JP2006182723A - Aqueous hair shampoo - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair shampoo which has a good lathering property and a good smooth foam property, when used for washing hair, gives a smooth touch, when rinsed, gives gloss and collectability to finished hair, has good low temperature stability, and is low irritative. <P>SOLUTION: This aqueous hair shampoo comprises the ingredients (A) to (B). (A) 5 to 30 wt.% of a sulfate type surfactant represented by the general formula: R-O-(C<SB>2</SB>H<SB>4</SB>O)<SB>n</SB>-SO<SB>3</SB>M (R is an 8 to 18C alkyl or alkenyl; (n) is 0 or a positive integer; M is sodium or ammonium), and comprising 30 to 45 wt.% of (n)=0, 18 to 27 wt.% of (n)=1, 10 to 20 wt.% of (n)=2, and the remainder of (n)≥3, wherein the total amount of n=0 to 2 is ≥70 wt.% based on the total sulfates. (B) 0.05 to 10 wt.% of an amino-modified silicone derivative having a group containing both OH and N atom as a side chain bound to Si atom. (C) 0.1 to 10 wt.% of a silicone oil represented by the general formula; R'(CH<SB>3</SB>)<SB>2</SB>SiO-[(CH<SB>3</SB>)<SB>2</SB>SiO]<SB>m</SB>-Si(CH<SB>3</SB>)<SB>2</SB>R' [R' is CH<SB>3</SB>or OH; (m) is 50 to 20,000] and having an average particle diameter of <50 μm as dispersed particles. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention contains a sulfate type surfactant and a modified silicone, has good foaming and abundant foam amount at the time of shampooing, gives excellent slipping feeling to the hair at the time of foaming and rinsing, and gives gloss. Further, the present invention relates to an aqueous hair cleansing agent that has a low temperature stability and good low temperature stability.

  In recent years, shampoos not only have basic performance such as detergency, good foaming, abundant foam amount, etc., but also have conditioning effects such as foam slipping feeling when foaming, slipping feeling when rinsing, and no creaking It is supposed to be. In order to meet such demands, various amino-modified silicones such as amodimethicone having an average molecular weight of about 3000 to 100,000 are described in CTFA, SM 8704C (Toray Dow Corning Silicone), DC929 (Dow Corning) ), KT1989 (GE Toshiba Corporation), etc., are blended in shampoos. However, shampoos using these amino-modified silicones are not sufficient in terms of foaming and foam amount, and have not yet provided satisfactory slipping feeling.

  As one means for improving the slipperiness, a hair cosmetic composition in which an amino-modified silicone derivative having a side chain bonded to a silicon atom having a group containing both a hydroxyl group and a nitrogen atom has been studied. For example, Patent Document 1 relates to a hair cosmetic containing an amino-modified silicone, and in particular, a shampoo composition using Example 1 sodium lauryl ether sulfate (Empicol ESB 3, Huntsman) having an average addition mole number of ethylene oxide of 2 as an anion activator. Is described. However, the shampoo composition containing the amino-modified silicone derivative has a problem that foaming deteriorates and the amount of foam decreases.

  On the other hand, a representative alkyl sulfate as a component of the cleaning agent has been most frequently used because of its high detergency and a large amount of foaming. However, when alkyl sulfates are used alone, there is a great dissatisfaction with the feeling of washing such as squeakiness, and polyoxyethylene addition type alkyl sulfates (alkyl ether sulfates), in particular ethylene oxide, average 2 in order to improve the feel. Addition of ˜3 moles has been used in shampoos because of its good feeling during washing. Although the squeaky feeling has been eliminated by adding ethylene oxide, the speed of the original foaming is greatly inferior, and in both methods, it is necessary to achieve both quick foaming, good foam feel, and reduction of squeaking feeling. It was insufficient.

International Publication No. 2003/066007 Pamphlet

  Therefore, the present invention has good foaming and abundant foam amount at the time of shampooing, has a smooth foam quality and a smooth feel at the time of rinsing, gives gloss to the finished hair, and has low temperature stability. An object is to provide an aqueous hair cleansing agent that is good and less irritating.

  In the polyoxyethylene addition type alkyl sulfate, the present inventors have a ratio of sulfate distributed on the side where the number of added moles of ethylene oxide is small, that is, the ratio of sulfates having 0 to 2 added moles within a certain range. When a sulfate component, an amino-modified silicone derivative having a group containing both a hydroxyl group and a nitrogen atom in the side chain bonded to a silicon atom, and a silicone oil having a small particle diameter are used in combination, a hair cleanser that satisfies the above requirements is obtained. I found out that

  That is, the present invention provides an aqueous hair cleanser containing the following components (A), (B) and (C).

