JP5235102B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention relates to an aqueous hair cleansing agent containing a specific alkyl ether sulfate.

  Alkyl sulfates typified by sodium dodecyl sulfate have long been used as a cleaning component for aqueous cleaning agents because of their high detergency and large amount of foaming. However, alkyl sulfates have the problem of stability that they are likely to precipitate at low temperatures, and when used as an aqueous hair cleanser, there is also a problem that the squeaky feel of the hair when rinsing the cleanser is strong. .

  Therefore, in order to solve these problems, polyoxyethylene addition type alkyl sulfates in which ethylene oxide is added between an alkyl group and a sulfate group have been developed and are now widely used as the main component of aqueous hair cleansing agents. . With regard to this polyoxyethylene alkyl ether sulfate, it is known that as the number of moles of ethylene oxide added increases, the stability at low temperature is improved and the squeaky feeling during rinsing is reduced. There is a problem that foam performance such as foaming and foam slipping is lowered. Furthermore, increasing the number of moles of ethylene oxide decreases the viscosity of the hair cleanser, so increase the amount of polyoxyethylene alkyl ether sulfate, or add a large amount of cosurfactant or thickener. There was also a problem from the viewpoint of cost that it was necessary to deal with such problems. Currently, polyoxyethylene alkyl ether sulfates with an average addition of 2 to 3 moles of ethylene oxide are most often used in hair cleansers, but their use feeling is not sufficient and low temperature stability. It was not enough from the viewpoint.

  As another technique for improving the low temperature stability of the alkyl sulfate, Patent Document 1 describes a hair cleansing agent containing an alkyl sulfate added with 1 to 10 moles of propylene oxide on average. The polyoxyethylene group has a linear oxyalkylene structure, whereas the polyoxypropylene group has a branched structure. Therefore, such a polyoxypropylene-added alkyl sulfate has a packing property between surfactant molecules. Although it has the effect of reducing the crystallinity at low temperature, there is also a problem that the squeaky feeling when rinsing the cleaning agent is still strong.

  Moreover, in patent document 2, the alkyl sulfate salt which added the average 1-10 mol propylene oxide and the average 0-33 mol ethylene oxide is reported. This document describes the use of the alkyl ether sulfate as a general cleaning agent, but there is no disclosure about the characteristics particularly when used as a hair cleaning agent. In Patent Document 2, as in Patent Document 1, by adding 1 mol or more of propylene oxide on average, the low-temperature stability is improved to some extent, but the squeaky feeling at the time of rinsing still remains strong. The problem of reducing the viscosity of the hair cleanser by introducing a group has not been solved.

JP 5-97633 A Special table 2007-534669 gazette

  The present invention provides an aqueous hair cleanser that has an appropriate viscosity, has good foaming and fine and slippery foam quality when shampooed, has a smooth feel when rinsed, and has good low-temperature stability. The purpose is to provide.

  In the hair cleansing agent, the present inventor has disclosed that an alkyl ether sulfate component in which the number of added moles of ethyleneoxy groups is within a certain range and an alkyl in which the number of moles of added alkyleneoxy groups having 3 or 4 carbon atoms are within a certain range It has been found that when the ether sulfate component is used in combination, the above requirement is satisfied.

That is, the present invention provides a polyoxyethylene alkyl ether sulfate represented by the general formula (1) [compound (1)] and a polyoxyalkylene alkyl ether sulfate represented by the general formula (2) [compound (2)]. An aqueous hair cleanser containing 5 to 30% by mass in total.
R ¹ O— (EO) _m —SO ₃ M (1)
_{^{R 2 O- (AO) n -SO}} 3 M (2)
[Wherein R ¹ and R ² represent the same or different alkyl group having an average carbon number of 8 to 24, EO represents an ethyleneoxy group, and m represents an EO average addition mole in the range of 0 <m ≦ 3. AO represents an alkyleneoxy group having 3 or 4 carbon atoms, n represents an AO average addition mole number in the range of 0 <n ≦ 3, and M represents a cation. ]

  The aqueous hair cleansing agent of the present invention has an appropriate viscosity, has good foaming and fine and slippery foam quality at the time of shampooing, has a smooth feel at the time of rinsing, and has good low-temperature stability. .

The average carbon number of the alkyl group of R ¹ in the general formula (1) and R ^{2 in} the general formula (2) is 8-24, preferably 8-16, more preferably 10-14. And particularly preferably 12-14. Furthermore, R ¹ and R ² are preferably straight chain alkyl groups derived from fats and oils from the viewpoint of performance such as foaming power and fineness of foam.

