JP6302671B2 - Skin cleanser composition - Google Patents

Description

  The present invention relates to a skin cleansing composition.

Conventionally, there has been a great need for women to effectively remove sebum dirt and make pores darker, and in response to this demand, face wash products that exhibit high cleaning performance against sebum have been put on the market. In recent years, makeup products that are less likely to break down against sweat and sebum have been increasing for the purpose of maintaining makeup, and these makeup products are less likely to fall off with regular makeup removal, and make-up removal that exhibits higher cleaning performance. It has been demanded. On the other hand, with a facial cleanser or makeup remover that exhibits high cleaning performance, the skin after cleaning may become rough due to physical condition or the like.
On the other hand, Patent Document 1 discloses a cleansing material containing a specific glycerin derivative, a polyhydric alcohol and a surfactant for the purpose of having a cleansing effect and less irritation to the eyes.
Patent Document 2 discloses a detergent composition containing a specific glycerin derivative, an amphoteric surfactant and an anionic surfactant containing a sulfate group for the purpose of moistening the skin after washing and preventing rough skin. Things are disclosed.
Patent Document 3 discloses a detergent composition containing a specific glycerin derivative and a higher fatty acid for the purpose of preventing the skin from becoming irritated after being dried.

JP 2006-232717 A JP 2006-249146 A Japanese Patent Laid-Open No. 2006-241413

However, these cleaning compositions still have insufficient cleaning power for sebum and difficult-to-remove makeup products. In addition, if the skin after washing becomes rough, the skin may dry, and desquamation, irregularities, etc. may be seen.As a result, if you apply makeup products such as a makeup base or foundation after washing, the skin may not adhere cleanly. there were.
Accordingly, there has been a demand for facial cleansers and makeup removers that have high cleaning performance for sebum and makeup products that are difficult to remove, and that the skin after washing becomes smooth and the makeup product to be applied after that can be applied cleanly.

  The present invention relates to a skin cleanser composition having high detergency, smooth skin after washing, and good makeup when applied with a makeup base or foundation. Makeup glue means that when a foundation is applied to the skin and visually observed, there is no desquamation, and pores and skin irregularities are not noticeable and adhere to the skin cleanly compared to the condition of the bare skin.

  The inventors have found that a skin cleansing composition that solves the above problems can be obtained by using a specific glycerin derivative, an alkyl ether carboxylic acid or a salt thereof, and a nonionic surfactant of HLB 8 or more in combination. .

The present invention includes the following components (A), (B), (C) and (D):
(A) General formula (1)

(In the formula, Gly represents a residue obtained by removing a hydroxyl group from glycerin, PO represents an oxypropylene group, EO represents an oxyethylene group, and a and b are average added moles of PO and EO, respectively. The mass ratio of PO to EO (PO / EO) is 1/5 to 5/1, BO represents an oxyalkylene group having 4 carbon atoms, and c represents the average added mole number of BO. And indicates a value of 1 to 5)
0.3 to 20% by mass of a glycerin derivative represented by
(B) General formula (2)

(In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, X represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an organic ammonium, or a basic amino acid. Show)
An alkyl ether carboxylic acid or a salt thereof represented by 0.3 to 20% by mass,
(C) HLB8 or more nonionic surfactant 0.5-20 mass%,
(D) It contains water, and the mass ratio (C) / ((A) + (B)) of the total amount of the component (C) and the acid equivalent amount of the components (A) and (B) is 0.05. It is related with the skin cleansing composition which is -2.

  The skin cleanser composition of the present invention has a high detergency against dirt mixed with foundation and sebum, and the skin after washing becomes smooth, and when applying a makeup base or foundation to the washed skin, the makeup paste is good Can be applied to the skin evenly.

  The glycerin derivative of component (A) used in the present invention is represented by the general formula (1), and propylene oxide and ethylene oxide are added to glycerin at a ratio of 3 to 150 molar equivalents with respect to glycerin, respectively. Thereafter, an alkylene oxide having 4 carbon atoms is added at a ratio of 3 to 15 molar equivalents with respect to glycerin. That is, the glycerin derivative of the general formula (1) can be obtained by synthesizing an adduct of PO and EO and then adding an alkylene oxide having 4 carbon atoms in a block form.

  The mass ratio (PO / EO) of propylene oxide (PO) and ethylene oxide (EO) is 1/5 or more from the viewpoint of the rough skin prevention effect and the elongation when the foundation is applied to the washed skin. Feels smooth, smoothes the skin after washing, improves foaming, is 5/1 or less from the viewpoint of preventing rough skin, is 1/5 to 5/1, and is an addition form of propylene oxide and ethylene oxide May be random or block. In order to further reduce the feeling of slimming during rinsing, it is preferable to add in a random state.

  The average added mole number of propylene oxide (PO) and ethylene oxide (EO) improves foaminess, does not feel slimy at the time of rinsing, from the effect of preventing rough skin, from the point of elongation when applying foundation to the washed skin, Each is 1 or more, and is 50 or less from the point of moistening the skin after use and smoothing the skin after washing, and is preferably in the range of 1 to 50 respectively.

  The average added mole number of alkylene oxide (BO) having 4 carbon atoms is 1 or more in terms of elongation when moisturizing the skin after use and applying foundation to the skin after washing, rinsing properties, foaming From the viewpoint of smoothing the skin after washing and washing, it is preferably 5 or less, and preferably in the range of 1 to 5.

  Examples of the alkylene oxide having 4 carbon atoms include 1,2-butylene oxide, 2,3-butylene oxide, and tetramethylene oxide (tetrahydrofuran). Among these, 1,2-butylene oxide is preferable from the viewpoint of easy availability and reaction control.

  Usually, when these alkylene oxides are added to glycerin, the addition reaction is performed using an alkali catalyst, a phase transfer catalyst, a Lewis acid catalyst, or the like. In general, it is preferable to use an alkali catalyst such as potassium hydroxide.

  Specific examples of the component (A) include those having an average added mole number of (EO) of 8, an average added mole number of (PO) of 5, and an average added mole number of (BO) of 3. Polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO) is preferable from the viewpoint of smoothness of the skin after washing and makeup. As a commercial product, Wilbride S-753 (manufactured by NOF Corporation) can be used.

  Component (A) can be used alone or in combination of two or more, and the content is 0 in the total composition from the point of smoothness of the skin after washing, uniformity when applying foundation, and makeup paste. 0.3 mass% or more, preferably 0.5 mass% or more, and more preferably 0.8 mass% or more. From the viewpoint of elongation and makeup paste when the foundation is applied to the washed skin, it is 20% by mass or less, preferably 13% by mass or less, and more preferably 6% by mass or less. Moreover, content of a component (A) is 0.3-20 mass% in the whole composition, 0.5-13 mass% is preferable, and 0.8-6 mass% is more preferable.

The alkyl ether carboxylic acid of component (B) used in the present invention is represented by the general formula (2).
In the formula, R ¹ is an alkyl group having 4 to 22 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms, and further an alkyl group having 8 to 16 carbon atoms. An alkyl group having 10 to 16 carbon atoms is more preferable. The alkyl chain of R ¹ may be either a straight chain or a branched chain, but a straight chain alkyl group is preferred from the viewpoint of foamability. Furthermore, the average carbon number of R ¹ is preferably 10.8 to 12.8, more preferably 10.8 to 12.5, more preferably 12.1 to 12.8 in terms of foamability and foam quality, and low temperature stability. 12.4 is more preferable.
Further, R ¹ is preferably contains two or more alkyl groups, from the viewpoint of excellent foam volume and foam quality of a component having the alkyl chain length most content, component (B) in more than 55 wt% It is preferably less than 97% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass.