(A) The following general formula (1)
R—O— (C ₂ H ₄ O) _n —SO ₃ M (1)
[Wherein, R represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, n represents 0 or a positive integer, and M represents sodium or ammonium. ]
Wherein n = 0 sulfate 30-45 wt%, n = 1 sulfate 18-27 wt%, n = 2 sulfate 10-20 wt%, and the balance is n = Sulphate type surfactant composed of 3 or more sulfates and n = 0 to 2 in total of 70% by weight or more of total sulfates 5 to 30% by weight

(B) Amino-modified silicone derivative having a group containing both a hydroxyl group and a nitrogen atom as a side chain bonded to a silicon atom 0.05 to 10% by weight

(C) Silicone oil represented by the following general formula (2) present as dispersed particles having an average particle size of less than 50 μm 0.1 to 10% by weight
R ′ (CH ₃ ) ₂ SiO — [(CH ₃ ) ₂ SiO] _m —Si (CH ₃ ) ₂ R ′ (2)
[Wherein, R ′ represents a methyl group or a hydroxy group, and m represents a number of 50 to 20,000. ]

  The hair cleanser of the present invention has good foaming, abundant foam amount, and smooth foam quality at the time of shampooing, has a smooth feel when rinsed, gives gloss to the finished hair, and is stable at low temperature Good in nature and hypoallergenic.

The sulfate type surfactant of component (A) of the present invention is represented by the general formula (1)
R—O— (C ₂ H ₄ O) _n —SO ₃ M (1)
It is represented by In the present invention, the number of moles of ethylene oxide added has a specific distribution and contains a large amount of sulfate having a small number of moles of addition, that is, n = 0 is 30 to 45% by weight, and n = 1 is 18 to 27% by weight. , N = 2 is 10 to 20% by weight, and the remainder has a distribution composed of sulfates of n = 3 or more, and the total of sulfates of n = 0 to 2 is 70% by weight or more in the total sulfates It has good foam quality, foam amount, and feel by the sulfate type surfactant. Here, the sulfate-type surfactant having a distribution is preferably a sulfate having the same alkyl chain length and differing only in the number of added moles of ethylene oxide.

  Among these, from the viewpoint of achieving both quick foaming and good foam feel, the distribution of the number of moles of added ethylene oxide n is 33 to 43% by weight n = 0, 20 to 25% by weight n = 1, and n = 2. It is preferably composed of 13 to 18% by weight, and the balance is composed of sulfates with n = 3 or more, in particular, n = 0 is 35 to 41% by weight, n = 1 is 21 to 23% by weight, and n = 2 More preferably, the content is 14 to 17% by weight, and the remainder is composed of n = 3 or more sulfates. In addition, the ratio of sulfate of n = 0 to 2 in the sulfate type surfactant component is 70% by weight or more from the same viewpoint, but is 70 to 85% by weight of the total sulfate. It is preferable.

Such a sulfate-type surfactant is obtained by using, for example, an alcohol ethoxylate obtained by adding 0.85 to 1.35 times moles of ethylene oxide with respect to a higher alcohol ROH, using 0.95 to 1.0 equivalent of SO _3. After sulfated, it can be produced by neutralizing with sodium hydroxide or ammonia. Further, M in the general formula (1) is more preferably ammonium from the viewpoint of foam feeling.

  The content of the component (A) sulfate-type surfactant is 5 to 30% by weight in the aqueous hair cleansing agent of the present invention. Good foaming, abundant foam amount, and slippery foam when washing hair From the viewpoint of quality, 7 to 23% by weight, particularly 10 to 20% by weight is preferable.

  The component (B) silicone derivative of the present invention has a group containing both a hydroxyl group and a nitrogen atom as a side chain bonded to a silicon atom, but as a preferred specific example, it is represented by the following average general formula (3): What is done.

[In the formula, each R ¹ independently represents a monovalent hydrocarbon group, a hydroxy group or an alkoxy group, each R ² independently represents a monovalent hydrocarbon group, and each R ³ independently represents Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ independently represents a group represented by the formula (4) or (5), a represents a number of 25 to 1000, b shows the number of 1-200.

