JP5600451B2 - Skin cleanser composition - Google Patents

Description

  The present invention relates to a skin cleanser composition having a good feeling during use.

  In recent years, due to diversification of user preferences, skin cleansers have emphasized the feeling of use during washing, rinsing and drying in addition to the detergency that is the original performance. On the other hand, along with an increase in users who suffer from rough skin, there is also a demand for gentleness to the skin, and a variety of surfactants are used, such as blending with surfactants that are gentle to the skin. Under such circumstances, there is a need for a feeling-of-use control technology that can be applied to various surfactant systems.

  For example, polyoxyethylene alkyl ether sulfate, which is a general-purpose surfactant, is a surfactant that is gentler to the skin than fatty acid salts (soap), but it has a slimy feel that lasts for a long time. I can't get it. Even in such a surfactant system that continues to have a slimy feel during rinsing, a technique that can provide a refreshing feel is required.

  In order to obtain a refreshing feel at the time of rinsing, for example, a skin cleansing composition containing a cationic group-containing polymer having a specific cationic charge density has also been proposed (Patent Document 1). A detergent composition comprising a cationic polymer obtained by copolymerizing a cationic vinyl monomer and a nonionic vinyl monomer having an amide bond in order to obtain smoothness and smoothness after washing and drying. Has been proposed (Patent Documents 2 and 3).

JP 2008-285479 A JP 2006-335959 A JP 2008-188953 A

  An object of the present invention is to provide a skin cleanser composition that can be quickly rinsed with water and can provide a refreshing feel during rinsing, especially in a surfactant system that continues to feel numb during rinsing. It is in.

The present invention relates to a skin cleanser composition containing the following components (A) and (B).
Component (A): Anionic group-containing surfactant Component (B): A structural unit (B-1) derived from a monomer represented by the general formula (I) and a single unit represented by the general formula (II) Copolymer containing structural unit (B-2) derived from monomer

(In the formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a methyl group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, R ¹⁰ represents a linear or branched alkyl group having 8 to 20 carbon atoms, X represents an alkylene group having 1 to 12 carbon atoms, —COOR ¹¹ —, —CONHR ¹¹ —, —OCOR ¹¹ —, —R ¹² —OCO—R ¹¹ —, wherein Y is a group selected from —COO—, —CONH—, —OCO—, wherein R ¹¹ , R is, Cl ^{- - 12} a is .Z each independently an alkylene group having 1 to 5 carbon atoms, or ^is - OSO ₃ C ₂ H _5).

  When the skin cleansing composition of the present invention is used, it can be quickly rinsed with water even in a surfactant system that continues to have a slimy feel, particularly during rinsing. In addition, a refreshing feel can be obtained during rinsing.

  In the present invention, by combining an anionic group-containing surfactant [component (A)] and a specific copolymer [component (B)], it can be quickly rinsed with water and has a refreshing feel upon rinsing. It has been found that it is effectively expressed. Hereinafter, each component of the present invention will be described.

[Component (A): Anionic group-containing surfactant]
The skin cleansing composition of the present invention contains an anionic group-containing surfactant as the component (A). As an anionic group-containing surfactant, an anionic surfactant or amphoteric one generally used in a skin cleanser containing a sulfuric acid group, a sulfonic acid group, a carboxylic acid group, a phosphoric acid group and a salt thereof. Any surfactant may be used. That is, as the component (A), an anionic surfactant having an anionic group selected from a sulfuric acid group, a sulfonic acid group, a carboxylic acid group, a phosphoric acid group and salts thereof, and an amphoteric surface activity having the anionic group 1 type or more chosen from an agent is mentioned. Among these, an anionic surfactant is preferable in terms of interaction with the copolymer of the following component (B).

  Examples of the anionic surfactant include sulfonic acid type surfactants such as alkylbenzene sulfonate, alkane (or alkene) sulfonate, α-sulfon fatty acid (or ester thereof) salt; alkyl (or alkenyl) sulfate ester salt, Sulfur ester type surfactants such as polyoxyethylene alkyl (or alkenyl) ether sulfates having an average addition mole number of 0.5 to 10; higher fatty acid salts, polyoxyethylene having an average addition mole number of 0.5 to 10 Carboxylic acid type surfactants such as alkyl (or alkenyl) ether carboxylate, acylated amino acid salt, acyl-L-glutamate; monoalkyl (or alkenyl) phosphate ester salt, average added mole number is 0.5 to 10 polyoxyethylene monoalkyl (or alkenyl) ether phosphates Phosphoric acid type surfactant and the like the like. As for carbon number of the alkyl group or alkenyl group of these anionic surfactants, 8-18 are all preferable.