Moreover, in formula, n shows the number of 0-20, and 0-12 are more preferable. In addition, n shows the addition mole number of ethylene oxyoxide, and the average addition mole number (average value of n) in the composition of a component (B) is 1.5-10 from the point that foam quality is favorable. Preferably, 2.5 to 4.5 is more preferable, 2.5 to 3.4 is more preferable, 2.8 to 3.4 is more preferable, and 2.8 to 3.1 is still more preferable.
The alkyl ether carboxylic acid of the component (B) preferably contains 2.8 to 30% by mass of the component of n = 0 in the general formula (2) from the viewpoint of reducing the squeaky feeling at the time of rinsing. It is more preferable to contain -30 mass%, 4.9-27 mass% is still more preferable, 9.6-27 mass% is more preferable, 9.9-16 mass% is still more preferable, 9.9-15 mass% More preferably.
Furthermore, the total content of the n = 1 component and the n = 2 component is preferably 42.8% by mass or less, more preferably less than 40% by mass, and more preferably 20 to 37% by mass from the viewpoints of foam quality and foam amount. Is more preferable, 27-36.5 mass% is more preferable, and 35-36.1 mass% is still more preferable.

  In the formula, X represents a hydrogen atom; an alkali metal such as sodium or potassium; an alkaline earth metal such as calcium or magnesium; an ammonium; an organic ammonium derived from an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine; Examples include basic amino acids such as L-arginine. Among these, alkali metals are preferable from the viewpoints of foamability, low-temperature stability, and lack of coloration over time.

  In the general formula (2), the alkyl ether carboxylic acid of the component (B) is such that the mass ratio of the components of n = 0, 1, 2, 3, 4 is (mass of the n = 0 component): (n = 1 component) Mass): (mass of n = 2 components): (mass of n = 3 components): (mass of n = 4 components) = 1: 0.99 to 3.50: 0.89 to 3.00: 0 .76 to 3.00: 0.63 to 1.6 is preferable from the viewpoint of foaming property, detergency, and suppression of squeaky feeling during rinsing.

  Furthermore, in the general formula (2), the component of n = 0 is contained in an amount of 9.6% by mass to less than 12% by mass, (n = 0 component mass): (n = 1 component mass): (n = 2 Component mass): (n = 3 component mass): (n = 4 component mass) = 1: 1.53-1.87: 1.59-2.25: 1.33-2.16: 1 .14 to 1.52, or 12 to 17% by mass of n = 0 component, (n = 0 component mass): (n = 1 component mass): (n = 2 Component mass): (n = 3 component mass): (n = 4 component mass) = 1: 0.99 to 1.34: 0.89 to 1.40: 0.76 to 1.23: 0 .63 to 0.99 is preferable from the viewpoints of foaming properties, rinsing properties, smoothness of the skin after washing, and makeup paste.

  Further, in the general formula (2), the component of n = 0 is included in the range of 9.9 to 11.5% by mass, (the mass of the n = 0 component): (the mass of the n = 1 component): (the n = 2 component) Mass): (mass of n = 3 components): (mass of n = 4 components) = 1: 1.58-1.84: 1.72-2.17: 1.49-2.00: 1.14 To 1.52 or, in general formula (2), 13 to 17% by mass of n = 0 component, (n = 0 component mass): (n = 1 component mass): (n = Mass of 2 components) :( mass of n = 3 components) :( mass of 4 components) = 1: 1.00 to 1.31: 0.93 to 1.34: 0.79 to 1.18 : 0.63 to 0.99 is preferable from the viewpoints of the amount of foam, foam quality and rinsing properties, smoothness of the skin after washing, and makeup paste.

In the component (B), in the general formula (2), R ¹ is an alkyl group having 4 to 22 carbon atoms, and the average carbon number of R ¹ is 10.8 to 12.8. The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, the average value is 1.5 to 10, and the component of n = 0 It is preferable that the total content of the component of n = 1 and the component of n = 2 is 20-42.8 mass% including 2.8-27 mass%. By doing in this way, foamability can be accelerated | stimulated, the uniformity (nonuniformity) when a foundation is apply | coated to the skin after washing | cleaning can be improved, and makeup glue can be improved more.

In the component (B), in the general formula (2), R ¹ is an alkyl group having 4 to 22 carbon atoms, and the average carbon number of R ¹ is 10.8 to 12.8. The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, the average value is 1.5 to 10, and the component of n = 0 It is preferable that the total content of the component of n = 1 and the component of n = 2 is 20-37 mass% including 4.9-27 mass%. By doing in this way, foamability can be accelerated.

In the component (B), in the general formula (2), R ¹ is an alkyl group having 6 to 20 carbon atoms, the average carbon number of R ¹ is 10.8 to 12.8, and the most content The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, an average value is 2.5 to 4.5, and n = 0. It is preferable that a component is contained 9.6-27 mass%, and the sum total content of the component of n = 1 and the component of n = 2 is 27-36.5 mass%. By doing in this way, foamability can be accelerated | stimulated and the smoothness of the skin after washing | cleaning and a makeup paste can be improved.

In the component (B), in the general formula (2), R ¹ is an alkyl group having 8 to 18 carbon atoms, the average carbon number of R ¹ is 10.8 to 12.8, and the most content The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, an average value is 2.5 to 3.4, and n = 0. It is preferable that a component is contained 9.6-27 mass%, and the sum total content of the component of n = 1 and the component of n = 2 is 27-36.5 mass%. By doing in this way, the uniformity (unevenness) when applying foundation to the skin after washing can be improved, and the makeup paste can be improved.

In the component (B), in the general formula (2), R ¹ is an alkyl group having 8 to 16 carbon atoms, the average carbon number of R ¹ is 10.8 to 12.5, and the most content The component having a large alkyl chain length is 60 to 95% by mass, n represents a number of 0 to 20, the average value is 2.8 to 3.4, and the component of n = 0 is 9 It is preferable that the total content of the component of n = 1 and the component of n = 2 is 27 to 36.5% by mass, including 6.6 to 27% by mass, preferably 9.9 to 16% by mass. By doing in this way, foam amount and foam quality can be improved.

In the component (B), in the general formula (2), R ¹ is an alkyl group having 10 to 16 carbon atoms, the average carbon number of R ¹ is 12.1 to 12.4, and the most content The component having a large alkyl chain length is 60 to 95% by mass, n represents a number of 0 to 20, the average value is 2.8 to 3.1, and the component of n = 0 is 9 It is preferable that the total content of the component of n = 1 and the component of n = 2 is 35 to 36.1% by mass. By doing this, the amount of foam, foam quality, difficulty of dripping foam, cleanability, smoothness of the skin after washing, elongation when foundation is applied to the skin after washing, foundation on the skin after washing Uniformity when applied and makeup paste can be improved.

Incidentally, in the components of the present invention (B), the distribution of alkyl chain length of R ^1, the average alkyl chain length of R ^1, components of n = 0, average addition mole number of n, n = 0, 1, 2, The mass ratio of the components 3 and 4 is determined as follows by analyzing the alkyl ether carboxylic acid represented by the general formula (2) by gas chromatography.

[Distribution of alkyl chain length of R ¹ ]
Of the peak areas obtained by gas chromatography, the peak area of each alkyl chain length corresponding to n = 0 mol was determined, and the sum of these was determined as 100, and the percentage of each alkyl chain length distribution was determined. also calculated similarly in n = 1 to 3 mol, and the average value of the percentage of each alkyl chain length distribution of n = 0 to 3 mol, determined the distribution of alkyl chain length of R ¹ (from which, R ¹ The alkyl group component containing the largest amount of the composition can be specified).

[Average alkyl chain length of R ¹ ]
From the distribution of the alkyl chain length of R ¹ determined as described above, the ratio of each component was determined, and the carbon number corresponding to the alkyl chain length corresponding to the ratio thus obtained was multiplied to obtain the sum of these. This was defined as the average alkyl chain length.

[Component content of n = 0, total content of component of n = 1 and component of n = 2]
Among the compositions of R ¹ , the most abundant alkyl chain length was specified, and the areas of gas chromatography corresponding to n = 0 to 10 of the components were totaled. The total amount was 100%, and the total content of n = 0, n = 1 and n = 2 was calculated.

