JP2009298744A - Aqueous hair detergent - Google Patents

Abstract

[PROBLEMS] To provide an aqueous hair cleansing agent that has good foaming and fine and smooth foam quality even in an environment where the temperature in winter is low, has a smooth feel when rinsed, and has good low-temperature stability. .
SOLUTION: The alkyl ether sulfate represented by the general formula (1) is contained in an amount of 5 to 30% by mass, or the alkyl ether sulfate represented by the general formula (1-1) and the general formula (2). An aqueous hair cleanser containing 5 to 30% by weight of a mixture of alkyl sulfates, wherein the average number of moles of PO added in the mixture is less than 1.
RO- (PO) _n SO ₃ M (1)
_{RO- (PO) m -SO 3 M} (1-1)
RO-SO ₃ M (2)
[R represents an alkyl group having an average carbon number of 8 to 24, PO represents a propyleneoxy group, n represents an average PO addition mole number in the range of 0 <n <1, and m represents an average PO addition mole number of 1 or more. , M represents a cation. ]
[Selection figure] None

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 a stability problem that they tend to precipitate at low temperatures, and as a result, foaming was not sufficient under low temperatures such as in winter. In addition, when used in an aqueous hair cleanser, there is also a problem that the squeaky feeling 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 the squeaky feeling during rinsing is reduced as the number of moles of ethylene oxide added is increased, but on the other hand, foaming, foam slipping, etc. There is a problem that the foam performance is lowered. Furthermore, the hair cleansing agent containing an alkyl ether sulfate to which ethylene oxide has been added has a problem that the viscosity is remarkably increased as the temperature is lowered, and as a result, foaming is further lowered at a low temperature compared to room temperature. At present, polyoxyethylene alkyl ether sulfates with an average addition of 2 to 3 moles of ethylene oxide are most frequently used in hair cleansing agents, but it has not been sufficient for foaming at low temperatures such as in winter.

  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 a low temperature, there is a problem that the thickening suppression effect at a low temperature is insufficient and 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 increased viscosity at low temperatures due to the introduction of groups has not been solved, and there has been a problem with foaming at low temperatures.

JP 5-97633 A Special table 2007-534669 gazette

  The present invention provides an aqueous hair cleansing agent that has good foaming and fine and slippery foam quality even in an environment where the temperature in winter is low, has a smooth feel when rinsed, and has good low-temperature stability. The purpose is to provide.

  The present inventor has found that the above requirement is satisfied if an alkyl ether sulfate having a propyleneoxy group addition mole number within a certain range is used for a hair cleanser.

That is, the present invention provides an aqueous hair cleanser containing 5 to 30% by mass of an alkyl ether sulfate represented by the general formula (1).
_{RO- (PO) n -SO 3 M} (1)
[Wherein, R represents an alkyl group having an average carbon number of 8 to 24, PO represents a propyleneoxy group, n represents an average PO addition mole number in a range of 0 <n <1, and M represents a cation. ]

Furthermore, the present invention contains 5 to 30% by mass of a mixture of an alkyl ether sulfate represented by the general formula (1-1) and an alkyl sulfate represented by the general formula (2), and PO average addition in the mixture An aqueous hair cleanser having a mole number of less than 1 is provided.
_{RO- (PO) m -SO 3 M} (1-1)
RO-SO ₃ M (2)
[Wherein, R represents an alkyl group having an average carbon number of 8 to 24, PO represents a propyleneoxy group, m represents an average number of moles of PO added of 1 or more, and M represents a cation. ]

  The aqueous hair cleansing agent of the present invention has good foaming and fine and slippery foam quality even in an environment where the temperature is low in winter, has a smooth feel when rinsed, and has good low-temperature stability. .

  In the alkyl ether sulfate represented by the general formula (1), the average carbon number of the R alkyl group in the general formula (1) is 8 to 24, preferably 8 to 16, more preferably. It is 10-14, Most preferably, it is 12-14. Furthermore, R is preferably a linear alkyl group derived from an oil or fat raw material in terms of performance such as foaming power and fineness of foam.

  The average PO added mole number n in the general formula (1) is 0 <n <1, but is preferably 0.1 to 0.9, more preferably 0.2 to 0.8, from the viewpoint of low temperature stability and foaming at low temperature. It is.

  M in the general formula (1) 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.

  The alkyl ether sulfate represented by the general formula (1) can be produced, for example, by a process including the following processes (I) and (II).

Step (I): Step of adding propylene oxide in an average range of more than 0 mol and less than 1 mol to 1 mol of alkanol having an alkyl group having an average carbon number of 8 to 24 Step (II): obtained in step (I) 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 Preferably it is 12-14. Furthermore, a linear alkyl group is preferable from the viewpoint of performance such as foaming power and foam quality.

  The amount of propylene oxide to be reacted with the alkanol may be an amount that provides a predetermined PO addition mole number.

  As a method for performing the step (I), a conventionally known method 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 as catalysts in an autoclave, and the temperature is increased and dehydrated, and a predetermined amount of propylene oxide is added at a temperature of 130 to 160 ° C. Just 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.