  Among these, when used for a skin cleanser, the effect of the present invention can be more remarkably exerted on an anionic surfactant that has a slimy feel when rinsed. Such anionic surfactants include polyoxyethylene alkyl (or alkenyl) ether sulfate, polyoxyethylene alkyl (or alkenyl) ether carboxylate, polyoxyethylene monoalkyl (or alkenyl) ether in the above Examples include phosphate ester salts. Among these, polyoxyethylene alkyl (or alkenyl) ether sulfate and polyoxyethylene alkyl (or alkenyl) ether carboxylate are particularly preferable.

  As the polyoxyethylene alkyl (or alkenyl) ether sulfate, those represented by the formula (a1) are preferable.

R ^1a —O— (CH ₂ CH ₂ O) _n —SO ₃ Z (a1)
[Wherein, R ^1a represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, n represents an average number of 0.5 to 5, and Z represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or Indicates organic ammonium. ]

In the formula, R ^1a is preferably an alkyl group having 12 to 14 carbon atoms. Further, n is preferably 1 to 4 on average. Z includes alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; basic such as arginine and lysine Examples include cations derived from amino acids.

  As a polyoxyethylene alkyl (or alkenyl) ether carboxylate, what is represented by a formula (a2) is preferable.

^{_{R 1a -O- (CH 2 CH 2}} O) m -COOZ (a2)
[In formula, R ^<1a >, Z shows the said meaning, m shows the number of 0.5-10 on an average. ]

In the formula, R ^1a is preferably an alkyl group having 12 to 16 carbon atoms. Further, m is preferably 1 to 6 on average. Z includes alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; basic such as arginine and lysine Examples include cations derived from amino acids.

  One or more anionic group-containing surfactants of the present invention can be used. Among them, it is preferable to use a sulfate ester type surfactant and a carboxylic acid type surfactant in combination, and further, a polyoxyethylene alkyl (or alkenyl) ether sulfate ester salt having an average addition mole number of 0.5 to 5, and an average It is preferable to use a polyoxyethylene alkyl (or alkenyl) ether carboxylate having an addition mole number of 0.5 to 10 in combination. Therefore, in the present invention, the component (A) is at least polyoxyethylene alkyl (or alkenyl) ether sulfate (average addition mole number is preferably 0.5 to 5), and polyoxyethylene alkyl (or alkenyl) ether carboxyl. It is preferable to include one or more selected from acid salts (average added mole number is preferably 0.5 to 10).

[Component (B): Copolymer]
The skin cleanser composition of the present invention comprises, as component (B), the structural unit (B-1) derived from the monomer represented by the general formula (I) and the single unit represented by the general formula (II). The copolymer containing the structural unit (B-2) derived from a monomer is contained.

In formula (I), X 1 to 12 carbon atoms, preferably 1 to 5, more preferably 1 to 3 alkylene ^{group, -COOR 11 -, - CONHR 11} -, - OCOR 11 -, - R 12 - It is a group selected from OCO—R ¹¹ —, preferably a group selected from —COOR ¹¹ — and —OCOR ¹¹ —.

In the general formula (II), R ¹⁰ represents a linear or branched alkyl group having 8 to 20, preferably 8 to 12, and more preferably 12 carbon atoms. In general formula (II), Y is a group selected from —COO—, —CONH—, and —OCO—, and preferably a group selected from —COO— and —OCO—.

  Specific examples of the monomer represented by the general formula (I) include methacryloyloxyethyltrimethylammonium chloride and methacryloyloxyethyldimethylethylammonium ethyl sulfate. Among them, methacryloyloxyethyltrimethylammonium chloride is preferable.

  Specific examples of the monomer represented by the general formula (II) include octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, and the like. Of these, lauryl methacrylate and 2-ethylhexyl methacrylate are preferable.

The copolymer of the component (B) has a weight ratio of the structural unit (B-1) to the structural unit (B-2) of (B-1) :( B-2) = 80: 20 to 50:50. Some are preferable, more preferably 70:30 to 50:50, and still more preferably 65:35 to 55:45. This weight ratio can be measured by ¹ H-NMR measurement or the like, but may be based on the charged amount at the time of synthesis of component (B).

  Although the copolymer of a component (B) may have structural units other than a structural unit (B-1) and a structural unit (B-2), a structural unit (B-1) and a structural unit (B- The total of 2) is preferably 90% by weight or more and more preferably 95% by weight in all the structural units.