(In the formula, each Y independently represents a hydrogen atom or a group —CH ₂ —CH (OH) —R ³ —OH, and each R ⁵ independently represents a hydrogen atom or a group —R ³ NY ₂ (Y And R ³ are the same as above, but not all Y are hydrogen atoms.)]

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

Examples of the monovalent hydrocarbon group for R ² include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, a xylyl group, and the like. Examples thereof include aryl groups having 6 to 10 carbon atoms; aralkyl groups having 6 to 10 carbon atoms such as benzyl group and phenethyl group. Especially, a C1-C3 alkyl group, especially a methyl group are preferable.

Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms of R ³ include methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, methyltrimethylene group, ethylethylene group, and dimethylethylene group. _{;-( CH 2) 2 -C 6 H} 4 - alkylene represented - an arylene group. Of these, an alkylene group having 2 to 4 carbon atoms is preferable.

R ⁴ is preferably a group represented by the formula (4), and R ⁵ is N- (2,3-dihydroxypropyl) aminoethyl or N, N-bis (2,3-dihydroxypropyl) aminoethyl. Is preferred. Of Y, the group —CH ₂ —CH (OH) —R ³ —OH is preferably a 2,3-dihydroxypropyl group.

  a is preferably 75 to 400, and b is preferably 1 to 20.

  The silicone derivative of component (B) can be synthesized, for example, by reacting an amino-modified silicone with an epoxy functional compound such as glycidol as described in EP0399706A2. Examples of the silicone derivative of component (B) include compounds represented by the following formula, and commercially available products include “8500 Conditioning Agent” (CAS No.237753-63-8) manufactured by Dow Corning. Is mentioned.

[Wherein R is a hydrocarbon group of C ₁₃ H _{27 to} C ₁₅ H ₃₁ ; Z is 75% of the group —CH ₂ CH (OH) CH ₂ OH, and the remainder is a hydrogen atom. ]

  Two or more kinds of component (B) may be used in combination, and the content thereof is 0.05 to 10% by weight in the cleaning composition of the present invention, but the hair slipping from shampooing to rinsing, softness, and From the viewpoint of slipping after drying, 0.07 to 5% by weight is preferable, and 0.1 to 3% by weight is particularly preferable.

  The silicone oil represented by the general formula (2) existing as dispersed particles having an average particle size of less than 50 μm, which is the component (C) of the present invention, is substantially water-insoluble and non-volatile. In particular, those provided as a water-insoluble highly polymerized dimethylpolysiloxane emulsion obtained by emulsion polymerization are preferred.

  The average particle size of the dispersed particles of silicone of component (C) is less than 50 μm, preferably 4 μm or less, particularly 3 μm or less, and more preferably 2 μm or less. The average particle size is preferably 0.1 μm or more from the viewpoint of the feeling of use and the conditioning effect.

  Examples of such silicone oil include “Silicone CF2450” from Toray Dow Corning Co., Ltd., which contains 60% by weight of dimethylpolysiloxane oil of formula (2) where m is 300 to 6500 and has an average particle size of 0.5 μm. Commercially available silicone emulsions can be used.

  The silicone oil having a small particle size such as component (C) is considered to be 0.01 to 10% by weight in the aqueous hair cleansing agent of the present invention from the viewpoint of foam feeling at the time of hair washing, feel after drying and improvement of gloss. Is preferably 0.05 to 6% by weight, more preferably 0.5 to 3% by weight, especially 1 to 2% by weight.

  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. Of these, alkylglycosides, polyoxyalkylene (C ₈ -C ₂₀ ) fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamides, monoalkyl glyceryl ethers and monoalkenyl glyceryl ethers are preferred.

  The fatty acid alkanolamide may be either a monoalkanolamide or a dialkanolamide, and preferably has an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms. In particular, 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.

  Of the monoalkyl glyceryl ethers and monoalkenyl glyceryl ethers, monoalkyl glyceryl ethers are preferable, and the alkyl 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 -Decyl group, isodecyl group and the like can be mentioned, and 2-ethylhexyl group and isodecyl group are particularly preferable.

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

  These nonionic or amphoteric surfactants can be used alone or in combination of two or more in the aqueous hair cleanser. However, when the aqueous hair cleanser of the present invention is in the form of an aqueous liquid cleanser. Using both fatty acid amide propyl betaine or fatty acid alkanolamide as a surfactant other than component (A) together with component (A) not only provides better foaming power but also provides appropriate liquidity. Particularly preferred.

