JP3929967B2 - Aqueous hair cleanser - Google Patents

Description

  The present invention has good foaming and slippery foam quality at the time of shampooing, has a smooth feel at the time of rinsing, gives gloss to the finished hair, and has low temperature stability and low irritation. It relates to an aqueous hair cleanser.

  Alkyl sulfates typified by sodium dodecyl sulfate have been most frequently used as cleaning components in aqueous cleaning agents because of their high detergency and large amount of foaming. However, when the alkyl sulfate was used alone, there was a great dissatisfaction with the feel at the time of washing such as a squeak. Therefore, polyoxyethylene-added alkyl sulfates (alkyl ether sulfates) in which ethylene oxide is added between alkyl groups and sulfate groups have been developed to improve the feel, especially those with an average of 2 to 3 moles of ethylene oxide added. However, it has come to be used a lot because of the good feel when washing. However, the addition of ethylene oxide has a problem that it is greatly inferior in terms of foaming speed as compared with alkyl sulfate. Although the foaming was slightly improved by mixing the alkyl sulfate and the alkyl ether sulfate, it was insufficient to achieve both quick foaming and good foam feel.

  By the way, typical alkyl ether sulfates that have been used in the past are those having an average addition mole number of ethylene oxide of 2 and those having an addition mole number of 0 are around 20% by weight, and those having an addition mole number of 1 to 3 are more than a dozen. % By weight, the balance being 4 or more added moles.

  As a technique for improving the performance of a hair washing agent by adjusting the composition ratio of the alkyl ether sulfate with respect to the number of moles of ethylene oxide added, a surfactant comprising an alkyl ether sulfate with an ethylene oxide addition mole number of 1 to 8 and an amphoteric surfactant. There is an aqueous shampoo composition having a high conditioning effect, containing 5 to 50% by weight of an agent component and containing less than 5% by weight of an alkyl ether sulfate having an addition mole number of 1 mol or less (Patent Document 1). In the description of Patent Document 1, it is unclear how to handle the number of added moles of 1, but in any case, this shampoo composition was completely insufficient in terms of foaming.

Japanese Patent No. 3260382

  Therefore, the present invention has good foaming and slippery foam quality at the time of shampooing, has a smooth feel at the time of rinsing, gives gloss to the finished hair, and has low stability at low temperatures. An object is to provide an aqueous hair cleanser that is irritating.

  As a result of examining the number of moles of ethylene oxide added in the polyoxyethylene addition type alkyl sulfate, the present inventors have used a sulfate component in which the ratio of the sulfate of addition mole number 0 to 2 is within a certain range. It has been found that a hair cleanser that satisfies the above requirements can be obtained.

That is, the present invention provides the following general formula (1)
_{R-O- (C 2 H 4} O) n -SO 3 M (1)
[Wherein, R represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, n represents 0 or a positive integer, and M represents sodium or ammonium. ]
30 to 45 wt% where n = 0, 18 to 27 wt% where n = 1, 10 to 20 wt% where n = 2, and the remaining n Aqueous hair containing 5 to 30% by weight of a sulfate-type surfactant composed of those having a value of 3 or more and the total of sulfates of n = 0 to 2 being 70% by weight or more of the total sulfates A cleaning agent is provided.

  The hair cleanser of the present invention has good foaming and slippery foam quality at the time of shampooing, has a smooth feel when rinsed, gives gloss to the finished hair, and has good low-temperature stability. It is hypoallergenic.

In the present invention, as the sulfate type surfactant, those having an ethylene oxide addition mole number within the above range are used from the viewpoint of achieving both quick foaming and good foam feel. Preferably 33 to 43% by weight, 20 to 25% by weight n = 1, 13 to 18% by weight n = 2, and the remaining n = 3 or more. In the total sulfate, 35 to 41% by weight where n = 0, 21 to 23% by weight where n = 1, 14 to 17% by weight where n = 2, and the remaining n = 3 or more More preferably, it is composed of one. In addition, the ratio of sulfate of n = 0 to 2 in the sulfate type surfactant component is 70% by weight or more from the same viewpoint, but is 70 to 85% by weight of the total sulfate. It is preferable. Such a sulfate-type surfactant is obtained by sulfating an alcohol ethoxylate obtained by adding 0.85 to 1.35 moles of ethylene oxide to higher alcohol ROH using 0.95 to 1.0 equivalent of SO ₃ . And then neutralized with sodium hydroxide or ammonia.