[Average number of moles of n added]
The most alkyl chain length contained in the composition of R ¹ was specified, and the areas of the gas chromatography corresponding to n = 0 to 10 of the components were totaled (the ones with n of 11 or more are trace amounts. Excluded). The total amount was set to 1, and the ratio of each of n = 0 to 10 was obtained. This ratio was multiplied by the number of moles added, and the sum of these was taken as the average number of moles added.

[Mass ratio of components of n = 0, n = 1, n = 2, n = 3, n = 4]
Regarding the ratio of each component having a different number of EO addition moles, the distribution of the alkyl chain length of R ¹ is obtained from the peak area obtained by gas chromatography by the method described above, and the maximum content of the R ¹ composition is determined. The alkyl chain length component was identified, and the maximum component was identified from the area ratio of n = 0, n = 1, n = 2, n = 3, and n = 4.

The component (B) alkyl ether carboxylic acid or salt thereof preferably has the above composition.
Component (B) is 0.3% by mass or more and preferably 0.5% by mass or more as an acid in the total composition from the viewpoint of elongation when foundation is applied to the washed skin. 0.8% by mass or more is more preferable. And it is 20 mass% or less in the whole composition, 15 mass% or less is preferable, and 8 mass% or less is more preferable. Moreover, content of a component (B) is 0.3-20 mass% in the whole composition, 0.5-15 mass% is preferable, and 0.8-8 mass% is more preferable.

Component (C) used in the present invention is a nonionic surfactant having HLB of 8 or more, preferably HLB of 8 to 18, more preferably of HLB of 10 to 18, and can obtain more excellent detergency.
Here, HLB is an index indicating a hydrophilic-lipophilic balance (Hydrophilic-Lypophilic Balance). In the present invention, a value calculated using the following equation by Oda and Teramura et al. Is used.

Examples of the component (C) include polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene polyoxypropylene glycol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene. Sorbit fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether fatty acid ester, sucrose fatty acid ester, alkyl polyglucoside, ( And poly) alkyl glyceryl ether. Among these, from the viewpoint of improving detergency, rinsability and stability, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy Ethylene hydrogenated castor oil fatty acid ester and alkyl polyglucoside are preferable, and polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, and alkyl polyglucoside are more preferable.
As the polyethylene glycol fatty acid ester, polyethylene glycol monolaurate (12EO) (HLB13.7) and the like are preferable, and as a commercially available product, Emanon 1112 (manufactured by Kao Corporation) and the like can be used. As polyoxyethylene alkyl ether, polyoxyethylene (20) octyldodecyl ether (HLB13.3), polyoxyethylene (25) octyldodecyl ether (HLB14.1) and the like are preferable, and Emulgen 2020G-HA and Emulgen 2025G (Kao) OD-20, OD-25 (manufactured by Nippon Emulsion Co., Ltd.) and the like can be used. As the alkyl polyglucoside, decyl glucoside, lauryl glucoside and the like are preferable, and Mydol 10 (HLB15.7) (manufactured by Kao Corporation) and the like can be used.

  Component (C) can be used singly or in combination of two or more. From the standpoint of detergency, uniformity when applying a foundation after washing (no unevenness), makeup paste and stability. Is 0.5 mass% or more in the total composition, preferably 0.8 mass% or more, more preferably 2 mass% or more, 20 mass% or less, preferably 17 mass% or less, and 12 mass% or less. Is more preferable. Moreover, content of a component (C) is 0.5-20 mass% in the whole composition, 0.8-17 mass% is preferable, and 2-12 mass% is more preferable.

  Moreover, a component (C) and the nonionic surfactant below HLB8 can be used in combination, and it is more preferable from the point of detergency and stability. Examples of nonionic surfactants less than HLB8 include ethylene glycol fatty acid esters such as ethylene glycol monostearate, polyethylene glycol fatty acid esters such as polyethylene glycol (2) monostearate, polyethylene glycol (5) decylpenta Polyethylene glycol surfactants such as polyethylene glycol alkyl ethers such as decyl ether, polyethylene glycol (5) hydrogenated castor oil monoisolaurate, and the like; propylene glycol fatty acid ester, polypropylene glycol fatty acid ester, propylene glycol alkyl Ethylene oxide of ether, polypropylene glycol alkyl ether, propylene glycol alkyl ether Propylene glycol surfactants such as derivatives; Glycerin fatty acid esters such as glycerin monoisostearic acid; Glycerin alkyl ethers such as glycerin monoisostearyl ether; Sorbitan fatty acid esters such as sorbitan monostearic acid ester; Examples include glycerin fatty acid esters. Of these, glycerin fatty acid ester, sorbitan fatty acid ester, and glycerin alkyl ether are preferable.

  Nonionic surfactants less than HLB8 can be used alone or in combination of two or more. From the viewpoint of rinsing properties and smoothness of the skin after washing, the content is not included in the total composition. Or 5% by mass or less, preferably 0.005% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and preferably 2% by mass or less, and 1% by mass. % Or less is more preferable. Moreover, 0.005 mass% or more and less than 5 mass% are preferable in the whole composition, and, as for content of the nonionic surfactant less than HLB8, 0.05-2 mass% is more preferable, 0.1-1 mass % Is more preferable.

  In the skin cleanser composition of the present invention, the mass ratio (C) / ((A) + (B)) of the total amount of the component (C) and the acid equivalent amount of the components (A) and (B) is washed. From the point of improving the smoothness of the later skin, the elongation when applying the foundation to the washed skin, uniformity (no unevenness) and the makeup paste when applying the makeup base and foundation to the washed skin, It is 0.05 or more, 0.3 or more is preferable, 0.45 or more is more preferable, 2 or less is preferable, 1.8 or less is preferable, and 1.5 or less is more preferable. Moreover, the mass ratio (C) / ((A) + (B)) of the total amount of the component (C) and the acid equivalent amounts of the components (A) and (B) is 0.05 to 2, and 0 .3-1.8 is preferable, and 0.45-1.5 is more preferable.

  Furthermore, in the skin cleanser composition of the present invention, the mass ratio (A) / ((B) + (C)) of the total amount of the component (A) and the acid equivalent amount of the components (C) and (B) is: , Smoothness of the skin after washing, elongation when applying foundation to the skin after washing, uniformity (no unevenness) and points to improve makeup paste when applying a makeup base or foundation to the skin after washing Therefore, 0.01 or more is preferable, 0.05 or more is more preferable, 0.1 or more is more preferable, 2 or less is preferable, 1.5 or less is more preferable, and 1 or less is still more preferable. In addition, the mass ratio (A) / ((B) + (C)) of the total amount of the component (A) and the acid equivalent amount of the components (C) and (B) is preferably 0.01 to 2, 0.05 to 1.5 is more preferable, and 0.1 to 1 is even more preferable.

  In the skin cleanser composition of the present invention, the acid equivalent amount of component (B) and the mass ratio (B) / (C) of component (C) are preferably 0.05 or more from the viewpoint of cleanability and feeling of use. 0.1 or more is more preferable, 0.15 or more is further preferable, 10 or less is preferable, 6 or less is more preferable, and 1 or less is still more preferable. Moreover, 0.05-10 are preferable, as for the mass ratio (B) / (C) of the acid conversion amount of a component (B) and a component (C), 0.1-6 are more preferable, 0.15-1 are Further preferred.

  Furthermore, in the skin cleanser composition of the present invention, the acid equivalent amount of component (B) and the total content (B) + (C) of component (C) are in the total composition from the viewpoint of cleanability and feeling of use. 1 mass% or more is preferable, 3 mass% or more is more preferable, 6 mass% or more is further more preferable, 25 mass% or less is preferable, 22 mass% or less is more preferable, and 18 mass% or less is still more preferable. Further, the acid equivalent amount of component (B) and the total content (B) + (C) of component (C) are preferably 1 to 25% by mass, more preferably 3 to 22% by mass in the total composition, 6 -18 mass% is still more preferable.

