JP5830343B2 - Skin cleanser composition - Google Patents

Description

  The present invention relates to a skin cleansing composition.

In recent years, along with an increase in users who suffer from rough skin, skin cleansers are required to be gentle to the skin. For this reason, it has been studied to add a skin-friendly surfactant to the skin cleanser. However, surfactants that are considered to be gentle to the skin generally have poor foam retention during washing, and the foam disappears in the latter half of washing, and it is difficult to give a feeling of washing.
In addition, such a cleaning agent has a problem that a refreshing feeling of use cannot be obtained because it has a sliminess during rinsing.

Patent Document 1 describes that a liquid detergent composition containing a phosphate ester and a water-soluble aluminum salt has low irritation to the skin, is excellent in rinsing properties, and provides a refreshing feeling.
Patent Documents 2 and 3 give a squeaky feeling by adding a polyvalent metal salt such as calcium salt to the composition using an anionic surfactant such as polyoxyethylene alkyl ether sulfate as a main ingredient. It is described.

JP-A-9-208989 JP 2007-112984 A Japanese National Patent Publication No. 11-508268

However, although these cleaning compositions have good rinsing properties, they contain a polyvalent metal salt, and thus have problems such as easy disappearance of bubbles during cleaning and weak cleaning feeling.
An object of the present invention is to provide a skin cleanser composition that is gentle on the skin, excellent in foam retention, difficult to disappear during washing, has a high cleaning feeling, and does not become slippery during rinsing and has a refreshed feeling of use. It is to provide.

  The present inventors have found that a skin cleansing composition that solves the above problems can be obtained by using a combination of an alkyl ether carboxylate having a specific distribution and a water-soluble polyvalent metal salt.

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

(In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic ammonium).
In which the average carbon number of R ¹ is 10.8 to 12.8, and the component of n = 0 exceeds 9.6% by mass and is 27% by mass or less, an alkyl ether carboxylic acid or a salt thereof containing from 0.1 to less than 40% by mass of a component of n = 1 and a component of n = 2 in total of 0.1 to 30% by mass,
(B) Water-soluble polyvalent metal salt 0.01-5% by mass,
(C) A skin cleansing composition containing water is provided.

  The skin cleanser composition of the present invention has excellent foam retention, high foam viscosity and elasticity, good foam feel, gentle to the skin, and the foam does not easily disappear during washing and is easy to wash. Therefore, a high cleaning feeling can be obtained. In addition, it is possible to obtain a refreshing feeling of use without being moist during rinsing.

The alkyl ether carboxylic acid of component (A) or a salt thereof used in the present invention is represented by the general formula (1).
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, 8 to 16 carbon atoms, and further 10 to 10 carbon atoms. 16 alkyl groups are more preferred. 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. The average carbon number of R ¹ is 10.8 to 12.8, preferably 10.8 to 12.5, and more preferably 12.1 to 12.4. If it is in this range, it is excellent in terms of foamability and foam quality, and stability at low temperature, which is preferable.
R ¹ preferably contains two or more alkyl groups, and the component having the largest alkyl chain length is preferably 55% by mass or more and less than 97% by mass, and 60 to 95% by mass. More preferably, it is preferably 70 to 95% by mass because the foam amount and foam quality are excellent.

Moreover, in formula, n shows the number of 0-20, and 0-12 are more preferable. In addition, although n shows the addition mole number of ethylene oxyoxide, the average addition mole number (average value of n) in a composition of a component (A) is 1.5-10 from the point that foaming is favorable. Preferably, 2.5 to 6.4 is more preferable, 2.5 to 3.7 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 more preferable.
In the general formula (1), the alkyl ether carboxylic acid of the component (A) or a salt thereof is more than 9.6% by mass and less than 27% by mass, preferably 9.8 to 27% by mass, compared with the component of n = 0. Preferably it contains 9.9-27 mass%, More preferably, it is 9.9-16 mass%, More preferably, it contains 9.9-15 mass%. By setting it within this range, the foam amount and foam quality are excellent.
Furthermore, the total of n = 1 component and n = 2 component is less than 21 to 40% by mass, preferably 27 to 37% by mass, more preferably 27 to 36.5% by mass, and further preferably 35 to 36.1. It is preferable from the viewpoint of the foam quality and the amount of foam to contain mass%.