  The content of the nonionic or amphoteric surfactant is preferably 0.1 to 15% by weight, more preferably 0.5 to 8% by weight, and particularly 1 to 6% by weight in the hair cleansing agent of the present invention. Is preferable.

  In the present invention, one or more anionic surfactants other than the sulfate type surfactant may be further contained. Examples include sulfonate type surfactants and carboxylate type surfactants, such as sulfosuccinic acid alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, higher fatty acid salts, alkane sulfonic acid salts, alkyl ether carboxylic acids. Examples thereof include acids or salts thereof.

  Furthermore, the aqueous hair cleansing agent of the present invention can contain a cationic polymer from the viewpoints of foam texture, foam slipperiness, crease reduction during washing, and smoothness during drying. Examples of cationic polymers include cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, homopolymers of diallyl quaternary ammonium salts, diallyl quaternary ammonium salts / acrylamide copolymers, quaternized polyvinyl pyrrolidone derivatives, polyglycols. Polyamine condensate, vinyl imidazolium trichloride / vinyl pyrrolidone copolymer, hydroxyethyl cellulose / dimethyldiallylammonium chloride copolymer, vinyl pyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinyl pyrrolidone / alkylamino acrylate copolymer , Polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer, vinylpyrrolidone / methacrylamidopropyl trimethyl chloride Ammonium copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (Cartaretin manufactured by Sandos, USA), JP-A-53-139734 And cationic polymers described in JP-A-60-36407. In particular, a cationized cellulose derivative, a cationized guar gum derivative, and a diallyl quaternary ammonium salt / acrylamide copolymer are preferable.

  Two or more kinds of cationic polymers may be used in combination, and the content thereof is the aqueous hair cleansing agent of the present invention from the viewpoints of improving the foam quality at the time of washing, collecting the hair after drying, and improving the touch. The content is preferably 0.02 to 5% by weight, more preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0.7% by weight.

  In order to improve the finish after drying, the aqueous hair cleansing agent of the present invention can further contain a cationic surfactant and conditioning components such as silicones other than the component (B).

  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) Alkyltrimethylammonium salt Examples include those represented by the following general formula.

R ¹¹ −N ⁺ (Me) ₃ X ⁻
[Wherein R ¹¹ represents an alkyl group having 12 to 22 carbon atoms, Me represents a methyl group, and X ⁻ represents a halogen (chlorine or bromine) ion or an alkyl sulfate ion having 1 to 2 carbon atoms. ]

(ii) Alkoxytrimethylammonium salt Examples include those represented by the following general formula.

R ¹² —O—R ¹³ —N ⁺ (Me) ₃ X ⁻
[Wherein R ¹² represents an alkyl group having 12 to 22 carbon atoms, R ¹³ represents an ethylene group or a propylene group, Me represents a methyl group, and X ⁻ is the same as described above. ]

(iii) Dialkyldimethylammonium salt Examples include those represented by the following general formula.

R ¹⁴ ₂ −N ⁺ (Me) ₂ X ⁻
[Wherein, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, Me represents a methyl group, and X ⁻ is the same as above. ]

(iv) Alkyldimethylamine (and its salts)
For example, what is represented by the following general formula is mentioned.

R ¹⁵ -N (Me) ₂
[Wherein, R ¹⁵ represents an alkyl group having 12 to 22 carbon atoms, and Me represents a methyl group. ]

(v) Alkoxydimethylamine and salts thereof Examples thereof include those represented by the following general formula.

R ¹⁶ —O—R ¹⁷ —N (Me) ₂
[Wherein R ¹⁶ represents an alkyl group having 12 to 22 carbon atoms, R ¹⁷ represents an ethylene group or a propylene group, and Me represents a methyl group]

(vi) alkylamidodimethylamine (and its salt)
For example, what is represented by the following general formula is mentioned.

R ¹⁸ —C (═O) NH—R ¹⁹ —N (Me) ₂
[Wherein, R ¹⁸ represents an alkyl group having 11 to 21 carbon atoms, R ¹⁹ represents an ethylene group or a propylene group, and Me represents a methyl group. ]

Examples of cationic surfactants other than the above (i) to (vi) include ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium (alkanoylaminopropyl dimethylethylammonium ethyl sulfate, alkanoyl group derived from lanolin), ethyl sulfate lanolin fatty acid aminoethyl triethylammonium, ethyl lanolin fatty acid aminopropyl triethylammonium sulfate, methyl sulfate lanolin fatty acid aminoethyl trimethylammonium 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, Aminopuro ethylsulfate isostearate Le dimethylammonium, ethyl sulfate, isononanoic acid aminopropyl ethyl dimethyl ammonium and alkyl trimethylammonium saccharin.