  The average added mole number m of EO in the general formula (1) is 0 <m ≦ 3. However, from the viewpoint of ease of foaming and performance such as smoothness when excessive, preferably 0 <m ≦ 2.5, and more preferably 0.1 ≦ m ≦ 2, particularly preferably 1 ≦ m ≦ 2.

  In addition, the alkylene group A in AO in the general formula (2) may have either a straight chain structure or a branched chain structure, more preferably a branched chain structure, and particularly preferably a propylene group. In addition, the average added mole number n of AO is 0 <n ≦ 3, but preferably 0.1 ≦ n ≦ 2, more preferably for performance such as thickening and smoothness during rinsing, and low temperature stability. Is 0.1 ≦ n ≦ 1.6, particularly preferably 0.2 ≦ n ≦ 1.

  From the comprehensive viewpoints of reactivity, usability and low-temperature stability during production, the EO average addition mole number m of the compound (1) and the AO average addition mole number n of the compound (2) are 0 <m ≦ 2.5 and 0.1 It is preferable that ≦ n ≦ 2, more preferably 0.1 ≦ m ≦ 2 and 0.1 ≦ n ≦ 1.6, and particularly preferably 1 ≦ m ≦ 2 and 0.2 ≦ n ≦ 1.

  M in the general formulas (1) and (2) is a cation that forms a salt, and examples thereof include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions. Examples of the alkali metal ion include sodium ion, potassium ion, lithium ion, the alkaline earth metal ion includes calcium ion, and the alkanol ammonium ion includes triethanolammonium ion. Among these, ammonium ion, sodium ion, and potassium ion are more preferable, and ammonium ion and sodium ion are particularly preferable.

  Such alkyl ether sulfates [compound (1) and compound (2)] can be produced, for example, by a process including the following processes (I) and (II).

Step (I): Step of adding a predetermined amount of ethylene oxide or alkylene oxide (propylene oxide or butylene oxide) to 1 mol of alkanol having an alkyl group having an average carbon number of 8 to 24 Step (II): In step (I) The step of sulfating and then neutralizing the resulting alkoxylate

  The average carbon number of the alkyl group of the alkanol used in the step (I) is 8 to 24, but 8 to 16 is preferable from the viewpoint of versatility and handleability of the raw material, more preferably 10 to 14 and particularly preferable. Is 12-14. Furthermore, a linear alkyl group is preferable from the viewpoint of performance such as foaming power and foam quality.

  As a method for carrying out the steps (I) and (II), conventionally known methods can be applied. That is, an alkanol and an alkali such as 0.5 to 1 mol% potassium hydroxide with respect to the alkanol are charged into an autoclave as a catalyst, and the temperature is increased and dehydrated, and a predetermined amount of alkylene oxide is added at a temperature of 130 to 160 ° C. You can do it. The autoclave to be used is preferably provided with a stirring device, a temperature control device, and an automatic introduction device.

  In the step (II), the method for sulfating alkoxylates includes a method using sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid and the like. From the viewpoint of preventing generation of waste hydrochloric acid or the like, a method of continuously supplying gaseous or liquid sulfur trioxide simultaneously with the alkoxylate is preferable.

  As a neutralization method of the obtained sulfur oxide, a batch type in which the sulfur oxide is neutralized while adding and stirring to a predetermined amount of the neutralizer, and the sulfur oxide and the neutralizer are continuously supplied into the pipe. The continuous type which neutralizes with a stirring mixer is mentioned, and any may be sufficient. Examples of the neutralizing agent include alkali metal hydroxides, ammonia, triethanolamine and the like, but alkali metal hydroxides are preferable, and sodium hydroxide is particularly preferable.

  The total content of compound (1) and compound (2) is 5 to 30% by mass in the aqueous hair cleansing agent of the present invention, but 7 to 23% by mass, particularly 10 to 20% by mass is preferable.

  The content ratio of the compound (1) and the compound (2) in the aqueous hair cleansing agent of the present invention is 10 to 90% by mass of the compound (1) in the total amount of the compound (1) and the compound (2). 20 to 80% by mass, particularly 30 to 70% by mass is preferable, and the compound (2) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.

  Further, when considering the average addition mole number of AO in all the alkyl ether sulfate components, the contents of the compound (1) and the compound (2) are expressed by the following formulas from the viewpoints of thickening, usability and low temperature stability: It is preferable that the condition represented by α) is satisfied.