  Further, the alkyl ether sulfate represented by the general formula (1) used in the present invention is an alkyl ether sulfate represented by the following general formula (1-1) and an alkyl sulfate represented by the general formula (2). It may be a case where the PO average added mole number n is more than 0 and less than 1 as a mixture obtained by mixing with a salt or as a mixture resulting from the combined use of both in a hair cleanser.

_{RO- (PO) m -SO 3 M} (1-1)
RO-SO ₃ M (2)
[Wherein, R, PO and M have the same meaning as described above. m represents an average added mole number of PO of 1 or more, preferably 1 to 10, particularly 2 to 6. ]

  In the present invention, the average of propylene oxide in the alkyl ether sulfate of the general formula (1) or a mixture of the alkyl ether sulfate of the general formula (1-1) and the alkyl sulfate of the general formula (2) The number of added moles can be determined from the reaction ratio (feeding ratio) of the raw materials in the PO addition reaction. Moreover, it can measure with the following method.

<Method of measuring the average number of moles of propylene oxide added>
(1) Sample preparation Under vacuum, about 30 mg of a sufficiently dried measurement sample is weighed into a ¹ H-NMR sample tube with a diameter of 5 mm, and about 0.5 mL of deuterated solvent is added and dissolved. Here, the deuterated solvent is a deuterated methanol solvent or the like, and a solvent capable of dissolving the sample is appropriately selected.

(2) NMR measurement and addition mole number calculation
¹ H-NMR measurement is performed under normal conditions using Mercury 400 manufactured by Varian Technologies Japan Limited. A signal derived from the methine group of the propyleneoxy group directly bonded to the sulfate group was observed at around 4.3 ppm, a signal derived from the methyl group of the propyleneoxy group linked to the propyleneoxy group was observed at around 2.1 ppm, and the alkyl chain Since the signal derived from the methyl group is observed at around 1.9 ppm, the number of added moles of propylene oxide can be calculated by the following calculation formula.

      Average number of moles of propylene oxide added = (3a / c) + (b / c)

a: Integral value of a signal derived from a methine group of propyleneoxy group directly bonded to a sulfate group near 4.3 ppm b: Integral value of a signal derived from a methyl group of propyleneoxy group linked to a propyleneoxy group near 2.1 ppm c : Integral value of signal derived from methyl group of alkyl chain around 1.9ppm

  The content of the alkyl ether sulfate represented by the general formula (1) is 5 to 30% by mass, preferably 7 to 23% by mass, particularly 10 to 20% by mass in the aqueous hair cleansing agent of the present invention. .

  The content of the mixture of the alkyl ether sulfate of the general formula (1-1) and the alkyl sulfate of the general formula (2) is 5 to 30% by mass in the aqueous hair cleanser of the present invention. It is preferably 7 to 23% by mass, particularly 10 to 20% by mass.

  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 more preferably 10 to 16 are preferred. Further, those having a hydroxyalkyl group having 2 to 3 carbon atoms are preferred, for example, oleic acid diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide. Coconut oil fatty acid monoethanolamide, lauric acid isopropanolamide, lauric acid monoethanolamide, and the like.

  Monoalkyl glyceryl ether 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 ¹ −N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein, R ¹ 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 ² —O—R ³ —N ⁺ (CH ₃ ) ₃ X ⁻
[Wherein R ² represents an alkyl group having 12 to 22 carbon atoms, R ³ represents an ethylene group or a propylene group optionally substituted by 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 ⁴ ) ₂ N ⁺ (CH ₃ ) ₂ X ⁻
[Wherein, R ⁴ 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 ⁵ —N (CH ₃ ) ₂
[Wherein, R ⁵ 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 ⁶ —O—R ⁷ —N (CH ₃ ) ₂
[Wherein R ⁶ represents an alkyl group having 12 to 22 carbon atoms, and R ⁷ 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 8 -CONH-R 9 -N (} CH 3) 2
[Wherein R ⁸ represents an alkyl group having 11 to 21 carbon atoms, and R ⁹ 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 ¹⁰ (CH ₃ ) ₂ SiO — [(CH ₃ ) ₂ SiO] _p —Si (CH ₃ ) ₂ R ¹⁰
[Wherein, R ¹⁰ 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 diameter 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 third edition of the CTFA Dictionary (US, Cosmetic Ingredient Dictionary) under the name Amodimethicone, the amino group being 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; oils and fats such as castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, coconut oil; beeswax, whale wax, Waxes such as lanolin and carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, myristyl alcohol, behenyl alcohol, cetostearyl alcohol; isopropyl palmitate, isopropyl myristate, 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
Charge 3447 g of linear alcohol with 12 carbon atoms (Calcoal 2098, Kao) and 5.2 g of potassium hydroxide into an autoclave equipped with a stirrer, temperature controller, and automatic introduction device at 110 ° C and 1.3 kPa. Dehydration was performed for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and 430 g of propylene oxide was charged. After addition reaction and aging at 120 ° C, the mixture was cooled to 80 ° C, and unreacted propylene oxide was removed at 4.0 kPa. Thereafter, 5.6 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes and then extracted to obtain an alkoxylate having an average PO addition mole number of 0.4 mol.
The resulting alkoxylate was sulfated in a falling thin film reactor (FFR) using SO ₃ gas. The obtained sulfate was neutralized with an aqueous sodium hydroxide solution to obtain an alkyl ether sulfate composition (sulfate 1).

