benzyloxyethanol, phenoxyethanol, clay minerals, salts (sodium chloride, ammonium chloride, Sodium citrate and the like), among which 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 components include, for example, preservatives; chelating agents; humectants such as sorbitol and panthenol; colorants such as dyes and pigments; polar solvent extracts of eucalyptus; proteins obtained from shells or pearls having a nacre Protein obtained from hydrolyzate, honey, royal jelly, 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, chlorella extract; pearl pigments such as mica titanium; fragrances; UV absorbers; antioxidants; other ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (Hunting, Anthony LL, published in 1983, 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 1-5 and Comparative Examples 1-6)
Hair cleaning 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) Speed of foaming Evaluation was performed by the apparatus and method described in JP-A-10-73584.
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 ○: 100 seconds or more and less than 200 seconds Δ: 200 seconds or more and less than 300 seconds ×: 300 seconds or more

(2) Anti-dandruff Property Ten male panelists were allowed to wash their hair once a day using each cleaning agent for one 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. The average value of the dandruff weight of 10 people was obtained and indicated by the following criteria.
A: Dandruff weight ≦ 30 mg
○: 30 mg <dandruff weight ≦ 40 mg
Δ: 40 mg <dandruff weight ≦ 50 mg
X: 50 mg <dandruff weight

(3) Swelling property of stratum corneum After disinfecting 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 standard is a relative value when the height when 0.8 mL of ion exchange water is added to 20 mg of the stratum corneum powder is 100%, and the larger the value, the more the stratum corneum swells. 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

(4) Itching suppression 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.

  From Table 1, in the composition of Examples 1-5, while being excellent in foaming and anti-dandruff property, the effect which suppresses stratum corneum swelling was high, and it had the effect which suppresses the itchy scalp.

(Prescription example)
(Example 6) Shampoo
(mass%)
Polyoxyethylene (2) sodium lauryl ether sulfate 12.5
Polyoxyethylene (4.5) sodium lauryl ether acetate 4.0
Zinc pyrithione 0.3
Benzalkonium chloride (C12 / C14 = 50/50) 0.2
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
Cetyl 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 pH adjuster (citric acid) Amount to reach pH 6.5 Ion-exchanged water Balance

(Example 7) Shampoo
(mass%)
Polyoxyethylene (1) Sodium lauryl ether sulfate 10.0
Polyoxyethylene (10) Myristyl ether sodium acetate 4.0
Cetylpyridinium chloride 1.5
Palm oil fatty acid monoethanolamide 0.5
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.)
Aminopolyether modified silicone 0.2
(“Silicone SILSTLE 104”, Toray Dow Corning)
Dipropylene glycol 3.0
Benzyloxyethanol 0.5
l-Menthol 1.0
Sodium chloride 0.2
Perfume Appropriate amount of pH adjuster (malic acid) Amount to reach pH 7.0 Ion-exchanged water Balance

  The hair cleansing agents of Examples 6 and 7 were excellent in foaming and anti-dandruff properties, and had the effect of suppressing stratum corneum swelling and suppressing scalp itching.

  In addition, although the example which uses a zinc pyrithione and a cetyl pyridinium chloride as a component (C) was shown typically in the above Example, also about the other antibacterial agents mentioned above, by using with a component (A) and (B), Similar effects can be obtained.

(Example 8, Comparative Example 7)
In this example, the ability to suppress stratum corneum swelling of a sample containing the component (A) was evaluated by the following method. The sample formulation and pH are shown in Table 2.

(Preparation of surfactant sample)
The following were used as the surfactant.
Component (A): Polyoxyethylene (1) Ammonium lauryl ether sulfate Component (B): Polyoxyethylene (4.5) Sodium lauryl ether acetate Comparative component (B ′): Sodium cocoyl methyl taurate Sample using malic acid or caustic soda The pH of the was adjusted to 6.0.

(Square layer swelling test)
It measured according to the said (3) stratum corneum swelling test about Examples 1-5 and Comparative Examples 1-6.
Specifically, components (A) and (B) or (B ′) are added to ion-exchanged water so that the surfactant concentration, that is, the total concentration of components (A) and (B) or (B ′) is 30 mM. ) Were added to prepare surfactant samples having various concentrations shown in Table 2. This surfactant concentration corresponds to the concentration when the shampoo is foamed and washed on the hair.
On the other hand, 20 mg of stratum corneum powder taken from a human sputum was placed in an NMR tube, and 0.8 mL of the surfactant sample was added and mixed.
After adding the surfactant sample, the height of the stratum corneum after standing for 2 hours was measured. The results are shown in FIG. In FIG. 2, the “swelling rate of the stratum corneum” on the vertical axis means that the height of the stratum corneum in the sample left to stand for 2 hours after adding 0.8 mL of ion-exchanged water instead of the surfactant sample is 100%. The measured values of the stratum corneum height of each sample are shown as relative numerical values. A larger value indicates that the stratum corneum swelled.

FIG. 2 shows that in Example 8, the swelling of the stratum corneum can be effectively suppressed by adding a small amount by using the component (B) together with the component (A) and lowering the pH.
In the above, for the sake of convenience, an example using the components (A) and (B) has been shown, but the tendency shown in FIG. 2 is similarly recognized when the component (C) is further contained.

1 Hair 10 Container 20 Lid 21 Projection 22 Projection 25 Injection Hole 30 Motor 50 Meter

Claims (3)

The following components (A), (B), (C):
(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, alkaline earth metal, ammonium, alkanolamine, or basic amino acid, n represents a number of 0 to 5 in terms of mass average.)
(B) an ether carboxylate type anionic surfactant represented by the following general formula (2) or (3),
R ² O (CH ₂ CH ₂ O) _m CH ₂ COOX (2)
R ² C (═O) NH (CH ₂ CH ₂ O) _m CH ₂ COOX (3)
(In the above general formulas (2) and (3), R ² represents an alkyl or alkenyl group having 10 to 18 carbon atoms, and X is derived from an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid. Represents a cation, and m represents a number of 1 to 6 on a mass average basis.)
(C) Triclosan, triclocarban, piroctone auramine, zinc pyrithione, 3-methyl-4- (1-methylethyl) phenol, a benzalkonium salt or a benzethonium salt represented by the general formula (4) and the general formula (6) ) An antibacterial agent selected from pyridinium salts represented by

(In the general formula (4), R ⁵ represents an alkyl group having 8 to 14 carbon atoms or a group represented by the following formula (5), and Z ⁻ represents a halogen ion.)

(In the above general formula (6), R ⁶ represents a linear or branched alkyl group having 6 to 18 carbon atoms, and Z ⁻ represents a halogen ion.)
And contain water,
The proportion of the components (A) and the component to the sum of (B) (B) is, in mass ratio, Ru der less 47% or more 27%, water-based shampoo.   The aqueous hair cleansing agent according to claim 1, wherein the content of the component (B) is 1% by mass or more and 8% by mass or less.   The aqueous hair cleaning agent according to claim 1 or 2, comprising 0.1 to 4% by mass of the component (C) with respect to the entire aqueous hair cleaning agent.

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