  The formula (α) means that the average added mole number of AO with respect to the total mole number of the compound (1) and the compound (2) is more than 0 and less than 2, but a more preferable range of this ratio is 0.2 to 1.8. A particularly preferred range is 0.4 to 1.6.

  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 as a surfactant other than the alkyl ether sulfate.

  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 glyceryl ether, 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 polyoxyethylene (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, and may be either monoalkanolamides or dialkanolamides, and those having an acyl group having an average carbon number of 8 to 18, and further 10 to 16 are preferable. 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 and monoalkenyl glyceryl ether are also suitable, and the alkyl group or alkenyl group is preferably a linear or branched alkyl group or alkenyl group having 4 to 10 carbon atoms, and more preferably 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 more preferable.

  Examples of amphoteric surfactants include betaine surfactants. Of these, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, alkylhydroxysulfobetaine and the like are more preferred, and fatty acid amidopropyl betaine is more preferred. Fatty acid amide propyl betaines preferably have an acyl group having an average carbon number of 8 to 18, more preferably 10 to 16, more preferably lauric acid amide propyl betaine, palm kernel oil fatty acid amide propyl betaine, coconut oil fatty acid amide propyl betaine, etc. Is preferred.

  These nonionic surfactants or amphoteric surfactants can be used alone or in combination of two or more in the aqueous hair cleanser, but the aqueous hair cleanser of the present invention is in the form of an aqueous liquid cleanser. In this case, it is preferable to use fatty acid amidopropyl betaine, fatty acid alkanolamide, or monoalkyl glyceryl ether because not only foaming power is improved but also appropriate liquidity is obtained.

  The content of the nonionic surfactant or amphoteric surfactant is preferably 0 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass in the aqueous hair cleansing agent of the present invention.

  In the aqueous hair cleansing agent of the present invention, a cationic surfactant and a cationic polymer can be further added to improve the finish after drying.

  Examples of the cationic surfactant include alkyltrimethylammonium salt, alkoxyalkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylamine and salt thereof, alkoxyalkyldimethylamine and salt thereof, alkylamidoalkyldimethylamine and salt thereof, and the like. Can be mentioned.

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

(ii) Alkoxyalkyltrimethylammonium salt Examples include those represented by the following general formula.
R ⁴ —O—R ⁵ —N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein, R ⁴ represents an alkyl group having 12 to 22 carbon atoms, R ⁵ represents an ethylene group or a propylene group which may be substituted with a hydroxy group, and X ⁻ is the same as above. ]
Specific examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride, and the like.

(iii) Dialkyldimethylammonium salt Examples include those represented by the following general formula.
(R ⁶ ) ₂ N ⁺ (CH ₃ ) ₂ X ⁻
[Wherein, R ⁶ independently represents an alkyl group having 12 to 22 carbon atoms or a benzyl group, and X ⁻ is the same as described above. ]
Specifically, distearyl dimethyl ammonium chloride etc. are mentioned.

(iv) Alkyldimethylamine and salts thereof Examples thereof include those represented by the following general formula and salts thereof.
R ⁷ -N (CH _{3) 2}
[Wherein, R ⁷ represents an alkyl group having 12 to 22 carbon atoms. ]
Specific examples include behenyl dimethylamine, stearyl dimethylamine and organic acid salts thereof.

(v) Alkoxyalkyldimethylamine and salts thereof Examples thereof include those represented by the following general formula and salts thereof.
R ⁸ —O—R ⁹ —N (CH ₃ ) ₂
[Wherein R ⁸ represents an alkyl group having 12 to 22 carbon atoms, and R ⁹ represents an ethylene group or a propylene group. ]

(vi) Alkylamidoalkyldimethylamine and salts thereof Examples thereof include those represented by the following general formula and salts thereof.
^{R 10 -CONH-R 11 -N (} CH 3) 2
[Wherein, R ¹⁰ represents an alkyl group having 11 to 21 carbon atoms, and R ¹¹ represents an ethylene group or a propylene group. ]