Production Example 2
In the same manner as in Production Example 1, an alkyl ether sulfate composition having a PO average addition mole number of 5 and an alkyl chain having an average carbon number of 12 was obtained, and this was combined with sodium alkyl sulfate having an average carbon number of 12 [Emar 0, Kao Corporation] was mixed at a molar ratio of 16:84 to obtain an alkyl ether sulfate composition (sulfate 2) having an average PO addition mole number of 0.8. Here, the average number of moles added of propylene oxide was confirmed by the above-described NMR method.

Comparative production example 1
In Production Example 1, ethylene oxide was used instead of propylene oxide, and an alkyl ether sulfate composition (comparative sulfate 1) having an average addition mole number of ethylene oxide of 0.4 and an average alkyl group carbon number of 12 was obtained. .

Comparative production example 2
In the same manner as in Production Example 1, an alkyl ether sulfate composition (Comparative sulfate 2) having an average PO addition mole number of 1.0 mol and an average alkyl group carbon number of 12 was obtained.

Comparative production example 3
Comparative alkyl sulfate 3 was sodium alkyl sulfate [Emar 0, Kao Co., Ltd.] having an alkyl group with an average carbon number of 12 and no addition of propylene oxide or ethylene oxide.

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

(Speed of foaming at low temperature)
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 an evaluation sample cooled to 5 ° C. was applied assuming winter. 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 1, the hair cleansing agent of the present invention using an alkyl ether sulfate having an average PO added mole number in an appropriate range does not become too high in viscosity even at low temperatures, and does not foam at low temperatures. The foam quality was quick and finely slid, and the slidability during rinsing and low-temperature stability were good. On the other hand, in Comparative Examples 1 and 4 using alkyl ether sulfate added with EO, viscosity increase at low temperature is large, foaming at low temperature, low temperature stability is insufficient, and foam quality is inferior. It was. Further, Comparative Examples 2 and 5 in which the PO average added mole number was too large also showed a large increase in viscosity at low temperature, poor foaming at low temperature, poor foam quality, and insufficient slip feeling during rinsing. Further, Comparative Examples 3 and 6 using alkyl sulfates were inferior in foaming at low temperature and low temperature stability, and had a strong squeaky feeling during rinsing.

Example 5 Conditioning Shampoo
(mass%)
Sulfate 1 13.0
Cationized tara gum (Catinal CTR-100, Toho Chemical Co., Ltd.) 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 6 Conditioning Shampoo
(mass%)
Sulfate 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 7 Conditioning Shampoo
(mass%)
Sulfate 1 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 8 Conditioning Shampoo
(mass%)
Sulfate 2 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 5 to 8 have quick foaming and fine foam quality at low temperatures, good foaming and slidability at the time of rinsing, and good gloss and cohesiveness of the finished hair, Excellent 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)

An aqueous hair cleanser containing 5 to 30% by mass of an alkyl ether sulfate represented by the general formula (1).
_{RO- (PO) n -SO 3 M} (1)
[Wherein, R represents an alkyl group having an average carbon number of 8 to 24, PO represents a propyleneoxy group, n represents an average PO addition mole number in a range of 0 <n <1, and M represents a cation. ] The aqueous hair cleansing agent according to claim 1, wherein the alkyl ether sulfate is produced by a step comprising steps (I) and (II).
Step (I): Step of adding propylene oxide in an average range of more than 0 mol and less than 1 mol to 1 mol of alkanol having an alkyl group having an average carbon number of 8 to 24 Step (II): obtained in step (I) Sulfating and then neutralizing the resulting alkoxylate 5 to 30% by mass of a mixture of the alkyl ether sulfate represented by the general formula (1-1) and the alkyl sulfate represented by the general formula (2), and the average PO addition mole number in the mixture is less than 1 An aqueous hair cleansing agent.
_{RO- (PO) m -SO 3 M} (1-1)
RO-SO ₃ M (2)
[Wherein, R represents an alkyl group having an average carbon number of 8 to 24, PO represents a propyleneoxy group, m represents an average number of moles of PO added of 1 or more, and M represents a cation. ]   Furthermore, the aqueous hair cleansing agent in any one of Claims 1-3 containing a nonionic surfactant or an amphoteric surfactant.   The aqueous hair cleanser according to any one of claims 1 to 4, further comprising a cationic polymer.   Furthermore, the aqueous hair cleaning agent in any one of Claims 1-5 containing silicones.   Furthermore, the aqueous hair cleaning agent in any one of Claims 1-6 containing ethylene glycol mono-fatty acid ester or ethylene glycol di-fatty acid ester.

Images