  The skin cleanser composition of the present invention contains component (D) water as a solvent, and the remainder of the above components and other components constituting the skin cleanser composition. The content of water is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, preferably 97% by mass or less, more preferably 95% by mass or less, and 93% by mass in the total composition. % Or less is more preferable. Moreover, 10-97 mass% is preferable in the whole composition, as for content of the water of a component (D), 15-95 mass% is more preferable, 30-93 mass% is still more preferable.

Furthermore, the skin cleansing composition of the invention can contain a component (E) amphoteric surfactant from the viewpoint of cleanability and foamability. Specific examples include betaine-type surfactants, amino acid-type surfactants, imidazoline-type surfactants, and amine oxide-type surfactants. Preferably, betaine-type surfactant is mentioned from the point of foam amount, More preferably, alkylamidopropyl betaine and alkylhydroxysulfobetaine are mentioned. Commercially available products such as Amphitol 20AB and Amphitol 20HD (manufactured by Kao Corporation) can be used.
The amphoteric surfactant can be used singly or in combination of two or more, and the content is preferably 0.1% by mass or more, and 0.5% by mass or more in the total composition for improving foam retention. More preferably, 1% by mass or more is further preferable, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 4% by mass or less is still more preferable. Moreover, 0.1-15 mass% is preferable in the whole composition, content of the amphoteric surfactant of a component (E) has more preferable 0.5-10 mass%, and 1-4 mass% is still more preferable.

The skin cleansing composition of the present invention can further contain a polyol other than the component (A) as the component (F). Examples of the polyol include polyhydric alcohol, polyglycerin, polyethylene glycol, polypropylene glycol, and sugar.
More specifically, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, isoprene glycol, 1,3-butylene glycol, hexylene glycol, trimethylolpropane, glycerin, PPG-9 diglyceryl and the like. Among these, propylene glycol, isoprene glycol, 1,3-butylene glycol, hexylene glycol, glycerin and PPG-9 diglyceryl are preferable, and 1,3-butylene glycol, propylene glycol, isoprene glycol, glycerin and PPG-9 di Glyceryl is more preferable from the viewpoint of improving the feeling of use and the elongation of the skin foundation after washing.

  Examples of polyglycerin, polyethylene glycol, and polypropylene glycol include polyglycerins having a molecular weight of 2000 or less, polyethylene glycol having a molecular weight of 10,000 or less, and polypropylene glycol having a molecular weight of 1000 or less. Among these, diglycerin, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 1000, polyethylene glycol 1540, polyethylene glycol 6000, diethylene glycol monoethyl ether, dipropylene glycol, polypropylene glycol (3), and polypropylene glycol (7) are used. It is preferable from the viewpoint of improving the feeling and elongation of the foundation of the skin after washing.

  Examples of the sugar include sorbitol, erythritol, pentaerythritol, methyl glucoside, ethyl glucoside, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside and the like, and alkyl glucosides having 2 or less carbon atoms in the alkyl chain are preferable. Of these, methyl glucoside, ethyl glucoside, polyoxyethylene methyl glucoside, and polyoxypropylene methyl glucoside are preferable, and polyoxyethylene methyl glucoside and polyoxypropylene methyl glucoside improve the feeling of use and the growth of the skin foundation after washing. This is more preferable.

  The polyol of component (F) can be used singly or in combination of two or more, and the content is all from the points of moisturizing feeling, non-stickiness of the skin after washing, and smoothness of the skin after washing. 0.1 mass% or more is preferable in a composition, 0.5 mass% or more is more preferable, 1 mass% or more is further more preferable, 1.5 mass% or more is further more preferable, 45 mass% or less is preferable, 35 mass% % Or less is more preferable, 25 mass% or less is more preferable, and 6 mass% or less is more preferable. Further, the content of the component (F) is preferably 0.1 to 45% by mass, more preferably 0.5 to 35% by mass, further preferably 1 to 25% by mass, and 1.5 to 6% in the entire composition. A mass% is even more preferable.

Furthermore, the skin cleansing composition of the present invention can contain a component (G) water-soluble polymer in order to improve the skin feel after washing.
From the viewpoint of detergency and stability, the water-soluble polymer is preferably a nonionic water-soluble polymer containing cellulose as a structural unit or an anionic water-soluble polymer containing a structural unit derived from acrylic acid or methacrylic acid.
Examples of the nonionic water-soluble polymer containing cellulose as a structural unit include alkyl celluloses such as methyl cellulose and ethyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methylcellulose.
Of these, hydroxyalkyl cellulose is preferable and hydroxyethyl cellulose is more preferable from the viewpoints of detergency, oiliness, and refreshing feeling.
Moreover, as a nonionic water-soluble polymer containing cellulose as a structural unit, those having a molecular weight of 50,000 to 5,000,000 are preferable, and those having a molecular weight of 100,000 to 4,000,000 are more preferable from the viewpoint of detergency, oiliness and refreshing. As a commercially available product, HEC Daicel SE400 (manufactured by Daicel Finechem) or the like can be used.

  An anionic water-soluble polymer containing a structural unit derived from acrylic acid or methacrylic acid is synthesized using acrylic acid or methacrylic acid as a monomer. For example, a carboxyvinyl polymer, an acrylic acid / alkyl methacrylate copolymer is used. Can be mentioned. Among these, acrylic acid / alkyl methacrylate copolymer is preferable from the viewpoint of storage stability and feeling of use, and a copolymer of (acrylic acid / acrylic acid) with acrylic acid and alkyl methacrylate having 10 to 30 carbon atoms. Alkyl (C10-30)) copolymers) are more preferred. PEMULEN TR-1, PEMULEN TR-2, Carbopol ETD2020 (manufactured by Lubrizol Advanced Materials) and the like can be used as commercially available products.

  The anionic water-soluble polymer containing a structural unit derived from acrylic acid or methacrylic acid is preferably used after neutralizing all or part of the units of acrylic acid or methacrylic acid using an alkaline agent. The alkali agent to be neutralized is not particularly limited as long as it is an alkali agent that can be usually added to cosmetics. For example, potassium hydroxide, sodium hydroxide, and the like can be used. The alkaline agent can be used alone or in combination of two or more, and is preferably contained in the skin cleanser composition in an amount of 0.001% by mass to 0.4% by mass, and the composition has a pH of 5 to 5. It is preferably 9 and more preferably adjusted to pH 5.5-8. In addition, the measurement of pH is a value obtained by diluting each skin cleansing composition 20 times with ion-exchanged water at 30 ° C.

  The water-soluble polymer of component (G) can be used singly or in combination of two or more, and has a detergency, stability, refreshing feeling, and impregnation when a skin cleansing composition is impregnated into a sheet. Therefore, the content is preferably 0.01% by mass or more, more preferably 0.025% by mass or more, still more preferably 0.05% by mass or more, preferably 1% by mass or less, and 0.7% by mass in the total composition. % Or less is more preferable, and 0.3 mass% or less is still more preferable. Further, the content of the component (G) is preferably 0.01 to 1% by mass, more preferably 0.025 to 0.7% by mass, and more preferably 0.05 to 0.3% by mass in the entire composition. .

  The skin cleanser composition of the present invention further comprises components used in ordinary skin cleanser compositions, for example, surfactants other than components (B), (C) and (E), components (A) and ( Moisturizers other than F), ethanol, oil components, bactericides, anti-inflammatory agents, antiseptics, chelating agents, thickeners other than component (G), salts, pearling agents, scrub agents, perfumes, cooling agents, It can contain a pigment, an ultraviolet absorber, an antioxidant, a plant extract and the like.