  In the formula, M represents a hydrogen atom; an alkali metal such as sodium or potassium; an alkaline earth metal such as calcium or magnesium; an ammonium; an ammonium derived from an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine; Can be mentioned. Among these, alkali metals are preferable from the viewpoints of foamability, low-temperature stability, and lack of coloration over time.

  In the general formula (1), the alkyl ether carboxylic acid of the component (A) or a salt thereof is such that the mass ratio of the components of n = 0, 1, 2, 3, 4 is (the mass of the n = 0 component): (n = Mass of 1 component): (mass of n = 2 component): (mass of n = 3 component): (mass of n = 4 component) = 1: 0.99-3.50: 0.89-3. It is preferable that it is 00: 0.76-3.00: 0.63-1.52 from the point of compatibility of foamability, detergency, and the squeak feeling at the time of a rinse.

  Moreover, in general formula (1), the component of n = 0 is contained 9.9 mass% or more and less than 12 mass%, (mass of n = 0 component) :( mass of n = 1 component) :( n = 2 component) Mass): (mass of n = 3 components): (mass of n = 4 components) = 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): (mass of n = 3 components): (mass of n = 4 components) = 1: 0.99-1.34: 0.89-1.40: 0.76-1.23: 0. A value of 63 to 0.99 is preferable from the viewpoint of foam quality and foam amount.

  Furthermore, in General formula (1), the component of n = 0 is included 9.9-11.5 mass%, (The mass of n = 0 component) :( The mass of n = 1 component) :( 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 the general formula (1), 13 to 15% 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 in terms of foam quality and foam amount.

In the component (A), in the general formula (1), R ¹ is an alkyl group having 4 to 22 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, and the average value of the number of added moles of n is 1.5 to 10, It is 2.5-6.4, It is preferable to contain 9.8-27 mass% of the component of n = 0, and 27-37 mass% of the component of n = 1 and the component of n = 2 in total. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. In this way, foaming can be accelerated.

In the component (A), in the general formula (1), R ¹ is preferably an alkyl group having 6 to 20 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 from 0 to 20, the average value of n is 2.5 to 3.7, and n = It is preferable to contain 9.8 to 27% by mass of 0 component and 27 to 37% by mass in total of n = 1 component and n = 2 component. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foamability can be accelerated.

In the component (A), in the general formula (1), 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, and the average value of n is 2.5 to 3.4. It is preferable to contain 9.9 to 27% by mass of 0 component and 27 to 36.5% by mass in total of n = 1 component and n = 2 component. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, the stop feeling property at the time of a rinse can be strengthened.

In the component (A), in the general formula (1), 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 of n is 2.8 to 3.4, and n = 0 Is preferably 9.9 to 16% by mass and contains 27 to 36.5% by mass in total of n = 1 and n = 2. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foam amount and foam quality can be improved.

In the component (A), in the general formula (1), 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 70 to 95% by mass, n represents a number of 0 to 20, the average value of n is 2.8 to 3.1, and n = 0 Is preferably 9.9 to 15% by mass and contains 35 to 36.1% by mass in total of n = 1 and n = 2. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, the amount of foams and foam quality can be improved.

Incidentally, in the components of the present invention (A), 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 performing analysis by gas chromatography on the alkyl ether carboxylic acid represented by the general formula (1).

[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 the 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 amount of n = 0, total amount 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 set to 100%, and the total amount 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 mass 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 composition of R ¹ The alkyl chain length component was identified from the area ratio of n = 0, n = 1, n = 2, n = 3, and n = 4 of the maximum component.

  The alkyl ether carboxylic acid of component (A) or a salt thereof has the composition as described above, and is contained in an amount of 0.1 to 30% by mass in the whole composition from the viewpoint of foamability and detergency. The content is preferably 5 to 20% by mass, and more preferably 2 to 15% by mass. In addition, content here shows content as alkyl ether carboxylic acid.