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

  Examples of silicones other than components (B) and (C) include those shown below.

(1) Dimethylpolysiloxane As dimethylpolysiloxane other than component (C), volatile dimethylpolysiloxane and low molecular weight liquid non-volatile dimethylpolysiloxane can be used in combination. Commercially available products include SH200 (Toray Dow Corning Silicone), KF96 (Shin-Etsu Chemical), and the like.

(2) Amino-modified silicone Various amino-modified silicones other than the component (B) of the present invention can be used, but in particular, the CTFA dictionary (US, Cosmetic Ingredient Dictionary under the name of Amodimethicone having an average molecular weight of about 3000 to 100,000. ) Those described in the third edition are preferred. This amino-modified silicone is preferably used as an aqueous emulsion. Examples of commercially available products include SM 8704C (Toray Dow Corning Silicone), DC 929 (Dow Corning), KT 1989 (GE Toshiba). It is done.

(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, etc. It is done.

  Two or more types of silicones other than components (B) and (C) may be used in combination, and from the point of smoothness from the time of shampooing to the time of rinsing, the content is determined in the aqueous hair cleansing agent of the present invention. 0.01 to 10% by weight, more preferably 0.05 to 6% by weight, particularly 0.3 to 3% by weight, especially 0.5 to 2% by weight.

  Moreover, an oil agent can be contained as another conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin; glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; beeswax, whale wax, lanolin, carnauba wax, etc. Waxes: Esters 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; myristyl al Lumpur, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, 2-octyldodecanol, higher alcohols such as cetostearyl alcohol, other isostearyl glyceryl ether, polyoxypropylene butyl ether. Of these, higher alcohols are preferable, and myristyl alcohol, cetyl alcohol, and stearyl alcohol are particularly preferable. These oil agents can be used alone or in combination of two or more, and the content thereof is preferably 0.2 to 2% by weight, more preferably 0.3 to 1.8% by weight, particularly 0.5 to 1.5% by weight in the aqueous hair cleansing agent of the present invention. % By weight is preferred.

  Further, a pearling agent containing ethylene glycol monoalkyl ester or ethylene glycol dialkyl ester can be contained in order to improve the texture and stability of the cleaning agent. Examples of the ethylene glycol monoalkyl ester include ethylene glycol monostearyl ester and ethylene glycol monobehenyl ester. Examples of the ethylene glycol dialkyl ester include ethylene glycol distearyl ester and ethylene glycol dibehenyl ester. Two or more of these may be used in combination, and the content thereof is preferably 0.5 to 8% by weight, more preferably 0.7 to 5% by weight, particularly 1 to 3% by weight in the aqueous hair cleansing agent of the present invention. preferable. From the viewpoint of improving the stability of the cleaning agent, the weight ratio (pearling agent / sulfate type surfactant) of the pearlizing agent and sulfate type surfactant in the hair cleaning agent of the present invention is 1 / 10 to 2/5 is preferable, 1/7 to 3/10, more preferably 1/6 to 1/4.

  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.) and the like. Among them, salts, particularly 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 weight in the aqueous hair cleansing agent of the present invention in terms of the amount of foam and foam quality, and more preferably 0.05 to 3% by weight, particularly 0.1 to 1.5% by weight is preferred.

  In addition to the above-described components, the aqueous hair cleansing agent of the present invention can be appropriately blended with components used in ordinary hair cleansing agents depending on the purpose. Such components include, for example, anti-dandruff agents; vitamin agents; bactericides; anti-inflammatory agents; antiseptics; chelating agents; moisturizers such as sorbitol, panthenol and glycerin; colorants such as dyes and pigments; Solvent extract, protein obtained from shell or pearl with pearl layer or hydrolyzate thereof, protein obtained from silk or hydrolyzate thereof, protein-containing extract obtained from legume seeds, ginseng extract, rice Germ extract, Hibamata extract, aloe extract, moon peach leaf extract, chlorella extract, etc .; Pearling agent such as titanium oxide; Fragrance; Dye; Ultraviolet absorber; Antioxidant; Other encyclopedia Ingredients described in OF shampooing Ingredients (ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS)).