The weight average molecular weight (Mw) of the component (B) copolymer is preferably 10,000 to 10,000,000, and more preferably 20,000 to 5,000,000. This weight average molecular weight was determined by gel permeation chromatography (GPC, manufactured by Tosoh Corporation), column: α-M + α-M (cation), eluent: 50 mmol / LiBr, (1% CH ₃ COOH / ethanol): Measured under the conditions of water = 3: 7, flow rate: 0.6 mL / min, measurement temperature: 40 ° C., detector: RI (polyethylene glycol conversion).

  The copolymer of component (B) is obtained by radical polymerization in an ethanol solution using 2,2'-azobis (2,4-dimethylvaleronitrile) as an initiator.

[Skin cleansing composition]
The skin cleansing composition of the present invention is characterized by containing the above components (A) and (B). The component (A) in the skin cleanser composition is preferably 1.5 to 25% by weight, more preferably 5 to 20% by weight, from the standpoint of stop feeling during rinsing and expression of a refreshing feel. More preferably, it contains 10 to 18% by weight. For the same reason, the component (B) is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, still more preferably 0.3 to 1% by weight in the skin cleansing composition. contains.

  The skin cleansing composition of the present invention preferably further contains an inorganic salt or an organic acid salt having 6 or less carbon atoms as the component (C). Examples of inorganic salts include salts of alkali metals, alkaline earth metals, ammonium, and the like, and halogens, sulfuric acid, sulfurous acid, phosphoric acid, and the like. Specifically, sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, Examples include sodium bromide, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, sodium dihydrogen phosphate, disodium hydrogen phosphate and the like. Examples of the organic acid salt include salts of carboxylic acid having 6 or less carbon atoms such as acetic acid, lactic acid, malic acid, citric acid, and succinic acid, and alkali metal, ammonium and the like. Among these, sodium chloride, sodium sulfate, sodium malate, sodium lactate, sodium citrate, and sodium succinate are preferable. One or more inorganic salts or organic acid salts having 6 or less carbon atoms of the present invention can be used as long as foamability and foam quality are not disturbed, and the content in the composition is 0.5 to 10 weights. % Is preferable in terms of blendability.

  In addition to the above components (A), (B) and (C), the skin cleanser composition of the present invention is a component usually used in a skin cleanser composition, for example, a viscosity modifier such as hydroxyethyl cellulose; a polyol Moisturizers such as non-ionic surfactants; oil agents such as silicone and ester oils; organic solvents such as ethanol; dilution solvents such as water; inorganic powders, pearling agents, preservatives, bactericides Antibacterial agents, anti-inflammatory agents, ultraviolet absorbers, pH adjusters, antioxidants, metal chelating agents, fragrances, pigments, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

  The skin cleansing composition of the present invention can be produced according to a conventional method. Moreover, the dosage form can also be made into arbitrary dosage forms, such as a liquid form, paste form, cream form, solid form, powder form. Among these, it is preferable to use liquid form, paste form, and cream form, and it is preferable to mix water as a diluent solvent.

The weight average molecular weights of the polymers obtained in the following synthesis examples and comparative synthesis examples were measured (in terms of polyethylene glycol) by gel permeation chromatography (GPC) under the following conditions. GPC measurement (HLC-8120 manufactured by Tosoh Corporation) was performed under the following conditions.
* GPC measurement conditions Column: α-M + α-M (cation)
Eluent: 50 mmol / LiBr, (1% CH ₃ COOH / ethanol): water = 3: 7
Flow rate: 0.6 mL / min
Measurement temperature: 40 ° C
Detector: RI

<Synthesis Example 1>
A glass separable flask having an internal volume of 300 mL was charged with 30.1 g of methacryloyloxyethyltrimethylammonium chloride, 19.9 g of lauryl methacrylate, and 69.8 g of ethanol, mixed uniformly, and stirred for a certain time under a nitrogen atmosphere. The reaction solution was heated to around 60 ° C., and a solution prepared by dissolving 0.17 g of 2,2′-azobis (2,4-dimethylvaleronitrile) in 5.0 g of ethanol was added thereto. Polymerization was carried out by holding at around 60 to 65 ° C. for 2 hours, and then the temperature was raised to around 70 ° C. and aging was carried out for 4 hours. After the reaction solution was cooled, copolymer 1 was obtained by reprecipitation with ethyl acetate or the like. From the results of GPC measurement, the obtained copolymer 1 had a weight average molecular weight of 71,000 (in terms of polyethylene glycol). Further, as a result of ¹ H-NMR measurement, the composition ratio of this polymer [weight ratio of structural unit (B-1): structural unit (B-2)] was methacryloyloxyethyltrimethylammonium chloride: lauryl methacrylate = 60: 40 (weight ratio). The charge amount, molecular weight, monomer composition, etc. are summarized in Table 1.