Examples of the water-soluble polyvalent metal salt of component (B) used in the present invention include inorganic substances such as aluminum, alkaline earth metals such as magnesium and calcium, and inorganic acids such as halogen, sulfuric acid, sulfonic acid, sulfurous acid and phosphoric acid. Examples thereof include salts or organic salts with organic acids such as lactic acid, acetic acid, and malic acid. For example, 1 selected from one or more water-soluble aluminum salts selected from potassium aluminum sulfate (alum), aluminum ammonium sulfate, aluminum chloride, aluminum sulfate, aluminum lactate, etc., magnesium sulfate, magnesium chloride, calcium chloride, etc. Examples include two or more types of alkaline earth metal salts. These can suppress the stickiness at the time of rinsing and can give a refreshing feeling of use.
Among these, when combined with the component (A) and washed, a water-soluble aluminum salt is preferable from the viewpoint of difficulty of disappearance of bubbles.

  One or more water-soluble polyvalent metal salts of the component (B) can be used, and from the viewpoint of rinsing properties, the total composition contains 0.01 to 5% by mass, and 0.05 to 3% by mass. Furthermore, it is preferable to contain 0.2-1 mass% further.

  In the present invention, the mass proportions of the components (A) and (B) are (A) / (B) = 1/1 to 100/1 from the point that bubbles are hard to disappear and there is little sliminess during rinsing. Is preferable, 3/1 to 50/1 is more preferable, and 5/1 to 20/1 is more preferable. In addition, the value of a component (A) here shows content as an alkyl ether carboxylic acid.

  The water of component (C) is used as a solvent in the skin cleanser composition, and can be contained in the total composition, preferably 30 to 98% by mass, more preferably 40 to 90% by mass. It becomes the remainder of the said component which comprises a thing, and another component.

The skin cleansing composition of the present invention can further contain an anionic surfactant other than the component (A) (D), improve the ease of foaming and maintain the foam quality over time, The gloss of the foam at the time of washing can be improved.
As such an anionic surfactant, any anionic surfactant may be used as long as it is used in ordinary detergent compositions. For example, fatty acid salts, alkyl (ether) sulfates, allyl (ether) sulfates, alkylbenzene sulfonates, alkane sulfonic acids. Salt, olefin sulfonate, alkyl ether sulfonate, glycerin ether sulfonate, α-methyl ester sulfonate, sulfo fatty acid salt, alkyl sulfate, fatty alcohol ether sulfate, glycerin ether sulfate, hydroxy mixed ether sulfate , Monoglyceride (ether) sulfate, fatty acid amide (ether) sulfate, monoalkylsulfosuccinate, dialkylsulfosuccinate, monoalkylsulfosuccinamide, dialkylsulfosuccinate, sulfotriglyceride, amino Ether carboxylates and salts thereof, fatty acid isethionate, fatty acid sarcosinate, fatty acid tauride; N-acyl amino acid salts such as acyl lactylate, acyl tartrate, acyl glutamate, acyl aspartate; alkyl oligoglucoside sulfate, protein fatty acid condensation Products (wheat-based plant products), alkyl (ether) phosphates and the like.

Of these, from the viewpoint of foaming properties and foam quality, one or more selected from fatty acid salts, alkyl (ether) sulfates, and N-acyl amino acid salts are preferred. Furthermore, 1 type (s) or 2 or more types chosen from alkyl (ether) sulfate and N-acyl amino acid salt are preferable at the point which maintains the foam retention at the time of washing | cleaning, and the glossiness of a bubble.
As the fatty acid salt, the general formula (2)

(Wherein R ² represents a linear or branched alkyl or alkenyl group having 9 to 21 carbon atoms, and Y represents an alkali metal, ammonium, alkanolamine-derived ammonium or basic amino acid)
The thing represented by these is preferable.
More specifically, for example, salts such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid and the like can be mentioned. Examples of these salts include alkali metals such as sodium and potassium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and basic amino acids such as arginine and lysine.

  Moreover, as alkyl (ether) sulfate, general formula (3)

(In the formula, R ³ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, p represents a number of 0 to 20, Z represents a hydrogen atom, an alkali metal, an alkaline earth, or the like. A cation selected from metal, ammonium, alkylammonium, alkanolammonium and glucammonium)
The thing represented by these is preferable.

Alkyl (ether) sulfate is a monoester salt of (alkoxyl) alcohol, and after sulfating polyoxyethylene alkyl ether or alcohol, it is neutralized with a base such as ammonia, sodium hydroxide or triethanolamine. Is obtained.
In the present invention, in general formula (3), R ³ is preferably a linear or branched alkyl group or alkenyl group having 12 to 18 carbon atoms, and further a linear or branched alkyl group having 12 to 14 carbon atoms. Or an alkenyl group is preferable.
In general formula (3), p is preferably 0.5 to 12, more preferably 0.5 to 5, and even more preferably 0.5 to 3.