Examples of cationic surfactants other than the above (i) to (vi) include ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, ethyl sulfate lanolin fatty acid aminoethyltriethylammonium, ethyl sulfate lanolin fatty acid aminopropyltriethylammonium, methyl sulfate lanolin fatty acid amino. trimethyl ammonium, methyl sulfate lanolin fatty acid aminopropyl ethyl dimethyl ammonium ethyl sulfate isoalkanes acid (C ₁₄ ~C ₂₀₎ aminopropyl dimethylammonium ethyl sulfate isoalkanes acid (C ₁₈ ~C ₂₂₎ aminopropyl dimethylammonium ethyl sulfate Aminopropylethyldimethylammonium isostearate, aminopropylethyldimethylammonium isononate, And methylammonium 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 thereof is preferably 0.01 to 10% by mass in the aqueous hair cleaning agent of the present invention. Furthermore, 0.05 to 6% by mass, particularly 0.1 to 3% by mass, particularly 0.2 to 2% by mass is preferable.

  Next, as the cationic polymer, cationized cellulose, cationized starch, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, cationized xanthan gum, diallyldialkyl 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 trimethyl chloride Monium 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, in particular, cationized cellulose, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, diallyldialkyl quaternary An ammonium salt / acrylamide copolymer is 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 methyl imidazolium salt; CTFA name polyquaternium-16), Gafquat 755N (ISP, copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate; CTFA name polyquaternium-11), Ucare polymer JR and LR series (Amercor, salt of reaction product of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name Polyquaternium-10), Poise C-60H, Poise C-80M, Poise C-150L (Kao Co., Ltd. Reaction salt of trimethylammonium substituted epoxide and hydroxyethyl cellulose; CTFA name Polyquaternium-10), Di Gar series (Rhodia, salt of reaction product of trimethylammonium substituted epoxide and guar gum), Katinaral CF-100 (Sho of reaction product of trimethylammonium substituted epoxide and fenugreek gum), Catinal CTR-100 ( Commercially available products such as Toho Chemical Industry Co., Ltd., a salt of a reaction product of trimethylammonium substituted epoxide and tara gum, and Katchinal CLB-100 (Toho Chemical Industry Co., Ltd., a salt of a reaction product of trimethylammonium substituted epoxide and locust bean gum). be able to.

  These cationic polymers may be used in combination of two or more, and the content thereof is preferably 0.01 to 3% by mass in the aqueous hair cleansing agent of the present invention from the point of smoothness from the time of shampooing to the time of rinsing. Further, 0.05 to 2% by mass, particularly 0.1 to 0.5% by mass is preferable.

  In order to improve the finish after drying, the aqueous hair cleansing agent of the present invention may further contain a conditioning component such as silicones. Examples of silicones include the following.

(i) Dimethylpolysiloxane Examples include those represented by the following general formula.
R ¹² (CH ₃ ) ₂ SiO — [(CH ₃ ) ₂ SiO] _p —Si (CH ₃ ) ₂ R ¹²
[Wherein R ¹² represents a methyl group or a hydroxy group, and p represents a number of 1 to 20,000. ]

Dimethylpolysiloxane, whipped time and smoothness during rinsing, from the viewpoint of smoothness after drying, a viscosity at 25 ° C., is preferably 10,000~30,000,000mm ² / s, more preferably 20,000～20,000,000Mm ² / s, particularly preferably 30,000 to 10,000,000 mm ² / s. Commercially available products include KF-96H-10,000 cs, KF-96H-50,000 cs, KF-96H-100,000 cs, KF-96H-1,000,000 cs (Shin-Etsu Chemical Co., Ltd.). These dimethylpolysiloxanes can be used alone or in combination of two or more. In particular, dimethylpolysiloxane having a viscosity of more than 1,000,000 mm ² / s, since the improving handling property, low viscosity polydimethylsiloxane having a viscosity of less than or equal to 10,000 mm ² / s, or octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane You may use what is marketed as a mixture with liquid cyclic silicones, such as siloxane and dodecamethylcyclohexasiloxane.

  Dimethylpolysiloxane is preferably used in the form of an aqueous emulsion. In preparing the aqueous emulsion, it is preferable to contain at least one emulsifier from the viewpoint of stabilizing the emulsion.

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

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

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

  The average particle size of the aqueous emulsion is preferably 50 μm or less, more preferably 20 μm or less, more preferably from the viewpoints of stability in the aqueous hair cleansing composition of the present invention, smoothness during rinsing and smoothness after drying. It is preferably 4 μm or less, particularly preferably 2 μm or less. The average particle diameter can be measured with a particle size measuring apparatus using laser light scattering, for example, using Coulter LS-130.