As surfactants other than the components (B), (C) and (E) used in the present invention, anionic surfactants other than the component (B) and cationic surfactants can be contained. From the viewpoint of foaming An anionic surfactant is preferred. Examples of the anionic surfactant include fatty acids having 12 to 22 carbon atoms or salts thereof, polyoxyethylene alkylsulfuric acid having 8 to 22 carbon atoms or salts thereof, and amino acid surfactants. From the viewpoint of foamability, A fatty acid having 12 to 22 carbon atoms or a salt thereof, a polyoxyethylene alkylsulfuric acid having 8 to 22 carbon atoms or a salt thereof is preferable. The content of the anionic surfactant is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 1.5 to 5% by mass in the total composition from the viewpoint of the amount of foam and rinsing properties. preferable. The content of the cationic surfactant is preferably 0.1 to 1% by mass, more preferably 0.15 to 0.8% by mass, and still more preferably 0.2 to 0.6% by mass in the total composition.
Ethanol can be blended from the point of refreshing the skin during application. As content of ethanol, 0.1-10 mass% is preferable in the whole composition, 0.3-5 mass% is more preferable, 0.5-3 mass% is still more preferable.

The skin cleansing composition of the present invention is produced by mixing the compounding ingredients by a usual method. The obtained skin cleanser composition may be either liquid or solid, but when it is liquid, the viscosity when measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 30 ° C. is 5 to 50000 mPa · It is preferably s, more preferably 6 to 10000 mPa · s, still more preferably 7 to 1000 mPa · s, and it can be adjusted by appropriately selecting the blending components.
In the present invention, the viscosity was measured using a B-type viscometer (TV-B type, Tokyo Keiki) at 30 ° C. and less than 100 mPa · s. 1, the rotation number is 60 rpm, the viscosity is 100 or more and less than 500 mPa · s. 1, the rotation number is 12 rpm, the viscosity is 500 or more and less than 1000 mPa · s. 1, the rotation number is 6 rpm, the viscosity is 1000 or more and less than 10,000 mPa · s. 3, with a rotational speed of 12 rpm and a viscosity of 10,000 mPa · s or higher, the rotor No. 4. Measure at 12 rpm. The measurement time is 1 minute.

The skin cleanser composition of the present invention is suitable as, for example, a cleansing agent, makeup remover, facial cleanser, body soap, hand soap, etc., and a cleansing agent and makeup remover that removes makeup cosmetics are preferred. Further, it is preferably used for cleansing makeup cosmetics applied to the face.
The skin cleansing composition of the present invention is, for example, a method of wiping the composition as it is or by shaking and separating the separated composition, immersing it in a sheet, etc. It can be used by a method of wiping, a method of rinsing after washing in a hand, a method of rinsing after immersing in a sheet or the like, a method of rinsing after wiping by the above method, and a method of rinsing. Furthermore, it can also be used as a form impregnated into the sheet. Moreover, the method of using as a sheet | seat soaking in cotton etc. as a sheet | seat and the method of using as a form impregnated to a sheet | seat is preferable, and the method of using as a form impregnated to a sheet | seat is more preferable.
Further, the skin cleanser composition of the present invention is filled with the composition as it is in the former container, the foam discharged from the former container is taken in hand, and directly applied to the skin as it is without diluting with water. It can be used by rinsing with water after massage and massage.
Regarding the above-described embodiments, the present invention further discloses the following compositions.

<1> The following components (A), (B), (C) and (D):
(A) General formula (1)

(In the formula, Gly represents a residue obtained by removing a hydroxyl group from glycerin, PO represents an oxypropylene group, EO represents an oxyethylene group, and a and b are average added moles of PO and EO, respectively. The mass ratio of PO to EO (PO / EO) is 1/5 to 5/1, BO represents an oxyalkylene group having 4 carbon atoms, and c represents the average added mole number of BO. And indicates a value of 1 to 5)
0.3 to 20% by mass of a glycerin derivative represented by
(B) General formula (2)

(In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, X represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an organic ammonium, or a basic amino acid. Show)
An alkyl ether carboxylic acid or a salt thereof represented by 0.3 to 20% by mass,
(C) HLB8 or more nonionic surfactant 0.5-20 mass%,
(D) It contains water, and the mass ratio (C) / ((A) + (B)) of the total amount of the component (C) and the acid equivalent amount of the components (A) and (B) is 0.05. A skin cleanser composition that is ~ 2.

<2> The skin cleanser composition according to <1>, wherein the component (A) is polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO).
The content of <3> component (A) is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, preferably 13% by mass or less, and preferably 6% by mass or less in the total composition. More preferably, the content of the component (A) is preferably 0.5 to 13% by mass in the total composition, and more preferably 0.8 to 6% by mass, the skin according to <1> or <2>. Cleaning composition.

<4> In the component (B), preferably, in the general formula (2), R ¹ is an alkyl group having 4 to 22 carbon atoms, and the average carbon number of R ¹ is 10.8 to 12.8. In addition, the component having the largest alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, and the average value is 1.5 to 10, Any of <1> to <3>, wherein the content of n = 0 is 2.8 to 27% by mass, and the total content of the component n = 1 and the component n = 2 is 20 to 42.8% by mass. 2. A skin cleanser composition according to claim 1.
<5> In the component (B), preferably, in the general formula (2), R ¹ is an alkyl group having 6 to 20 carbon atoms, and the average carbon number of R ¹ is 10.8 to 12.8. Moreover, the component which has the alkyl chain length with the largest content is 55 mass% or more and less than 97 mass%, Furthermore, n shows the number of 0-20, and an average value is 2.5-4.5. <1> to <4>, wherein the content of n = 0 is 9.6 to 27% by mass, and the total content of the component n = 1 and the component n = 2 is 27 to 36.5% by mass. A skin cleanser composition according to any one of the above.
<6> In component (B), preferably, in general formula (2), R ¹ is an alkyl group having 10 to 16 carbon atoms, and R ^{1 has} an average carbon number of 12.1 to 12.4. Moreover, the component which has the alkyl chain length with the largest content is 60-95 mass%, Furthermore, n shows the number of 0-20, an average value is 2.8-3.1, n Any of the above <1> to <5>, which contains 9.9 to 15% by mass of the component of = 0, and the total content of the component of n = 1 and the component of n = 2 is 35 to 36.1% by mass 1. A skin cleanser composition according to 1.
The content of <7> component (B) is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and preferably 15% by mass or less, and 8% by mass as an acid in the total composition. % Or less is more preferable, and the content of the component (B) is preferably 0.5 to 15% by mass in the total composition, and more preferably 0.8 to 8% by mass. <1> to <6> A skin cleanser composition according to any one of the above.

<8> Component (C) is preferably HLB 8-18, more preferably a nonionic surfactant of HLB 10-18, any one of <1> to <7> above. Composition.
<9> The component (C) is preferably a skin cleanser composition according to any one of <1> to <8>, which is a glycerin fatty acid ester, a sorbitan fatty acid ester, or a glycerin alkyl ether.
The content of <10> component (C) is preferably 0.8% by mass or more, more preferably 2% by mass or more, preferably 17% by mass or less, more preferably 12% by mass or less in the total composition. The content of component (C) is preferably 0.8 to 17% by mass in the total composition, and more preferably 2 to 12% by mass. The skin according to any one of <1> to <9> Cleaning composition.