  The content of the sulfate-type surfactant is 5 to 30% by weight in the aqueous hair cleansing agent of the present invention, but 7 to 23% by weight, particularly 10 to 20% by weight is preferable.

  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 sulfate type surfactant.

Nonionic surfactants include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbite fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl. Examples include phenyl ethers, polyoxyalkylene (cured) castor oils, sucrose fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, fatty acid alkanolamides, alkyl glycosides, and the like. Of these, alkylglycosides, polyoxyalkylene (C ₈ -C ₂₀ ) fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamides are preferred. As the fatty acid alkanolamide, those having an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms are preferable. The fatty acid alkanolamide may be either a monoalkanolamide or a dialkanolamide, and preferably has a hydroxyalkyl group having 2 to 3 carbon atoms, such as oleic acid diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil. Examples include fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, coconut oil fatty acid monoethanolamide, lauric acid isopropanolamide, and lauric acid monoethanolamide.

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

  The nonionic surfactant and the amphoteric surfactant can be blended in the aqueous hair cleansing agent of the present invention as necessary, and two or more kinds can be used in combination. In the case of an aqueous liquid detergent, it is particularly preferable to use fatty acid amide propyl betaine or fatty acid alkanolamide because not only foaming power is improved but also an appropriate liquid property is obtained.

  The content of the nonionic surfactant is 0 to 15% by weight, more preferably 0.5 to 10% by weight, particularly 1 to 5% by weight in the aqueous hair cleansing agent of the present invention. 0 to 10% by weight, more preferably 0.5 to 8% by weight, particularly 1 to 5% by weight in the aqueous hair cleansing agent of the invention is preferred.

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

  Two or more kinds of cationic polymers may be used in combination, and the content thereof is the aqueous hair cleansing agent of the present invention from the viewpoints of improving the foam quality at the time of washing, collecting the hair after drying, and improving the touch. The content is preferably 0.02 to 5% by weight, more preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0.3% by weight.

  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.

(1) Dimethylpolysiloxane Examples include those represented by the following general formula.
(Me) ₃ SiO-[(Me) ₂ SiO] _d -Si (Me) ₃
[In formula, Me shows a methyl group and d shows the number of 3-20000. ]

(2) Amino-modified silicones Various amino-modified silicones can be used, but are described in the 3rd edition of the CTFA Dictionary (US, Cosmetic Ingredient Dictionary) under the name of Amodimethicone, especially having an average molecular weight of about 3000 to 100,000. Is preferred. This amino-modified silicone is preferably used as an aqueous emulsion. Examples of commercially available products include SM 8704C (Toray Dow Corning Silicone) and DC 929 (Dow Corning).

(3) Other silicones Other than the above, polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone, etc. It is done.

  Two or more types of silicones may be used in combination, and the content is preferably 0.01 to 10% by weight in the aqueous hair cleansing agent of the present invention from the viewpoint of smooth feeling after drying and gloss improvement. 0.05 to 6% by weight, particularly 0.5 to 3% by weight, especially 2 to 3% by weight is preferred.

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

  The aqueous hair cleanser of the present invention preferably has a pH (diluted 20 times by weight with water, 25 ° C.) of 2 to 6 when applied to hair, from the viewpoint of improving the gloss and unity of the hair, The pH is preferably 3 to 5, particularly preferably pH 3.5 to 4.5. As the pH adjuster, it is preferable to use an organic acid, particularly α-hydroxy acid, and specifically, malic acid, citric acid, lactic acid, and glycolic acid are preferable. Two or more of these organic acids may be used in combination, and the amount used is 0.01 to 5% by weight in the aqueous hair cleanser of the present invention in terms of foam quality and improvement in hair flexibility during hair washing. More preferably, it is 0.1 to 3% by weight, particularly 0.3 to 2% by weight. Further, as other pH adjusting agent, a base such as sodium hydroxide, potassium hydroxide, ammonium chloride may be used in combination with these organic acids.