  The aqueous hair cleanser of the present invention preferably has a pH (diluted 20 times by weight with water, 25 ° C.) of 2 to 6 when applied to hair, from the viewpoint of improving the gloss and unity of the hair, The pH is preferably 3 to 5, particularly preferably pH 3.5 to 4.5. As the pH adjuster, it is preferable to use an organic acid, particularly α-hydroxy acid, and specifically, malic acid, citric acid, lactic acid, and glycolic acid are preferable. Two or more of these organic acids may be used in combination, and the amount used is 0.01 to 5% by weight in the aqueous hair cleanser 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 weight, particularly 0.3 to 2% by weight. Further, as other pH adjusting agent, a base such as sodium hydroxide, potassium hydroxide, ammonium chloride may be used in combination with these organic acids.

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

Production Example 1: Production of ammonium lauryl ether sulfate having an average addition mole number of 1.0 EO Charcoal 2470 (Kao Corporation, dodecyl alcohol: tetradecyl alcohol = about 3: 1) 2000 g and potassium hydroxide 1.45 g were charged into a pressure-resistant sealed reactor, After dehydration at 110 ° C. and 10 mmHg for 30 minutes, the system was heated to 165 ° C. After the temperature rise, 456 g of ethylene oxide was injected and an addition reaction was performed at that temperature for 30 minutes. Then, it cooled to 80 degreeC and neutralized with 1.3 g of acetic acid, and the ethylene oxide addition product of the said raw material alcohol was obtained.

  Next, 1793 g of the mixture obtained by the above operation and 607 g of sulfuric acid gas were used to carry out a sulfation reaction at 40 ° C. After the reaction, neutralization was performed with 150 g of 28 wt% aqueous ammonia and 600 g of ion exchange water. Further, the concentration and pH were adjusted using 28 wt% aqueous ammonia and ion-exchanged water to obtain 10000 g of sulfate 1 (25 wt% aqueous solution) shown in Table 1.

  The obtained sulfate was confirmed to be sulfate, anion and EO chain according to the cosmetic raw material standards, and the composition ratio was measured by gas chromatography and shown in Table 1.

Production Example 2: Production of ammonium lauryl ether sulfate having an EO average addition mole number of 1.3 According to Production Example 1 except that the reaction ratio of the raw materials was changed, sulfate 2 (25% by weight aqueous solution) shown in Table 1 was obtained.

  The obtained sulfate was confirmed to be sulfate, anion and EO chain according to the cosmetic raw material standards, and the composition ratio was measured by gas chromatography and shown in Table 1.

Production Example 3: Production of sodium lauryl ether sulfate having an EO average addition mole number of 1.0 Using 1793 g of the ethylene oxide adduct of the raw material alcohol obtained in Production Example 1 and 607 g of sulfuric acid gas, a sulfation reaction was carried out at 40 ° C. After the reaction, neutralization was performed with 132 g of a 23 wt% sodium hydroxide aqueous solution and 556 g of ion-exchanged water. Further, the concentration and pH were adjusted using 23 wt% sodium hydroxide aqueous solution, 75 wt% phosphoric acid and ion-exchanged water, and 10000 g of sulfate 3 (25 wt% aqueous solution) shown in Table 1 was obtained.

  The obtained sulfate was confirmed to be sodium salt, sulfate, anion and EO chain in accordance with cosmetic raw material standards, and the composition ratio was measured by gas chromatography and shown in Table 1.

* 1: Comparative sulfate 1
EMAL 227-PH11 (sodium lauryl ether sulfate with an average added mole number of EO of 2.0), which is a 27% by weight aqueous solution of sulfate.
* 2: Comparative sulfate 2
A mixture of sodium lauryl ether sulfate and sodium lauryl sulfate with an average EO addition mole number of 2.0.

  Eomaru 227-PH11 (1000 g) from Kao Corporation and Emar 2F-HP (500 g) were mixed to obtain a 27 wt% aqueous solution of sulfate.

Examples 1-6 and Comparative Examples 1-3
Using the sulfate type surfactants shown in Table 1, hair cleaning agents shown in Table 2 were prepared, and the speed of foaming, the feeling of slipping during hair washing, the gloss of hair after drying, and the texture were evaluated. The pH is a value at 25 ° C. diluted 20 times by weight with water.

(Speed of foaming)
According to the apparatus and conditions described in [0053] and [0054] of JP-A-10-73584, the amount of foaming is measured with an evaluation sample of 1.5 mL and model sebum of 0.3 mL, and depending on the time until the amount of foam reaches 25 mL evaluated.