<11> The mass ratio (C) / ((A) + (B)) of the total amount of the component (C) and the acid equivalent amount of the components (A) and (B) is preferably 0.3 or more. Yes, 0.45 or more is more preferable, 1.8 or less is preferable, 1.5 or less is more preferable, and the mass ratio of the total amount of the component (C) and the acid conversion amount of the components (A) and (B) ( C) / ((A) + (B)) is preferably 0.3 to 1.8, and more preferably 0.45 to 1.5. Any one of the above items <1> to <10> Skin cleansing composition.
<12> The mass ratio (A) / ((B) + (C)) of the total amount of the component (A) and the acid equivalent amount of the components (C) and (B) is preferably 0.01 or more. Yes, 0.05 or more is more preferable, 0.1 or more is more preferable, 2 or less is preferable, 1.5 or less is more preferable, 1 or less is still more preferable, Component (A), Component (C) and (B )) The total mass ratio (A) / ((B) + (C)) of the acid conversion amount is preferably 0.01 to 2, more preferably 0.05 to 1.5, and The skin cleansing composition according to any one of <1> to <11>, wherein 1 to 1 are more preferable.
<13> The acid equivalent amount of component (B) and the mass ratio (B) / (C) of component (C) are preferably 0.05 or more, more preferably 0.1 or more, and 0.15 or more. Is more preferably 10 or less, more preferably 6 or less, still more preferably 1 or less, and the acid equivalent amount of the component (B) and the mass ratio (B) / (C) of the component (C) are preferably 0. The skin cleansing composition according to any one of <1> to <12>, which is 0.05 to 10, more preferably 0.1 to 6, and still more preferably 0.15 to 1.
<14> The acid equivalent amount of component (B) and the total content (B) + (C) of component (C) are preferably 1% by mass or more and more preferably 3% by mass or more in the total composition. 6 mass% or more is more preferable, 25 mass% or less is preferable, 22 mass% or less is more preferable, 18 mass% or less is still more preferable, and the acid conversion amount of component (B) and the total content of component (C) ( B) + (C) is preferably 1 to 25% by mass in the total composition, more preferably 3 to 22% by mass, and even more preferably 6 to 18% by mass, any one of <1> to <13> 2. A skin cleanser composition according to claim 1.

<15> Component (D) The content of water is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, and preferably 97% by mass or less in the total composition. 95 mass% or less is more preferable, 93 mass% or less is still more preferable, Content of the water of a component (D) becomes like this. Preferably, it is 10-97 mass% in a whole composition, and 15-95 mass% is more preferable. The skin cleanser composition according to any one of <1> to <14>, wherein 30 to 93% by mass is more preferable.
<16> The skin cleanser composition according to any one of <1> to <15>, further comprising a component (E) amphoteric surfactant.
<17> The skin cleanser composition according to any one of <1> to <16>, further comprising a polyol other than the component (A) as the component (F).
<18> The skin cleanser composition according to any one of <1> to <17>, which may further contain a component (G) a water-soluble polymer.

<19> Any of the above <1> to <18>, wherein a method of immersing and wiping in cotton or the like as a sheet, a method of using as a form impregnated in a sheet is preferable, and a method of using as a form impregnated in a sheet is more preferable 1. A skin cleanser composition according to 1.
<20> Fill the foam container as it is, take the foam discharged from the foam container, apply it directly to the skin without diluting it with water, massage it thoroughly and massage. The skin cleanser composition according to any one of <1> to <18>, which can be used by rinsing away.

The alkyl ether carboxylic acid and salt of component (B) used in the skin cleansing composition of the present invention can be produced, for example, as follows.
Unless otherwise indicated, “%” indicates mass%. Moreover, the alkyl composition of the alkyl ether carboxylic acid in the reaction mixture produced | generated by reaction, EO addition molar distribution, and the ratio of each component were measured with the following analysis methods by gas chromatography (GC).

(GC analysis conditions)
GC equipment; Agilent Technologies, 7890A
Column; manufactured by Agilent Technologies, DB-5
(30m, inner diameter 0.25mm, film thickness 0.25μm)
Detector; FID
Carrier; helium gas, 1mL / min
Temperature rising condition: Temperature raised from 100 ° C. to 325 ° C. at 5 ° C./min. Then, hold 325 ° C. for 35 minutes.

(Sample pretreatment method)
150 mg of alkyl ether carboxylate was dissolved in 50 mL of methanol. Moreover, about the skin cleansing composition, it extract | collected so that it might become 150 mg as alkyl ether carboxylate, and melt | dissolved in methanol 50mL. When the skin cleanser composition contained a strong anionic surfactant such as polyoxyethylene alkyl ether sulfate, it was collected so that it was 250 mg or less. Take 1 mL of this solution and apply it to a solid-phase cartridge (Biotage, Isolute SAX, 1 g, 3 mL, 500-0100-B) that has been conditioned in advance with 4 mL of methanol, and collect the passing solution in a 10 mL round bottom test tube. Gathered. Thereafter, elution was performed with 6 mL of a solution obtained by adding 100 mL of methanol to 4.6 g of formic acid, and the eluate was also collected in the same test tube. The collected solution was placed in a block heater heated to 50 ° C., blown with nitrogen gas, concentrated to about 1 mL, and further blown with nitrogen gas at room temperature to dry. Thereto, 2 mL of a diazomethane-ether solution was added, and the mixture was allowed to stand at room temperature for 10 minutes with stirring for derivatization. Thereafter, nitrogen gas was blown at room temperature, and the mixture was concentrated to 500 μL or less, and then chloroform was added to make 500 μL, which was subjected to GC analysis.
In addition, the diazomethane-ether solution was prepared in the following procedures using the diazomethane production | generation apparatus (Miyamoto Riken Kogyo make, GM-50). The first and second receptacles, and the second and third receptacles are connected with a silicone rubber stopper and a Teflon (registered trademark) tube. In a second receiver, 0.8 g of N-methyl-N′-nitro-N-nitrosoguanidine was collected and 2.5 mL of ion exchange water was added. In a third receiver, 10 mL of t-butyl methyl ether was collected. The first, second and third receivers were ice-cooled. Subsequently, a plastic syringe was attached to the second receiver, and 3 mL of a solution in which 20 g of sodium hydroxide was dissolved in 100 mL of ion-exchanged water was placed in this syringe. This sodium hydroxide aqueous solution is slowly added dropwise to produce diazomethane gas, and nitrogen gas is gently blown from the first receiver side, dissolved in t-butyl methyl ether of the third receiver, and diazomethane-ether A solution was obtained.
The following reagents were used in the sample pretreatment.
Methanol (manufactured by Kanto Chemical, for high performance liquid chromatography, 25183-1B)
Formic acid (manufactured by Wako Pure Chemical Industries, reagent special grade, 066-00461)
Chloroform (manufactured by Kanto Chemical, deer grade 1, 07278-01)
N-methyl-N'-nitro-N-nitrosoguanidine (manufactured by Kanto Chemical, deer grade 1, 25596-51)
t-Butyl methyl ether (manufactured by Kanto Chemical, deer special grade, 04418-00)
Sodium hydroxide (Wako Pure Chemical Industries, special grade, 196-13761)

Production Example 1
In a stainless steel autoclave equipped with stirring and temperature control functions, 1144 g (6.14 mol) of lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], 60.2 g (0 trade name: Calcoal 4098, manufactured by Kao) .281 mol) and 2.68 g (0.0478 mol) of potassium hydroxide were added and dehydration under reduced pressure was performed. Next, 996 g (22.6 mol) of ethylene oxide (EO) was introduced at 155 ° C., and the reaction was carried out at a reaction temperature of 155 ° C. and a reaction pressure of 0.4 MPa for 2 hours. After completion of the reaction, the mixture was stirred for 30 minutes at 80 ° C. under reduced pressure of 6 kPa to remove unreacted ethylene oxide, and then nitrogen was introduced to normal pressure, and 4.82 g (0.0482 mol) of 90% lactic acid was autoclaved. In addition, the mixture was stirred at 80 ° C. for 30 minutes to obtain an alkyl ethoxylate (hereinafter also referred to as “produced AE”) having an EO addition mole number of 3.55 mol.
In a glass reaction vessel equipped with a stirring function, temperature control function and oxygen gas introduction tube, 90 g (0.2 mol) of the above product and 16.7 g of 48% aqueous sodium hydroxide solution (0.2 mol as sodium hydroxide) ), Palladium-platinum-bismuth catalyst (supporting 4% palladium, 1% platinum and 5% bismuth on activated carbon, water content 50%) 0.9 g and 494.4 g water, respectively. Under stirring conditions, the liquid temperature was raised to 70 ° C., and a catalytic oxidation reaction was performed at a reaction temperature of 70 ° C. for 3.5 hours while blowing oxygen at a rate of 27 mol% (vs. production AE / hour). The reaction rate was 89%.
After completion of the reaction, the catalyst was filtered off from the reaction solution to obtain an aqueous solution of alkyl ether carboxylic acid Na salt. Subsequently, 35% hydrochloric acid was added, and a liquid separation operation was performed to obtain an alkyl ether carboxylic acid. This is EC1.