  As N-acylamino acid salt, general formula (4)

(Wherein R ⁴ represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ⁶ represents A hydrogen atom or — (CH ₂ ) _q R ⁷ (R ⁷ represents a hydrogen atom, a hydroxyl group or —COOM, q represents 0 to 3), and M represents a hydrogen atom, an alkali metal or an alkanolamine)
The thing represented by these is preferable.

In formula (4), R ⁴ is preferably an alkyl group having 6 to 18 carbon atoms, and more preferably an alkyl group having 10 to 16 carbon atoms. R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. R ⁶ is preferably a hydrogen atom, — (CH ₂ ) _q R ⁷ . M is preferably an alkali metal.

  Among the N-acylamino acid salts represented by the formula (4), preferred are N-cocoyl glycine, N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-lauroyl-N-methyl glycine, N-lauroyl-β. -Alanine, N-myristoyl-β-alanine, N-lauroylaspartic acid, N-lauroylserine, etc .; and alkali metal salts such as sodium and potassium; Alkanolamine salts such as monoethanolamine, diethanolamine, triethanolamine, etc. Is mentioned. The compound represented by the general formula (4) includes L-form, D-form, and racemate, and any of these can be used in the present invention.

  One or more types of component (D) can be used, and from the viewpoint of foaming and rinsing properties, it is preferably contained in an amount of 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. Furthermore, it is preferable to contain 1-7 mass%. Here, it is assumed that the component (D) forms a salt, and the content is specified.

  In the present invention, the mass ratio of the components (A) and (D) is preferably (A) / (D) = 1/10 to 10/1 from the viewpoint of increasing the amount of foam and improving rinsing properties. 2 to 5/1 is more preferable. In addition, the mass ratio of a component (A) here shows content as alkyl ether carboxylic acid.

  The skin cleanser composition of the present invention can further contain (E) one or more surfactants selected from amphoteric surfactants and nonionic surfactants, while maintaining the foam quality. The amount can be increased.

Examples of amphoteric surfactants include betaine acetate type surfactants such as lauryldimethylaminoacetic acid betaine, amine oxide type surfactants such as lauryldimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazo. Examples thereof include imidazolinium betaine type surfactants such as linium betaine, amide betaine type surfactants such as amidopropyl betaine laurate, and sulfobetaine type surfactants such as lauryl hydroxysulfobetaine.
Examples of the nonionic surfactant include alkyl glucoside, alkyl glyceryl ether, fatty acid glycerin, fatty acid polyglycerin and the like.

  As the component (E), fatty acid amidopropyl betaine, hydroxypropyl sulfobetaine, and alkyl glucoside are preferable from the viewpoint of improving the amount of foam.

  As the component (E), one or more kinds can be used. From the viewpoint of increasing the amount of foam, the total composition preferably contains 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. Furthermore, it is preferable to contain 1-10 mass%.

  The skin cleanser composition of the present invention further comprises components used in ordinary cleansing agents, for example, surfactants other than components (A), (D) and (E), moisturizers, oily components, fungicides, Anti-inflammatory agent, antiseptic agent, chelating agent, pearlizing agent, scrub agent, fragrance, cooling agent, pigment, UV absorber, antioxidant, plant extract, pH adjuster, thickener, touch modifier, ingredient ( Inorganic salts and organic acid salts other than B) can be contained.

The skin cleansing composition of the present invention is produced by mixing the compounding ingredients by a usual method. The obtained detergent 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 25 ° C. is 200 to 80,000 mPa · s. It is preferable that it can be adjusted by appropriately selecting the blending components.
The pH is preferably 3 to 12, more preferably 5 to 10.5, and even more preferably 5 to 7. In addition, the measurement of pH is a value obtained by diluting each cleaning composition 20 times with ion-exchanged water at 25 ° C.

The skin cleansing composition of the present invention is applied to body skin such as the face, limbs and torso, used for cleaning, and suitable for rinsing after washing. For example, it is suitable as a face wash, body soap, hand soap, etc., and body soap is particularly preferred.
The method for washing the skin using the skin cleansing composition of the present invention is, for example, as follows. That is, the skin cleansing composition of the present invention is a method of applying an appropriate amount to the body, that is, the body skin such as the face, limbs, and torso, washing with foaming, and then rinsing using warm water such as a shower. In addition, an appropriate amount can be applied to cleaning aids such as towels, sponges, brushes, etc., and foamed for cleaning.