  The aqueous hair cleansing agent of the present invention may contain a viscosity modifier, and examples of the viscosity modifier include hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, clay minerals, salts (sodium chloride, ammonium chloride, sodium citrate, etc.) Among them, salts, particularly sodium chloride and sodium citrate are preferable. Two or more types of viscosity modifiers may be used in combination, and the amount used thereof is preferably 0.01 to 5% by weight in the aqueous hair cleansing agent of the present invention in terms of the amount of foam and foam quality, and more preferably 0.05 to 3% by weight, particularly 0.1 to 1.5% by weight is preferred.

  The aqueous hair cleanser of the present invention contains a finish improver such as benzyl alcohol, benzyloxyethanol, panthenol, hydrolyzed silk protein, silk extract, etc. from the viewpoint of improving the feel of hair after drying and gloss. Can do. Two or more kinds of these finish improvers may be used in combination, and the content thereof is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, particularly 0.1 to 1.5% by weight in the aqueous hair cleansing agent of the present invention. % By weight is preferred.

  In addition to the above-described components, the aqueous hair cleansing agent of the present invention can be appropriately blended with components used in ordinary hair cleansing agents depending on the purpose. Such components include, for example, anti-dandruff agents; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; moisturizers such as sorbitol and panthenol; colorants such as dyes and pigments; plant extracts; Pearling agents such as titanium; fragrances; dyes; ultraviolet absorbers; antioxidants; and other components described in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) It is done.

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

Production Example 1
Calcol 2470 (Kao Corporation, dodecyl alcohol: tetradecyl alcohol = about 3: 1) 2000 g and potassium hydroxide 1.45 g were charged into a pressure-resistant sealed reactor, dehydrated at 110 ° C. and 10 mmHg for 30 minutes, and then the inside of the system was The temperature was raised to 165 ° C. After the temperature rise, 456 g of ethylene oxide was injected and an addition reaction was performed at that temperature for 30 minutes. Then, it cooled to 80 degreeC and neutralized with 1.3 g of acetic acid, and the ethylene oxide addition product of the said raw material alcohol was obtained.
Next, 1793 g of the mixture obtained by the above operation and 607 g of sulfuric acid gas were used for sulfation reaction at 40 ° C. After the reaction, neutralization was performed with 132 g of a 23 wt% sodium hydroxide aqueous solution and 556 g of ion-exchanged water. Further, the concentration and pH were adjusted using a 23 wt% sodium hydroxide aqueous solution, 75 wt% phosphoric acid and ion-exchanged water, and 10000 g of a 25 wt% aqueous solution of sulfate 1 shown in Table 1 was obtained.
The obtained sulfate was confirmed for sodium salt, sulfate, anion and EO chain according to the cosmetic raw material standard (published in 1999).

Production Example 2
A 25 wt% aqueous solution of sulfate 2 shown in Table 1 was obtained according to Production Example 1 except that the reaction ratio of the raw materials was changed.
The obtained sulfate was confirmed for sodium salt, sulfate, anion, and EO chain according to the cosmetic raw material standard (published in 1999).

Production Example 3
Using 1793 g of the ethylene oxide adduct of the raw material alcohol obtained in Production Example 1 and 607 g of sulfuric acid gas, a sulfation reaction was carried out at 40 ° C. After the reaction, neutralization was performed with 150 g of 28 wt% aqueous ammonia and 600 g of ion exchange water. Further, the concentration and pH were adjusted using 28 wt% ammonia water and ion exchange water, and 10000 g of a 25 wt% aqueous solution of sulfate 3 shown in Table 1 was obtained.
The obtained sulfate was confirmed for sulfate, anion and EO chain according to the cosmetic raw material standard (published in 1999).

Examples 1-11 and Comparative Examples 1-4
Using the sulfate type surfactant (sodium lauryl ether sulfate) shown in Table 1, the hair cleansing agents shown in Tables 2 and 3 were prepared, and the speed of foaming, the feeling of slipping during shampooing, and the hair after drying We evaluated gloss and unity. The composition ratios in Table 1 were measured by gas chromatography.