Such dimethylpolysiloxane emulsion, for example, after a kinematic viscosity at 25 ° C. were mixed polydimethylsiloxane is 8,000,000mm ² / s and 5,000 mm ² / s at 1 to 1 ratio, cetyltrimethylammonium chloride in emulsified, average and those commercially available as "silicone CF2460" Toray Dow Corning is a particle size 20 [mu] m, kinematic viscosity at 25 ° C. is 6,000,000mm ² / s and 500 mm ² / s polydimethylsiloxane Can be used which is commercially available as “Silicone CF2450” manufactured by Toray Dow Corning Co., Ltd., having an average particle size of 0.8 μm, mixed in a ratio of 3 to 7 and then emulsified with polyoxyethylene lauryl ether.

(ii) Amino-modified silicone A variety of amino-modified silicones can be used, especially those described in the 3rd edition of the CTFA Dictionary (US, Cosmetic Ingredient Dictionary) under the name Amodimethicone, and the amino group is propylene glycol. A modified type of amino-modified silicone and a type of amino-modified silicone in which a polyether group is modified in the main chain or side chain are preferred. Examples of commercially available products include SM 8704C, Dow Corning Toray JP-8500 Conditioning Agent, Dow Corning Toray SS-3588, Dow Corning Toray Silstyle 104 (Toray Dow Corning), DC 929 (Dow Corning), and the like.

(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.

  Two or more kinds of silicones may be used in combination. From the viewpoint of smoothness after drying and improvement of gloss, the content is preferably 0.01 to 10% by mass in the aqueous hair cleansing agent of the present invention. 0.05-6 mass%, 0.5-3 mass%, especially 0.8-2 mass% are particularly preferred.

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

  Examples of the ethylene glycol monofatty acid ester include ethylene glycol monostearate and ethylene glycol monobehenate, and examples of the ethylene glycol difatty acid ester include ethylene glycol distearate and ethylene glycol dibehenate. . Examples of the ethylene glycol monoalkyl ether include ethylene glycol monostearyl ether, and examples of the ethylene glycol dialkyl ether include ethylene glycol distearyl ether.

  Two or more of these may be used in combination, and the content of the aqueous hair of the present invention is from the viewpoint of good pearl appearance and storage stability of the hair cleansing agent, and smoothness improvement during foaming and rinsing. 0.1-10 mass% is preferable in a cleaning agent, Furthermore, 0.5-5 mass%, Furthermore, 1-4 mass% is preferable.

  Moreover, the hair washing agent of this invention can contain an oil agent as another conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin; fats and oils such as castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, coconut oil; beeswax, whale wax, Waxes such as lanolin and carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, myristyl alcohol, behenyl alcohol, cetostearyl alcohol; isopropyl palmitate, isopropyl myristate, myristic acid Octyldodecyl, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, Ester oils such as tridecyl sononanoate; higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearic acid, isopalmitic acid; other isostearyl glyceryl ethers, Examples include polyoxypropylene butyl ether. Of these, higher alcohols and fats are preferable, and myristyl alcohol, cetyl alcohol, stearyl alcohol, sunflower oil, and camellia oil 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 in the aqueous hair cleansing agent of the present invention, more preferably 0.2 to 1.5% by mass, Especially 0.3-1.0 mass% is preferable.

  The aqueous hair cleansing agent of the present invention may contain a viscosity modifier, and as the viscosity modifier, hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, isoprene glycol, ethanol, benzyl alcohol Benzyloxyethanol, phenoxyethanol, clay minerals, salts (sodium chloride, ammonium chloride, sodium citrate, etc.), among which benzyl alcohol, ethanol, polypropylene glycol, sodium chloride, and sodium citrate are preferred. Two or more types of viscosity modifiers may be used in combination, and the amount used thereof is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% in the aqueous hair cleansing agent of the present invention from the viewpoint of the amount of foam and foam quality. % By mass, particularly 0.1 to 3% by mass 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; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; humectants such as glycerin, sorbitol, and panthenol; colorants such as dyes and pigments; Solvent extract, protein obtained from shell or pearl with pearl layer or hydrolyzate thereof, honey, royal jelly, protein obtained from silk or hydrolyzate thereof, protein-containing extract obtained from legume seed, ginseng Extracts, rice germ extract, hibamata extract, aloe extract, moon peach leaf extract, chlorella extract and other extracts; pearling agents such as titanium oxide; fragrances; pigments; ultraviolet absorbers; antioxidants; Ingredients listed in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) It is.