(Measuring method)
In the present invention, the alkyl composition, EO addition molar distribution, and ratio of each component of the alkyl ether carboxylic acid were measured by gas chromatography (GC) by the following analytical method.

(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 carboxylic acid was dissolved in 50 mL of methanol. Moreover, about the cleaning composition, it extract | collected so that it might become 150 mg as alkyl ether carboxylic acid, and melt | dissolved in 50 mL of methanol. In addition, when the detergent composition contained a strong anionic surfactant such as polyoxyethylene alkyl ether sulfate, it was collected so as to be 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)

  The alkyl ether carboxylic acid of component (A) used in the skin cleansing composition of the present invention can be produced, for example, as follows. Unless otherwise indicated, “%” indicates mass%.

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 carried out 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 M = H in the general formula (1), R ¹ is lauryl group / myristyl group = 95/5, the average carbon number is 12.1, and the 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 general formula (1), M = 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
372 g (2.00 mol) of lauryl alcohol was charged into a glass reaction vessel equipped with stirring and temperature control functions, the liquid temperature was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate. 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 (1), M = 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 (1), M = 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 analysis by gas chromatography, in general formula (1), M = 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 general formula (1), M = 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 general formula (1), M = 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 (1), M = 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 general formula (1), M = 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 the alkyl ether carboxylic acid obtained in Production Example 4 were mixed at a mass ratio of 40/60 to obtain E4.

  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.

  In the examples, regarding EC7, EC1 obtained in Production Example 1 and commercially available AKYPO RLM45 (manufactured by Kao Corporation) were mixed at a mass ratio of 50/50 to obtain EC7.

  In the examples, regarding EC8, EC1 obtained in Production Example 1 and commercially available AKYPO RLM100NV (manufactured by Kao Corporation) were mixed at a mass ratio of 50/50 to obtain EC8.

Examples 1-16, Comparative Examples 1-3
Skin cleansing compositions having the compositions shown in Tables 3 and 4 were produced and evaluated for foaming, foam amount, foam viscosity, foam retention, and non-stickiness during rinsing. The results are shown in Tables 3 and 4 together.
In addition, the structure of the component (A) used in the Example is as showing in Table 1 and Table 2.
Moreover, the average EO addition mole number of the commercially available alkyl ether carboxylic acid (AKYPO RLM45 (made by Kao company)) used in the Example referred to the catalog value of each company vendor, and the value currently published on the homepage. The unknown alkyl composition, the component amount of n = 0, and the total amount of the component of n = 1 and the component of n = 2 were analyzed by the above method.
Examples 1 to 8 are reference examples and are not included in the scope of the present invention.

(Production method)
(1) Examples 1-7:
Water excluding the water that dissolves component (A) and component (B) is heated to 60-70 ° C. and mixed, and if necessary, 50% malic acid and some 48% sodium hydroxide are added, Stir until uniform. Furthermore, 20 times the amount of the component (B) and the component (B) (C) were mixed at 70 to 80 ° C., dissolved and added, and stirred until uniform. The pH was adjusted to about 6.2 with sodium hydroxide, stirred until uniform, and cooled to 30 ° C. to obtain a skin cleansing composition.

(2) Examples 8-22:
Water excluding the water that dissolves the component (A) and the component (B) is heated to 60 to 70 ° C. and mixed, and if necessary, 50% malic acid and a part of sodium hydroxide are added. Stir until. Furthermore, component (B) and component (C) 20 times the amount of component (B) were mixed at 70 to 80 ° C., dissolved, and added, and mixed uniformly. Furthermore, components (D), (E) and other components are added as necessary and stirred until uniform. Furthermore, it adjusted to about pH 6.2 using sodium hydroxide, and it cooled to 30 degreeC, and obtained the skin cleansing composition.

(Evaluation method)
(1) Foaming:
Three professional evaluators took 1 g of each skin cleanser in one hand, diluted with tap water and foamed, and evaluated the ease of initial foaming according to the following criteria. The results are shown as average values.
5; I felt that foaming was very fast.
4; I felt that foaming was fast.
3; Neither can be said.
2; I felt that foaming was a little slow.
1; I felt that foaming was slow.