・ Evaluation criteria ◎: Less than 100 seconds ○: More than 100 and less than 200 seconds △: More than 200 and less than 300 seconds ×: More than 300 seconds

(Slip feeling when washing and rinsing)
A human hair bundle having a length of 25 cm, a width of 5.5 cm, and a weight of 10 g was lightly rinsed with warm water at 40 ° C., and then excess water was removed and foamed sufficiently for about 30 seconds using 0.5 g of a hair cleaning agent. Sensory evaluation of the feeling of slipping of the bristles with bubbles was performed, followed by sensory evaluation of the feeling of slipping while rinsing the hair bundles with 40 ° C hot water. The evaluation was performed by five people, and the total value of the evaluation was shown.

・ Evaluation criteria 4: Slip well 3: Slightly slip 2: Not slippery 1: Not slippery

(Glossy and unity after drying)
The hair bundle treated in the same way as the slip evaluation was rinsed with running water (2 L / min) at 40 ° C. for 30 seconds, and then the moisture was sufficiently wiped off with a towel and air-dried. 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.

・ Evaluation criteria 4: Good 3: Somewhat good 2: Not very good 1: Not good

* 3: DC8500 (Dow Corning)

R: hydrocarbon group of C ₁₃ H _{27 to} C ₁₅ H ₃₁ Z: 75% is a group —CH ₂ CH (OH) CH ₂ OH, and 25% is a hydrogen atom

* 4: KT1989 (GE Toshiba)

* 5: Highly polymerized methylpolysiloxane, average particle size of 0.5μm, 60% by weight

Example 7 Pearl Appearance Shampoo
(weight%)
Sulfate 3 of Production Example 3 (sodium salt, 25% by weight aqueous solution) 48.0
Sodium cocoamphoacetate 0.5
Cocoyl monoethanolamide 0.3
Polyoxyethylene (14) lauryl ether 1.0
Ethylene glycol distearate 2.0
Cationized hydroxyethyl cellulose (Polymer JR-400, Amerchol) 0.4
Amino-modified silicone derivative ^{* 3} 1.0
Highly polymerized methylpolysiloxane emulsion (Silicone CF2450, Toray Dow Corning) 1.5
Panthenol 0.05
Silk extract 0.05
Sodium chloride 1.0
Lactic acid Amount of pH 6.0 Ion-exchanged water Remaining

Example 8 Conditioning Shampoo
(weight%)
Sulfate 1 of Production Example 1 (ammonium salt, 25% by weight aqueous solution) 52.0
Isodecyl glyceryl ether 0.7
Laurylamidopropylbetaine 2.0
Cocoyl monoethanolamide 0.5
Myristyl alcohol 1.5
Polyoxyethylene (16) lauryl ether 1.0
Ethylene glycol distearate 2.0
Cationized hydroxyethyl cellulose (Poise C-80M, Kao) 0.5
Diallyl quaternary ammonium salt / acrylamide copolymer (Marcote 550, Calgon) 0.2
Amino-modified silicone derivative ^{* 3} 0.4
Highly polymerized methylpolysiloxane emulsion (Silicone CF2450, Toray Dow Corning) 4.0
Benzyl alcohol 0.4
Polypropylene glycol (Mw = 400) 0.2
Sodium chloride 1.0
Hydrolyzed conchiolin solution (dry weight 3% by weight) 0.05
Panax ginseng extract (dry weight 3%) 0.05
Soybean extract (0.4% dry matter) 0.05
Eucalyptus extract (dry weight 0.2% by weight) 0.05
Rice germ oil 0.05
Malic acid 0.5
Sodium hydroxide pH 3.9 Amount of ion-exchanged water Remaining

Example 9 Conditioning Shampoo
(weight%)
Sulfate 1 of Production Example 1 (ammonium salt, 25% by weight aqueous solution) 64.0
2-Ethylhexyl glyceryl ether 0.3
Cocoyl monoethanolamide 0.5
Myristyl alcohol 1.0
Cetanol 0.5
Ethylene glycol distearate 3.0
Cationized hydroxyethyl cellulose (Polymer JR-30M, Amerchol) 0.2
Cationized guar gum (Jaguar C-13S, Rhodia) 0.3
Glycerin 1.0
Amino-modified silicone derivative ^{* 3} 1.5
Highly Polymerized Methyl Polysiloxane Emulsion (Silicone CF2450, Toray Dow Corning) 1.0
Sodium chloride 0.2
Benzyloxyethanol 0.5
Malic acid 0.7
Lactic acid Amount of pH 3.7 Deionized water Remaining