  The aqueous hair cleansing agent of the present invention preferably has a pH (diluted 20 times by weight, 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 preferably 0.01 to 5% by mass in the aqueous hair cleansing agent of the present invention from the viewpoint of improving foam quality and hair flexibility during hair washing. Further, 0.1 to 3% by mass, particularly 0.3 to 2% by mass is preferable. 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 a liquid form, a gel form, etc., but a liquid form using water or a lower alcohol, particularly water, as a solvent is preferable.

  In the following examples and comparative examples, the numerical value shown as the pH of each hair cleaning agent is a measurement value at 25 ° C. when the hair cleaning agent is diluted 20 mass times with water.

Production Example 1
12 g of alkyl ether having 2 mol of EO average addition mole (carbon number 12/14 = 75 mass% / 25 mass%) ether sulfate, and alkyl having 12 mol of PO average addition mole (carbon number 12/14 = 72% by mass / 28% by mass) Sulfate composition 1 was prepared by mixing 8 g of sodium ether sulfate. The value of the formula (α) is 0.4.

Production Example 2
EO average addition mole number 2 mol alkyl (carbon number 12/14 = 75 mass% / 25 mass%) ether ether sulfate 8g, PO average addition mole number 1 mol alkyl (carbon number 12/14 = 72 mass% / 28 mass%) 12 g of sodium ether sulfate was mixed to prepare sulfate composition 2. The value of the formula (α) is 0.6.

Production Example 3
EO average addition mole number 2 mol alkyl (carbon number 12/14 = 75 mass% / 25 mass%) sodium ether sulfate 8 g and PO average addition mole number 2 mol alkyl (carbon number 12/14 = (72% by mass / 28% by mass) 12 g of sodium ether sulfate was mixed to prepare sulfate composition 3. The value of formula (α) is 1.2.

Production Example 4
EO average addition mole number 2 mol alkyl (carbon number 12/14 = 75 mass% / 25 mass%) sodium ether sulfate 4g, PO average addition mole number 2 mol alkyl (carbon number 12/14 = (72% by mass / 28% by mass) 16 g of sodium ether sulfate was mixed to prepare sulfate composition 3. The value of the formula (α) is 1.6.

Comparative production example 1
Alkyl (carbon number 12/14 = 75% by mass / 25% by mass) sodium ether sulfate having an EO average addition mole number of 2 mol was used as comparative sulfate composition 1. The value of the formula (α) is 0.

Comparative production example 2
Alkyl (carbon number 12/14 = 75% by mass / 25% by mass) sodium sulfate having an EO average addition mole number of 0 mol was used as comparative sulfate composition 2. The value of the formula (α) is 0.

Test Example 1 (Confirmation of thickening effect)
Sodium chloride and ion-exchanged water were added to the obtained various alkyl ether sulfate compositions to prepare an evaluation sample composed of 20% by mass of a surfactant effective amount, 1.5% by mass of sodium chloride and 78.5% by mass of water. .
The viscosity of the obtained evaluation sample was measured with a B-type viscometer. The measurement conditions are shown below. Table 1 shows the evaluation sample composition (surfactant concentration, sodium chloride concentration) and viscosity measurement results.
(Measurement condition)
・ Viscosity measuring equipment: B-type viscometer, TOKIMEC "DVL-B II"
・ Sample temperature: 30 ℃
・ Measurement time: 90 seconds ・ Rotor No .: 1-4
・ Rotation speed: 30rpm

  As apparent from Table 1, the surfactant composition containing the sulfate compositions 1 to 4 has a better thickening effect (salts) than the surfactant composition containing the comparative sulfate composition 1 or 2. Thickening effect in the presence). For this reason, when the combination of the alkyl ether sulfate in this invention is employ | adopted, even when there are few compounding quantities of surfactant and a thickener, it is easy to prepare the hair washing agent which has a suitable viscosity.

Examples 1 to 6 and Comparative Examples 1 to 4 (Usage feeling and low temperature stability of the hair cleanser)
The hair cleansing agents shown in Table 2 were prepared, and the speed of foaming, the feeling of slipping at the time of washing the hair, the fineness of foam, the feeling of slipping at the time of rinsing, the gloss of the hair after drying, the unity, and the low temperature stability were evaluated.