(2) Foam amount:
Three professional evaluators took 1 g of each skin cleanser in one hand, diluted with tap water, and evaluated the amount of foam when foamed for 20 seconds according to the following criteria. The results are shown as average values.
5; I felt that the amount of foam was very large.
4; I felt that the amount of foam was large.
3; Neither can be said.
2; I felt that the amount of foam was slightly small.
1; I felt that the amount of foam was small.

(3) Foam viscosity:
Nylon towel (manufactured by Wing Co., body towel, soft texture, size of about 30 × 100 cm) was wetted with 38-41 ° C. hot water, squeezed, applied with 6 mL of each skin cleanser, and foamed 30 times to rub. Fill this foam into a death cup (Teraoka Co., Ltd., 100cc) and immediately measure it using a viscometer (Toki Sangyo Co., Ltd., VISCOMETER TV-10). Is about 1 minute) (rotor: No. 3, rotation speed: 30 rpm, 60 s).

(4) Foam retention:
Nylon towel (manufactured by Wing Co., body towel, soft texture, size of about 30 × 100 cm) was wetted with 38-41 ° C. hot water, squeezed, applied with 6 mL of each skin cleanser, and foamed 30 times to rub. A full amount of this foam was put into Pack Ace (Terraca, 120 cc, height 7 cm), and the height of the foam remaining after 5 minutes was measured. (The part that became liquid was removed from the measurement target.)

(5) No sliminess when rinsing:
Take 1g of each skin cleanser in one hand, dilute with tap water, lather, wash one arm (from elbow to tip), apply tap water with the other hand, The number of water on the forearm was measured. The results are shown by the following criteria.
A: The number of applied water is 5 times or less.
B: The number of times of water applied was 6 to 10 times.
C: The number of times of water applied is 11 to 15 times.
D: The number of applied water was 16 to 20 times.
E: The number of splashed water was 21 times or more.

Example 17
A skin cleanser composition having the following composition was prepared (adjusted to pH 6.2).
(component)
Ingredient (A) EC1 4 (mass%)
Ingredient (B) Potassium aluminum sulfate 0.35
Component (D) Polyoxyethylene lauryl ether ammonium 3
Component (E) alkyl (C8-16) glucoside 4
Ingredient (E) Amidopropyl betaine laurate 3
Sodium benzoate 0.35
Sodium chloride 0.5
48% sodium hydroxide
Ingredient (C) Water balance
Total 100

Example 18
A skin cleanser composition having the following composition was prepared (adjusted to pH 6.2).
(component)
Ingredient (A) EC2 4 (mass%)
Ingredient (B) Potassium aluminum sulfate 0.35
Component (D) Polyoxyethylene lauryl ether ammonium 3
Component (E) alkyl (C8-16) glucoside 4
Ingredient (E) Amidopropyl betaine laurate 3
Sodium benzoate 0.35
Sodium chloride 0.5
48% sodium hydroxide
Ingredient (C) Water balance
Total 100

Example 19
A skin cleanser composition having the following composition was prepared (adjusted to pH 6.2).
(component)
Ingredient (A) EC3 4 (mass%)
Ingredient (B) Potassium aluminum sulfate 0.35
Component (D) Polyoxyethylene lauryl ether ammonium 3
Component (E) alkyl (C8-16) glucoside 4
Ingredient (E) Amidopropyl betaine laurate 3
Sodium benzoate 0.35
Sodium chloride 0.5
48% sodium hydroxide
Ingredient (C) Water balance
Total 100

Example 20
A skin cleanser composition having the following composition was prepared (adjusted to pH 6.2).
(component)
Ingredient (A) EC4 4 (mass%)
Ingredient (B) Potassium aluminum sulfate 0.35
Component (D) Polyoxyethylene lauryl ether ammonium 3
Component (E) alkyl (C8-16) glucoside 4
Ingredient (E) Amidopropyl betaine laurate 3
Sodium benzoate 0.35
Sodium chloride 0.5
48% sodium hydroxide
Ingredient (C) Water balance
Total 100