<Synthesis Examples 2 and 3>
Copolymers 2 and 3 were obtained in the same manner as in Synthesis Example 1 except that the conditions were changed as shown in Table 1. Each charge amount, molecular weight, monomer composition, etc. are summarized in Table 1.

<Comparative Synthesis Examples 1-3>
Copolymers 4, 5, and 6 were obtained in the same manner as in Synthesis Example 1 except that the conditions were changed as shown in Table 1. Each charge amount, molecular weight, monomer composition, etc. are summarized in Table 1.

The symbols in the table have the following meanings.
・ QDM: methacryloyloxyethyltrimethylammonium chloride (manufactured by MRC Unitech Co., Ltd.)
・ LMA: Lauryl methacrylate (Mitsubishi Gas Chemical Co., Ltd.)
2-EHMA: 2-ethylhexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
N-BMA: n-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
T-BMA: t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65B: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Examples 1-3 and Comparative Examples 1-5>
Each component was mix | blended with the composition shown in Table 2, and fully stirred at 50 degreeC, and the skin cleansing composition was manufactured. About the compounding quantity of the component (A) of Table 2, a component (B), and a component (B '), the compounding quantity as each effective part is shown. When added as a solution or dispersion, the blending amount is determined excluding the weight of the solvent or dispersion medium. Finally, balance is achieved by the amount of ion-exchanged water.

  These skin cleansing compositions were used to evaluate the feel during rinsing by the following method. The evaluation results are also shown in Table 2.

<Evaluation method>
(1) Speed to completion of rinsing After taking 1.0 g of each skin cleansing composition in one hand, diluting with tap water and foaming, both forearms were washed and rinsed with tap water. . At that time, rinsing was carried out while rubbing both forearms, and the number of rubbing until a stop feeling was felt was evaluated. Ten professional panelists evaluated and ranked the average number of times according to the following evaluation criteria.
5: The number of rubbing is less than 10 4: The number of rubbing is 10 to less than 15 3: The number of rubbing is 15 to less than 20 2: The number of rubbing is 20 to less than 25 1: The number of rubbing More than 25 times

(2) Touch at the end of rinsing In the evaluation test of (1) above, the touch at the end of rinsing was evaluated. Evaluation was performed according to the following criteria from the evaluation results of 10 professional panelists.
A: Eight or more people answered that the stop feeling at the end of rinsing and the refreshing feeling were stronger than in Comparative Example 4.
B: 5 to 7 people answered that the feeling of stop feeling at the end of rinsing and a refreshing feeling were stronger than those of Comparative Example 4.
C: 2 to 4 people answered that the stop feeling at the end of rinsing and the refreshing feeling were stronger than in Comparative Example 4.
D: One or less people answered that the stop feeling at the end of rinsing and the refreshing feeling were stronger than in Comparative Example 4.

Claims (3)

A skin cleanser composition containing the following components (A) , ( B) and (C) .
Component (A): Anionic group-containing surfactant Component (B): A structural unit (B-1) derived from a monomer represented by the general formula (I) and a single unit represented by the general formula (II) look including the dimers derived structural unit (B-2), the weight ratio of the structural unit (B-1) and the structural unit (B-2) is, (B-1) :( B -2) = 80: Copolymer having a ratio of 20 to 50:50, and the total of the structural unit (B-1) and the structural unit (B-2) is 90% by weight or more in all the structural units.

(In the formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a methyl group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or represents an alkyl group having 1 to 3 carbon atoms, R ¹⁰ is .X representing a linear or branched alkyl group having 8-12 carbon atoms - COOR ¹¹ - a pressurized et chosen group .Y is -COO - it is where, R ¹¹ is an alkylene group having a carbon number of 1 to 5 .Z ^-. is, Cl ^{-, or} - an OSO ₃ C ₂ H _5).
Component (C): inorganic salt or organic acid salt having 6 or less carbon atoms Component (A) 1.5 to 25 wt%, Ingredient to (B) 0.05 to 5% by weight, and containing 0.5 to 10% by weight of component (C), skin cleansing of claim 1, wherein Agent composition.   The skin according to claim 1 or 2, wherein the component (A) comprises at least one selected from polyoxyethylene alkyl (or alkenyl) ether sulfate and polyoxyethylene alkyl (or alkenyl) ether carboxylate. Cleaning composition.