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

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

  First, the hair was wetted with 30 g of water, 0.3 mL of model sebum composed of lanolin was added, and then 1.5 mL of the evaluation sample was applied. Next, the container 10 is rotated at 70 revolutions per minute to slide the hair 1 and the protrusions 21 and 22, and the generated foam is collected in the measuring instrument 50. Depending on the time until the foam amount reaches 250 mL, Evaluation was made according to the following criteria.

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

(Slip feeling when washing hair)
After rinsing a human hair bundle 25cm long, 5.5cm wide and 10g in weight with warm water at 40 ° C, excess water was removed, and 0.5g of hair cleanser was used to foam well for about 30 seconds by hand. . Thereafter, the slipperiness of the bristles with bubbles was subjected to sensory evaluation. 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

(Fine texture when washing hair)
After foaming in the same manner as described above, the fineness of the foam was visually evaluated. The evaluation was performed by five people, and the total value of the evaluation was shown.

・ Evaluation criteria 4: Fine 3: Slightly fine 2: Not very fine 1: Not fine

(Slip feeling when rinsing)
The feeling of slipping was evaluated while rinsing the lather bubbled in the same manner as above with running water (2 L / min) at 40 ° C. 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

(Evaluation of low temperature stability)
After filling a 110 mL glass bottle with the hair cleanser, a sample stored for 1 month at −5 ° C. and a sample stored for 1 month at room temperature (standard product) were compared and visually evaluated.

・ Evaluation criteria ○: Same as standard product, no change △: Slightly changed compared to standard product ×: Clearly changed compared to standard product

  As is apparent from Table 2, the hair cleansing agent of the present invention using an alkyl ether sulfate having an EO addition mole number within a certain range and an alkyl ether sulfate having an AO addition mole number within a certain range, Foaming was quick and fine and fine foam quality was obtained, and sliding at the time of rinsing and low-temperature stability were also good. On the other hand, Comparative Examples 1 and 3 using only the alkyl ether sulfate added with EO were inferior in foam quality and slippage during rinsing. Further, Comparative Examples 2 and 4 using an alkyl sulfate had a strong squeak feeling during rinsing and were inferior in low-temperature stability.

Example 7 Conditioning Shampoo
(mass%)
Sulfate composition 1 13.0
Cationized tara gum (Catinal CTR-100, Toho Chemical Industries) 0.3
Isodecyl glyceryl ether 0.5
Amino-modified silicone (8500 Conditioning Agent, Toray Dow Corning) 0.3
Cationized cellulose (Poise C-80M, Kao) 0.3
Cationized guar gum (Jaguar C-17, Rhodia) 0.1
Diallyldimethylammonium chloride / acrylamide copolymer (Mercoat 550, Narco, effective content 8.5% by mass) 1.2
Dimethylpolysiloxane emulsion (silicone viscosity 10,000mm ² / s, average particle size 4μm, silicone effective 60% by mass) 1.7
Ethylene glycol distearate 2.0
Laurylamidopropylbetaine 1.0
Lauryl hydroxysulfobetaine 0.1
Myristyl alcohol 0.4
Cetyl alcohol 0.1
Cocoyl monoethanolamide 0.5
Polyoxyethylene (16) lauryl ether 0.7
Polypropylene glycol (mass average molecular weight 400) 0.5
Benzyl alcohol 0.3
Ethanol 3.0
Camellia oil 0.01
Panthenol 0.05
Royal Jelly 0.01
Refined honey 0.01
Silk extract 0.05
Sodium chloride 0.2
Perfume Appropriate amount Malic acid 0.5
pH adjuster (lactic acid) Amount to reach pH 3.9 Ion-exchanged water Balance

Example 8 Conditioning Shampoo
(mass%)
Sulfate composition 2 10.0
Palm oil fatty acid methyl taurine sodium 4.0
Cationized locust bean gum (Catinal CLB-100, Toho Chemical Industries) 0.4
Isodecyl glyceryl ether 0.7
Amino-modified silicone (SS-3588, Dow Corning Toray) 0.1
Cationized guar gum (Jaguar C-17, Rhodia) 0.1
Diallyldimethyl quaternary ammonium salt homopolymer (Mercoat 100, NALCO, effective 40% by mass) 0.8
Highly polymerized dimethylpolysiloxane emulsion (silicone CF2450, Toray Dow Corning, particle size 0.2-0.8μm,
Silicone effective component 60% by mass) 2.0
Ethylene glycol distearate 3.0
Laurylamidopropylbetaine 2.0
Cocoyl monoethanolamide 0.5
Myristyl alcohol 0.5
Cetyl alcohol 0.5
Polyoxyethylene (16) lauryl ether 1.0
Benzyl alcohol 1.0
Polypropylene glycol (mass average molecular weight 400) 0.2
Sodium chloride 1.0
Hydrolyzed conchiolin solution (dry matter 3% by mass) 0.05
Panax ginseng extract (dry matter 3% by weight) 0.05
Soybean extract (0.4% by weight of dry matter) 0.05
Eucalyptus extract (dry matter 0.2% by mass) 0.05
Rice germ oil 0.05
Glycolic acid 1.0
Perfume
pH adjuster (sodium hydroxide) Amount to reach pH 3.9 Ion-exchanged water Balance