Example 21
A skin cleanser composition having the following composition was prepared (adjusted to pH 6.2).
(component)
Ingredient (A) EC5 4 (mass%)
Ingredient (B) Potassium aluminum sulfate 0.35
Component (D) Polyoxyethylene lauryl ether ammonium 3
Component (E) alkyl (C8-16) glucoside 4
Ingredient (E) Amidopropyl betaine laurate 3
Sodium benzoate 0.35
Sodium chloride 0.5
48% sodium hydroxide
Ingredient (C) Water balance
Total 100

Example 22
A skin cleanser composition having the following composition was prepared (adjusted to pH 6.2).
(component)
Ingredient (A) EC6 4 (mass%)
Ingredient (B) Potassium aluminum sulfate 0.35
Component (D) Polyoxyethylene lauryl ether ammonium 3
Component (E) alkyl (C8-16) glucoside 4
Ingredient (E) Amidopropyl betaine laurate 3
Sodium benzoate 0.35
Sodium chloride 0.5
48% sodium hydroxide
Ingredient (C) Water balance
Total 100

  Using the skin cleanser compositions of Examples 17 to 22, the whole body was washed and each evaluation was performed. As a result, all of the foams had excellent foam retention, high foam viscosity, and elasticity. Bubbles did not disappear easily, and a high cleaning feeling was obtained. In addition, a refreshing feeling of use was obtained without being moist during rinsing.

Claims (12)

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

(In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic ammonium).
In which the average carbon number of R ¹ is 10.8 to 12.8, and the component of n = 0 exceeds 9.6% by mass and is 27% by mass or less, Alkyl ether carboxylic acid or salt thereof containing n = 1 and n = 2 in total and not less than 21% by mass and less than 40% by mass and having an average value of n of 2.5 to 6.4 mass%,
(B) Water-soluble polyvalent metal salt 0.01-5% by mass
(C) Water (D) An anionic surfactant other than the component (A) is contained, and the mass ratio of the components (A) and (D) is (A) / (D) = 1/2 to 5/1. A certain skin cleansing composition. In the component (A), in the general formula (1), R ¹ is an alkyl group having 6 to 20 carbon atoms, an average value of n is 2.5 to 3.7, and a component of n = 0 is 9. The skin cleanser composition according to claim 1, comprising 9 to 27% by mass. In the component (A), in the formula (1), R ¹ is an alkyl group having 8 to 18 carbon atoms, skin cleansing according to claim 1 or 2, wherein the average value of n is 2.5 to 3.4 Agent composition. In the component (A), in the general formula (1), R ¹ is an alkyl group having 8 to 16 carbon atoms, the average alkyl is 10.8 to 12.5, and the average value of n is 2.8 to 3 4, wherein 9.9 to 16% by mass of the n = 0 component and 27 to 36.5% by mass of the n = 1 and n = 2 components in total. The skin cleansing composition according to Item.   In component (A), in general formula (1), (mass of n = 0 component): (mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): ( n = mass of four components) = 1: 0.99 to 3.50: 0.89 to 3.00: 0.76 to 3.00: 0.63 to 1.52 A skin cleanser composition according to claim 1. In component (A), in general formula (1), R ¹ contains two or more alkyl groups, and the component having the largest alkyl chain length is 55% by mass or more and less than 97% by mass. The skin cleansing composition according to any one of 1 to 5.   In the component (A), in the general formula (1), the component of n = 0 is included in the range of 9.9% by mass to less than 12% by mass, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (n = mass of 3 component): (n = mass of 4 component) = 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 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 0.99-1.34: 0.89-1.40: 0.76-1. 23: The skin cleanser composition according to any one of claims 1 to 6, wherein the composition is 23: 0.63 to 0.99.   The skin cleansing composition according to any one of claims 1 to 7, wherein the component (B) is a water-soluble aluminum salt.   The skin cleansing composition according to any one of claims 1 to 8, wherein the mass ratio of the components (A) and (B) is (A) / (B) = 1/1 to 100/1.   The skin cleansing composition according to any one of claims 1 to 9, wherein a mass ratio of the components (A) and (B) is (A) / (B) = 3/1 to 50/1.   The skin cleanser composition according to any one of claims 1 to 10, further comprising (E) one or more surfactants selected from amphoteric surfactants and nonionic surfactants.   A method for rinsing the skin after applying the skin cleansing composition according to any one of claims 1 to 11 to a body skin part and cleaning the body skin part.