Example 10 Conditioning Shampoo
(weight%)
Sulfate 2 of Production Example 2 (ammonium salt, 25% by weight aqueous solution) 40.0
Laurylamidopropylbetaine 3.0
Polyoxyethylene (16) lauryl ether 2.0
Stearoxypropyldimethylamine malate 0.5
Ethylene glycol distearate 2.0
Cationized guar gum (Jaguar C-13S, Rhodia) 0.3
Polypropylene glycol (Mw = 400) 0.5
Amino-modified silicone derivative ^{* 3} 0.8
Highly polymerized methylpolysiloxane emulsion (Silicone CF2450, Toray Dow Corning) 4.0
Sodium chloride 1.0
Malic acid 0.8
Glycolic acid 0.75
Sodium hydroxide pH 3.5 Amount of ion-exchanged water remaining

Example 11 Pearl Appearance Anti Dandruff Shampoo
(weight%)
Sulfate 1 of Production Example 1 (ammonium salt, 25% by weight aqueous solution) 52.0
Isodecyl glyceryl ether 1.5
Cocoylamidopropylbetaine 1.0
Lauryl hydroxysulfobetaine 1.0
Lauric acid 0.5
Oleic acid 0.7
Distearyl ether 2.0
Cocoyl benzalkonium chloride 0.5
Cationized hydroxyethyl cellulose (Polymer JR-400, Amerchol) 0.4
Ethanol 0.5
Amino-modified silicone derivative ^{* 3} 0.2
Highly polymerized methylpolysiloxane emulsion (silicone CF2450, Toray Dow Corning) 2.0
Hibamata extract 0.05
Malic acid 0.7
Sodium hydroxide pH 5.5 Amount of ion-exchanged water Remaining

  The cleaning agents of Examples 7 to 11 all had quick foaming at the time of washing, good foam sliding, and a feeling of slipping at the time of rinsing, and the gloss and cohesiveness of the finished hair were good.

Claims (7)

An aqueous hair cleanser containing the following components (A), (B) and (C).
(A) The following general formula (1)
R—O— (C ₂ H ₄ O) _n —SO ₃ M (1)
[Wherein, R represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, n represents 0 or a positive integer, and M represents sodium or ammonium. ]
Wherein n = 0 sulfate 30-45 wt%, n = 1 sulfate 18-27 wt%, n = 2 sulfate 10-20 wt%, and the balance is n = Sulphate type surfactant composed of 3 or more sulfates and n = 0 to 2 in total of 70% by weight or more of total sulfates 5 to 30% by weight
(B) Amino-modified silicone derivative having a group containing both a hydroxyl group and a nitrogen atom as a side chain bonded to a silicon atom 0.05 to 10% by weight
(C) Silicone oil represented by the following general formula (2) present as dispersed particles having an average particle size of less than 50 μm 0.1 to 10% by weight
R ′ (CH ₃ ) ₂ SiO — [(CH ₃ ) ₂ SiO] _m —Si (CH ₃ ) ₂ R ′ (2)
[Wherein, R ′ represents a methyl group or a hydroxy group, and m represents a number of 50 to 20,000. ] The aqueous hair cleanser according to claim 1, wherein component (B) is an amino-modified silicone derivative represented by the following general formula (3).
[In the formula, each R ¹ independently represents a monovalent hydrocarbon group, a hydroxy group or an alkoxy group, each R ² independently represents a monovalent hydrocarbon group, and each R ³ independently represents Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ independently represents a group represented by the formula (4) or (5), a represents a number of 25 to 1000, b shows the number of 1-200.
(In the formula, each Y independently represents a hydrogen atom or a group —CH ₂ —CH (OH) —R ³ —OH, and each R ⁵ independently represents a hydrogen atom or a group —R ³ NY ₂ (Y And R ³ are the same as above, but not all Y are hydrogen atoms.)]   The aqueous hair cleanser according to claim 1 or 2, further comprising a nonionic surfactant or an amphoteric surfactant.   The aqueous hair cleanser according to any one of claims 1 to 3, further comprising a cationic polymer.   Furthermore, the aqueous hair cleansing agent in any one of Claims 1-4 containing silicones other than a component (B) and (C).   Furthermore, the aqueous hair cleansing agent in any one of Claims 1-5 containing the pearling agent containing ethylene glycol monoalkyl ester or ethylene glycol dialkyl ester.   Furthermore, the aqueous hair cleaning agent in any one of Claims 1-6 containing higher alcohols.