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

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

(Slip feeling when washing hair)
A human hair bundle having a length of 25 cm, a width of 5.5 cm, and a weight of 10 g was lightly rinsed with warm water at 40 ° C., and then excess water was removed and foamed sufficiently for about 30 seconds using 0.5 g of a hair cleaning agent. 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

(Glossy and unity after drying)
The hair bundles treated in the same manner as the slip evaluation were 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

Sulfate 1: Obtained in Production Example 1 Sulfate 2: Obtained in Production Example 2 Sulfate 3: Obtained in Production Example 3 Comparative sulfates 1 and 2: EO average added mole number of 2.0 Mixture of lauryl ether sulfate (Comparative sulfate 3) and lauryl sulfate Comparative sulfate 3: EO average addition mole number 2.0 (Emar 227-PH11, Kao)

Example 12 Pearl Appearance Shampoo
(weight%)
Sulfate 1 15.0
Laurylamidopropylbetaine 0.5
Cocoyl monoethanolamide 0.3
Ethylene glycol distearate 2.0
Cationized hydroxyethyl cellulose 0.2
Glycerin 1.0
Salicylic acid Amount of pH 3.7 Ion exchange water Balance

  The shampoo had quick foaming and good foam slip, and had good gloss and cohesion of the finished hair.

Example 13 Conditioning Shampoo
(weight%)
Sulfate 1 13.0
Cocoyl monoethanolamide 0.7
Myristyl alcohol 1.0
Distearyl ether 3.0
Cationized hydroxyethyl cellulose 0.5
Glycerin 1.0
Sodium chloride 1.0
Lactic acid 0.5
Malic acid Amount of pH 3.7 Ion-exchanged water Balance

  The shampoo had quick foaming and good foam slip, and had good gloss and cohesion of the finished hair.

Example 14 Conditioning Shampoo
(weight%)
Sulfate 1 13.0
Cocoyl monoethanolamide 1.0
Myristyl alcohol 1.0
Cetanol 0.5
Ethylene glycol distearate 3.0
Cationized hydroxyethyl cellulose 0.1
Cationized guar gum 0.3
Glycerin 1.0
Dimethicone (400,000 mPa · s) 0.5
Sodium chloride 0.2
Benzyl alcohol 0.5
Malic acid 0.7
Ion exchange water balance

  The shampoo had quick foaming and good foam slip, and had good gloss and cohesion of the finished hair.

Example 15 Conditioning Shampoo
(weight%)
Sulfate 1 10.0
Laurylamidopropylbetaine 3.0
Myristyl alcohol 1.0
Cetanol 0.5
Behenyltrimonium chloride 0.5
Ethylene glycol distearate 2.0
Cationized guar gum 0.3
Panthenol 0.1
Hydrolyzed silk protein 0.3
Sodium chloride 1.0
Malic acid 0.75
Lactic acid 0.75
Sodium hydroxide pH 3.5 amount Ion-exchanged water Balance

  The shampoo had quick foaming and good foam slip, and had good gloss and cohesion of the finished hair.

Example 16 Pearl Appearance Anti Dandruff Shampoo
(weight%)
Sulfate 1 13.0
Cocoyl monoethanolamide 0.5
Myristyl alcohol 1.0
Cetanol 0.5
Distearyl ether 2.0
Cocoyl benzalkonium chloride 0.5
Cationized hydroxyethyl cellulose 0.3
Cationized guar gum 0.3
Glycerin 1.0
Dimethicone (400,000 mPa · s) 1.0
Sodium hydroxide 0.2
Benzyloxyethanol 0.5
Malic acid 0.7
Ion exchange water balance

  The shampoo had quick foaming and good foam slip, and had good gloss and cohesion of the finished hair.

Claims (5)

The following general formula (1)
_{R-O- (C 2 H 4} O) n -SO 3 M (1)
[Wherein, R represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, n represents 0 or a positive integer, and M represents sodium or ammonium. ]
30 to 45% by weight of n = 0, 18 to 27% by weight of n = 1, 10 to 20% by weight of n = 2, and the remaining n = Aqueous hair containing 5 to 30% by weight of a sulfate-type surfactant composed of those of 3 or more and the total of sulfates of n = 0 to 2 being 70% by weight or more of the total sulfate Washing soap.   The aqueous hair cleanser according to claim 1, further comprising a nonionic surfactant or an amphoteric surfactant.   Furthermore, the aqueous hair cleansing agent of Claim 1 or 2 containing a cationic polymer.   Furthermore, the aqueous hair cleaning agent in any one of Claims 1-3 containing silicones. Furthermore, the aqueous hair cleaning agent in any one of Claims 1-4 containing the pearling agent containing ethylene glycol monoalkyl ester or ethylene glycol dialkyl ester.