As a result of analysis by gas chromatography, EC1 is represented by the following formula (2): X = H, R ¹ is lauryl group / myristyl group = 95/5, average carbon number is 12.1, and average value of n is 2. 8, The component of n = 0 was contained 14.7 mass%, and the total amount of the component of n = 1 and the component of n = 2 was 36.1 mass%.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.22: 1.23: 1.06: 0.83.

Production Example 2
Following production example 1, decyl alcohol [trade name: Calcoal 1098, manufactured by Kao], lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], myristyl alcohol [trade name: Calcoal 4098, manufactured by Kao], cetyl alcohol [trade name] : Calcoal 6098, manufactured by Kao] at a mass ratio of 10/70/15/5 was reacted with EO to obtain an alkyl ethoxylate having 3.55 mol of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.

As a result of analysis by gas chromatography, in the general formula (2), X = H, R ¹ is decyl group / lauryl group / myristyl group / palmityl group = 10/70/15/5, average carbon number is 12.3, The average value of n was 3.3 and 15.2% by mass of n = 0 components, and the total amount of n = 1 and n = 2 components was 31.4% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (n = mass of 3 component): (mass of n = 4 component) = 1: 1.07: 1.00: 0.85: 0.67.

Production Example 3
A glass reaction vessel equipped with stirring and temperature control functions was charged with 372 g (2.00 mol) of lauryl alcohol, the temperature was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate was added. The reaction was carried out for 5 hours while adding 88 g (2.20 mol) of sodium hydroxide in portions. After completion of the reaction, the precipitate was separated by filtration and subsequently acidified by adding 35% hydrochloric acid to obtain an alkyl ether carboxylic acid (in the general formula (2), X = H, R ¹ is a lauryl group, n = 0).

Production Example 4
Following Production Example 1, EO was reacted with decyl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of gas chromatography analysis, in general formula (2), X = H, R ¹ is a decyl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.

Production Example 5
Following Production Example 1, EO was reacted with lauryl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of gas chromatography analysis, in general formula (2), X = H, R ¹ is a lauryl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.

Production Example 6
According to Production Example 1, EO was reacted with myristyl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in the general formula (2), X = H, R ¹ is a myristyl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.

Production Example 7
Following Production Example 1, EO was added to a raw material in which lauryl alcohol and cetyl alcohol were mixed at a mass ratio of 20/80 to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in the general formula (2), X = H, R ¹ is lauryl group / palmityl group = 20/80, n average value is 3.1, and n = 0 is 16% by mass. In addition, the total amount of the n = 1 component and the n = 2 component was 37% by mass.

Production Example 8
Following Production Example 1, lauryl alcohol was subjected to EO reaction as a raw material to obtain an alkyl ethoxylate having 4.05 moles of EO added. This was subjected to an oxidation reaction as in Production Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.

As a result of analysis by gas chromatography, in general formula (2), X = H, R ¹ is a lauryl group, n has an average value of 3.5, and n = 0 contains 11.4% by mass, n = 1 The total amount of the components and n = 2 was 30.6% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1.1.31: 1.38: 1.25: 1.06.

Production Example 9
In a stainless steel autoclave equipped with stirring and temperature control functions, 1144 g (6.14 mol) of lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], 60.2 g (0 trade name: Calcoal 4098, manufactured by Kao) .281 mol) and 2.6 g (0.0478 mol) of potassium hydroxide were added and dehydration under reduced pressure was performed. Subsequently, 718 g (16.3 mol) of ethylene oxide (EO) was introduced at 155 ° C., and the reaction was carried out at a reaction temperature of 155 ° C. and a reaction pressure of 0.4 MPa for 2 hours. After completion of the reaction, the mixture was cooled and stirred at 80 ° C. under a reduced pressure of 6 kPa for 30 minutes to remove unreacted ethylene oxide, then nitrogen was introduced to normal pressure, and 4.82 g (0.0482 mol) of 90% Lactic acid was added to the autoclave and stirred at 80 ° C. for 30 minutes to obtain an alkyl ethoxylate having 2.55 mol of EO added.
A glass reaction vessel equipped with stirring and temperature control functions was charged with 600 g (2.00 mol) of the above product, the temperature of the solution was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate was added. ) And 88 g (2.20 mol) of sodium hydroxide were added in portions, and the reaction was carried out for 5 hours. After completion of the reaction, 35% hydrochloric acid was added until the pH reached 2.8 to convert it into an acid form, and the oil layer was separated to obtain an alkyl ether carboxylic acid. This is EC6.

As a result of analysis by gas chromatography, in the general formula (2), X = H, R ¹ is lauryl group / myristyl group = 94/6, average carbon number is 12.1, average value of n is 3.1, n = 0% component was included, and the total amount of the n = 1 component and the n = 2 component was 35.4% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.65: 1.92: 1.74: 1.32.

  In the examples, regarding EC2, the alkyl ether carboxylic acids obtained in Production Example 5, Production Example 6 and Production Example 7 were mixed at a mass ratio of 78.75 / 15 / 6.25, respectively. did.

  In the examples, regarding EC3, the alkyl ether carboxylic acids obtained in Production Example 2 and Production Example 3 were mixed at a mass ratio of 90/10 to obtain EC3.

  In the examples, regarding EC4, EC1 obtained in Production Example 1 and alkyl ether carboxylic acid obtained in Production Example 4 were mixed in a mass ratio of 40/60 to obtain EC4.

  In the examples, regarding EC5, the alkyl ether carboxylic acids obtained in Production Example 2 and Production Example 8 were mixed at a mass ratio of 40/60 to obtain EC5.

Examples 1-22, Comparative Examples 1-4
Manufactures a skin cleanser composition having the composition shown in Tables 4-6, cleansability for sebum and foundation, smoothness of the skin after washing, elongation when the foundation is applied to the washed skin, and after washing The uniformity (non-uniformity) when the foundation was applied, the covering power when applying the foundation to the washed skin, makeup paste (sensory evaluation), and makeup paste (quantitative evaluation) were evaluated. The results are shown in Tables 4-6.
Examples 1, 5, 6 and 10 are reference examples and are not included in the scope of the present invention.
In addition, the structure of the component (B) used in the Example is as showing in Table 2 and Table 3.
Moreover, the average EO addition mole number of the commercially available alkyl ether carboxylic acid (AKYPO RLM25 (made by Kao Co., Ltd.), AKYPO RLM45 (made by Kao Co., Ltd.), and the view light LCA (manufactured by Sanyo Chemical Co., Ltd.) used in the Examples is the distributor of each company The catalog values and the values published on the homepage were referred to, and the unknown alkyl composition, the component amount of n = 0, the total amount of the component of n = 1 and the component of n = 2 were analyzed by the above method.

(Production method)
Components (A), (B) and (C) were added to component (D) heated to 70 ° C. and stirred until uniform. Thereafter, other components were further added and mixed, and the mixture was cooled to room temperature with stirring to obtain a skin cleansing composition.

(Evaluation method)
(1) Detergency for sebum and foundation:
Model comedo sebum (composition of Table 1) was heated to 50 ° C., stirred with a stirrer for 1 minute to be uniform, and cooled. On the artificial leather (made by Okamoto Chemicals), the model sebum was applied in a size of about 60 μL, about 7 cm × about 4 cm, and allowed to air dry for 30 minutes. In addition, about 18mg of foundation (Sofina Prima Vista Liquid Foundation Ocher 05 mixed with 10% black iron oxide. Use the puff attached to the foundation. The same foundation is used in the evaluation method of (7)). Applied. Then, the model sebum and the foundation applied on the artificial leather were wiped with a cotton nonwoven fabric obtained by uniformly immersing 4 g of each skin cleaning composition in 1 g of a cotton nonwoven fabric under a load of 200 g and once. The expert panelist evaluated in the following 5 grades, and judged by the total score of 3 persons.
5: It fell very well.
4: It fell well.
3: It fell.
2: Cannot drop much.
1: Cannot be dropped.