Example 9 Conditioning Shampoo
(mass%)
Sulfate composition 4 16.0
Cationized guar gum (Jaguar C-13S, Rhodia) 0.3
2-Ethylhexyl glyceryl ether 0.3
Amino-modified silicone (8500 Conditioning Agent, Toray Dow Corning) 0.5
Highly polymerized dimethylpolysiloxane emulsion (silicone CF2460, Toray Dow Corning, average particle size 20μm,
Silicone effective content 75% by mass) 3.0
Ethylene glycol distearate 2.0
Cocoyl monoethanolamide 0.8
Cetyl alcohol 1.0
Glycerin 1.0
Sodium chloride 0.2
Benzyloxyethanol 0.5
Malic acid 0.7
Perfume Appropriate amount of lactic acid 0.1
pH adjuster (citric acid) Amount to reach pH 5.5 Ion exchange water Balance

Example 10 Conditioning Shampoo
(mass%)
Sulfate composition 1 15.0
Cationized fenugreek gum (Catinal CF-100, Toho Chemical Industry Co., Ltd.) 0.3
2-Ethylhexyl glyceryl ether 1.5
Amino-modified silicone (SILSTYLE 104, Toray Dow Corning) 1.0
Cationized locust bean gum (Kachinar CLB-100, Toho Chemical Industry Co., Ltd.) 0.2
Methyl polysiloxane emulsion (silicone viscosity 5,000mm ² / s, particle size 0.2 ~ 0.8μm, silicone effective 65% by mass) 2.0
Ethylene glycol distearate 2.0
Laurylamidopropylbetaine 3.0
Cocoyl monoethanolamide 0.8
Polyoxyethylene (16) lauryl ether 2.0
Sodium cocoamphoacetate 1.0
Stearoxypropyldimethylamine malate 0.5
Polypropylene glycol (mass average molecular weight 400) 0.5
Sodium chloride 1.0
Malic acid 0.8
Citric acid 0.75
pH adjuster (sodium hydroxide) Amount to reach pH 5.5 Ion exchange water Balance

  The hair cleansing agents of Examples 7 to 10 have an appropriate viscosity, quick foaming and fine foam quality, good foaming and slidability during rinsing, and gloss and cohesiveness of the finished hair. It was good and excellent in low temperature stability.

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

Explanation of symbols

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

Claims (7)

A total of 5 polyoxyethylene alkyl ether sulfates represented by general formula (1) [compound (1)] and polyoxyalkylene alkyl ether sulfates represented by general formula (2) [compound (2)] An aqueous hair cleanser containing ~ 30% by weight.
R ¹ O— (EO) _m —SO ₃ M (1)
_{^{R 2 O- (AO) n -SO}} 3 M (2)
[Wherein R ¹ and R ² represent the same or different alkyl group having an average carbon number of 8 to 24, EO represents an ethyleneoxy group, and m represents an EO average addition mole in the range of 0 <m ≦ 3. AO represents an alkyleneoxy group having 3 carbon atoms, n represents an AO average addition mole number in the range of 0 <n ≦ 3, and M represents a cation. ] 2. The aqueous hair cleanser according to claim 1, wherein the contents of the compound (1) and the compound (2) satisfy the condition represented by the formula (α).
  The aqueous hair according to claim 1 or 2, wherein in the total amount of the compound (1) and the compound (2), the ratio of the compound (1) is 10 to 90% by mass and the ratio of the compound (2) is 10 to 90% by mass. Washing soap.   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.   Furthermore, the aqueous hair cleaning agent in any one of Claims 1-5 containing 0.01-5 mass% of organic acids.   The aqueous hair cleanser according to any one of claims 1 to 6, which has a pH of 2 to 6 at 25 ° C when diluted 20 times by mass with water.