(2) Skin smoothness after washing:
3 expert panelists are cotton non-woven fabrics in which 4 g of each skin cleanser composition is uniformly dipped in 1 g of cotton non-woven fabric. Foundation (Sofina Prima Vista Liquid Foundation Ocle 05. Use puff attached to skin for application (The same foundation was also used in the evaluation methods (3) to (6)). Ten minutes later, the wiped skin was touched with a finger, and the smoothness was subjected to sensory evaluation in the following five stages, and the total score of three persons was determined. Smoothness indicates that the finger moves without resistance when touching the skin with the finger.
5: Very smooth.
4: Smooth.
3: Slightly smooth.
2: Not very smooth.
1: Not smooth.

(3) Elongation when foundation is applied to washed skin:
Three professional panelists wiped the face to which the same foundation as (2) was applied with a cotton nonwoven fabric in which 4 g of each skin cleansing composition was uniformly immersed in 1 g of cotton nonwoven fabric. Ten minutes later, the same foundation was applied to the face, and the elongation when applied was subjected to sensory evaluation in the following five stages, and judged by the total score of three people.
5: Very good growth.
4: Elongation is good.
3: Slightly good growth.
2: Not so good 1: Not good.

(4) Uniformity (non-uniformity) when foundation is applied to washed skin:
Three professional panelists wiped the face to which the same foundation as (2) was applied with a cotton nonwoven fabric in which 4 g of each skin cleansing composition was uniformly immersed in 1 g of cotton nonwoven fabric. Ten minutes later, the same foundation was applied to the face, and the uniformity of the foundation was subjected to sensory evaluation in the following five stages, and judged by the total score of three persons. Uniformity indicates the non-uniformity of the foundation.
5: There is no unevenness.
4: There is almost no unevenness.
3: Not very uneven.
2: There is some unevenness.
1: There is unevenness.

(5) Covering power when applying foundation to washed skin:
Three professional panelists wiped the face to which the same foundation as (2) was applied with a cotton nonwoven fabric in which 4 g of each skin cleansing composition was uniformly immersed in 1 g of cotton nonwoven fabric. Ten minutes later, the same foundation was applied to the face, and the covering power was sensory-evaluated in the following five stages, and judged by the total score of three people.
5: Very good covering power.
4: Excellent covering power.
3: Slightly excellent covering power.
2: The covering power is not very good.
1: The covering power is not excellent.

(6) Cosmetic paste (sensory evaluation):
Three professional panelists wiped the face to which the same foundation as (2) was applied with a cotton nonwoven fabric in which 4 g of each skin cleansing composition was uniformly immersed in 1 g of cotton nonwoven fabric. Ten minutes later, the same foundation was reapplied to the face, and sensory evaluation of the makeup paste was performed in the following five stages, and the total score of three persons was determined. Makeup glue means that when a foundation is applied to the skin and visually observed, there is no desquamation, and pores and skin irregularities are not noticeable and adhere to the skin cleanly compared to the state of bare skin.
5: The makeup paste is very good.
4: Excellent makeup paste.
3: Slightly excellent makeup paste.
2: The makeup paste is not very good.
1: The makeup paste is not excellent.

(7) Makeup glue (quantitative evaluation):
The model comedo sebum (composition of Table 1) was heated to 50 ° C., stirred with a stirrer for 1 minute so as to be uniform, and then cooled. On the artificial leather (made by Okamoto Chemicals Co., Ltd.), the model sebum was applied to a size of about 60 μL, about 7 cm × about 4 cm, and naturally dried for 30 minutes. Further, about 18 mg of the same foundation as (1) was applied thereon. Then, the model sebum and the foundation on the artificial leather were wiped once with a cotton nonwoven fabric obtained by uniformly immersing 4 g of each skin cleaning composition in 1 g of the cotton nonwoven fabric under a load of 200 g. After 1 hour, about 18 mg of the same foundation as (1) was applied to the wiped site. Then, the brightness | luminance of the site | part which apply | coated the foundation was measured, and it evaluated about the cosmetic paste.

(Measurement method for luminance measurement)
・ Device: VHX-100 DIGITAL MICROSCOPE KEYENCE (Keyence Corporation)
・ Magnification: 100 times ・ Brightness: Approx. 65 on the scale when the minimum knob dial is 0 and the maximum is 100
・ Luminance range: 0-255

The evaluation of the makeup paste by luminance was estimated from the following calculation method.
The measurement result of the luminance is indicated by a curve with the luminance range on the horizontal axis and the frequency on the vertical axis. Then, makeup paste was estimated based on the area surrounded by the horizontal axis, the vertical axis, and the curve. First, the area surrounded by the curve and the range of the luminance range 0 to 255 is calculated (measured value of the luminance range 0 to 255). Then, the area surrounded by the curve and the range of the luminance range 170 to 255 is calculated (measured value in the range of the luminance range 170 to 255). Here, the range of the luminance range 170 to 255 is the luminance when measured in the best state of the makeup paste in a state where the foundation used in the evaluation is applied on the artificial leather and the washing and the foundation are not repainted. A range that includes a curve. And makeup glue
It was calculated from “makeup paste (%) = (measured value in the range of luminance range 170 to 255) / (measured value in the range of luminance range 0 to 255) × 100”. The higher the value, the better the makeup.

Example 23
A skin cleanser composition having the following composition can be produced in the same manner as in Examples 1 to 22. The resulting skin cleanser composition has a high detergency against dirt mixed with foundation and sebum, smoothing the skin after washing, and applying a makeup base or foundation to the washed skin gives a good makeup paste and is uniform Can be applied to the skin.

(component)
Polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO) * 6 2.5 (mass%)
25CA * 1 2.5
Polyethylene glycol monolaurate * 7 5.0
Lauryl hydroxysultain * 10 1.5
PPG-9 Diglyceryl * 11 2.0
Glycerin 2.0
48% KOH 0.36
Water balance <br/> Total 100
* 1: AKYPO RLM25 (Kao Corporation)
* 6: Will Bride S-753 (manufactured by NOF Corporation)
* 7: Emanon 1112 (manufactured by Kao Corporation, HLB13.3)
* 10: Amphitol 20HD (Kao Corporation, 30% active ingredient)
* 11: SY-DP9 (Sakamoto Pharmaceutical Co., Ltd.)

Claims (4)

The following components (A), (B), (C) and (D):
(A) General formula (1)

(In the formula, Gly represents a residue obtained by removing a hydroxyl group from glycerin, PO represents an oxypropylene group, EO represents an oxyethylene group, and a and b are average added moles of PO and EO, respectively. The mass ratio of PO to EO (PO / EO) is 1/5 to 5/1, BO represents an oxyalkylene group having 4 carbon atoms, and c represents the average added mole number of BO. And indicates a value of 1 to 5)
0.3 to 20% by mass of a glycerin derivative represented by
(B) General formula (2)

(In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, X represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an organic ammonium, or a basic amino acid. Show)
An alkyl ether carboxylic acid or a salt thereof represented by 0.3 to 20% by mass,
(C) HLB8 or more nonionic surfactant 0.5-20 mass%,
(D) It contains water, and the mass ratio (C) / ((A) + (B)) of the total amount of the component (C) and the acid equivalents of the components (A) and (B) is 0.4. The skin cleaning composition which is -1.8, and the acid conversion amount of a component (B) and the mass ratio (B) / (C) of a component (C) are 0.15-6 .   The skin cleansing composition according to claim 1, wherein the component (A) is polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO).   The mass ratio (A) / ((B) + (C)) of the total amount of the component (A) and the acid equivalent amount of the components (C) and (B) is 0.01 to 2. 2. A skin cleanser composition according to 2. A cleaning method in which the skin cleaning composition according to any one of claims 1 to 3 is used by impregnating a sheet.