JP5802576B2 - Skin cleanser composition - Google Patents

Description

  The present invention relates to a skin cleansing composition.

  A skin cleanser product that is used by filling a liquid discharge composition into a foam discharge container and discharged as fine bubbles has the advantages of eliminating the need for foaming and reducing skin irritation. In such detergent products, it is considered preferable to maintain the composition at a low viscosity in order to obtain uniform foam, and various studies have been made on methods for improving the cleaning power and foam quality.

  For example, it contains (a) a specific polyoxyethylene alkyl ether sulfate and (b) a cleaning composition containing polyglycerin fatty acid ester (Patent Document 1), polyoxyethylene alkyl ether sulfate and cationized cellulose. A skin cleanser (Patent Document 2) obtained by filling a foam discharge container with an aqueous liquid cleanser composition is being studied.

JP 2005-89571 A JP 2005-162666 A

In the case of washing with a skin cleansing agent filled in a foam discharge container, there is a problem that the foam tends to disappear, and that sufficient removal of dirt and a feeling of washing cannot be obtained.
In addition to the cleaning agent filled in the foam discharge container, in the case of cleaning agents for hand-washing, especially when the number of hand-washing is increased, especially in winter, the moisture content of the skin tends to be lower than before washing, causing rough hands. There was a problem that it was easy to become.
Further, there is a problem that the cleaning power against the dirty dirt is not sufficient.

  An object of the present invention is to provide a skin cleanser composition that is excellent in cleanability, excellent in foam amount during cleaning, feels the thickness of the foam, and has mildness sufficient for repeated cleaning.

  When the present inventors use a combination of an alkyl ether carboxylic acid having a specific distribution or a salt thereof and a specific nonionic surfactant in combination, the foaming and the amount of foam are excellent, and the thickness of the foam is felt during washing. Skin that is easy to hold, provides a good feeling of cleansing, has excellent cleaning power, especially cleaning against dirt, and is gentle to the skin. It has been found that a cleaning composition can be obtained.

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 a component of n = 1 and a component of n = 2 in total of 21% by mass or more and less than 40% by mass,
(B) a polyoxyethylene alkyl ether type nonionic surfactant having an HLB of 10 or more,
(C) A skin cleansing composition containing water and having a total content of components (A) and (B) of 2 to 20% by mass is provided.

  The skin cleansing composition of the present invention is excellent in the amount of foam at the time of washing, feels the thickness of the foam, and has good foam retention. In particular, it has a high detergency against mud stains, is gentle to the skin, and even if the skin is repeatedly washed, the moisture content of the skin is maintained and rough skin is suppressed.

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 an alkyl having the maximum content in the composition of R ¹ in which the mass ratio of the components of n = 0, 1, 2, 3, 4 is R ^1. In the chain length 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 3.50: 0.89 to 3.00: 0.76 to 3.00: 0.63 to 1.52 is foaming property, detergency, and squeaky feeling during rinsing From the viewpoint of compatibility of reduction of the above, it is preferable.

Further, in the general formula (1), the component of n = 0 include less than 9.9 wt% 12 wt%, in the alkyl chain length components of the maximum content of the composition of R ^1, the (n = 0 component mass ): (Mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.53-1.87: 1. 59 to 2.25: 1.33 to 2.16: 1.14 to 1.52, or 12 to 17% by mass of the n = 0 component, and the maximum among the compositions of R ¹ In the alkyl chain length component of content, (mass of n = 0 component): (mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): (n = 4 component) Mass) = 1: 0.99 to 1.34: 0.89 to 1.40: 0.76 to 1.23: 0.63 to 1 is preferable from the viewpoints of foam quality and foam amount.

Further, in the general formula (1), the component of n = 0 contains 9.9 to 11.5% by mass, and in the alkyl chain length component of the maximum content in the composition of R ¹ , (mass of n = 0 component) : (N = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 1.58-1.84: 1.72 To 2.17: 1.49 to 2.00: 1.14 to 1.52, or, in the general formula (1), the component of n = 0 is contained in an amount of 13 to 15% by mass, and the composition of R ¹ In the maximum alkyl chain length component, (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = Mass of four components) = 1: 1.00 to 1.31: 0.93 to 1.34: 0.79 to 1.18: 0.63 to 1 in terms of foam quality and amount of foam To preferred.

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. By doing in this way, the elasticity of a bubble can be improved.

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, the elasticity of a bubble can be improved further.

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, the amount of foam discharged from the former container and the foam quality (foam texture, foam retention) 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 foam and foam quality (foaming of a foam, holding of a foam, etc.) 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 analyzing the alkyl ether carboxylic acid represented by the general formula (1) 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 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 or salt thereof as component (A) has the above-described composition. From the viewpoint of the amount of foam and the moisture retention of the skin after washing, preferably 0 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass.

The component (B) polyoxyethylene alkyl ether type nonionic surfactant used in the present invention is HLB10 or more, preferably 10-20, more preferably HLB13-16. Such an HLB material is preferable in combination with the component A from the viewpoint of imparting the foam thickness during cleaning.
HLB is an index indicating a hydrophilic-lipophilic balance, and in the present invention, a value calculated using the following equation by Oda / Teramura et al. Is used.

  Specific examples of the component (B) polyoxyethylene alkyl ether type nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene palmityl ether, polyoxyethylene isostearyl ether, Examples include polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene hexyl decyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene behenyl ether and the like.

  Component (B) polyoxyethylene alkyl ether type nonionic surfactants are commercially available products such as polyoxyethylene (21) lauryl ether (Emulgen 121-G (HLB14), manufactured by Kao Corporation), polyoxyethylene ( 20) 2-hexyldecyl ether (Emulgen 1620G (HLB14), manufactured by Kao Corporation), polyoxyethylene (20) octyldodecyl ether (Emulgen 2020G (HLB13), manufactured by Kao Corporation) and the like can be suitably used.

  Component (B) may be used alone or in combination of two or more. From the viewpoint of foam thickness and foam retention at the time of washing, the total composition is preferably 0.1 to 10% by mass, more preferably 0.8. It is contained in an amount of 2 to 5% by mass, more preferably 1 to 3% by mass.

In the present invention, the total content of components (A) and (B) is 2 to 20% by mass, preferably 2 to 15% by mass, and more preferably 3 to 11% by mass. Within this range, it is preferable because it is excellent in cleaning power, particularly cleaning power against dirt.
In addition, the mass ratio of the components (A) and (B) is preferably (A) / (B) = 0.5 to 10 and more preferably 0.5 to 3 in terms of the thickness of the foam. preferable.

The water of component (C) used in the present invention is the remainder of each component, and is preferably contained in the total composition in an amount of 40 to 97% by mass, and more preferably 70 to 90% by mass.
The skin cleanser composition of the present invention is an aqueous liquid containing water.

The skin cleansing composition of the present invention can further contain (D) polyoxyethylene alkyl ether sulfate, and can increase the amount of foam during cleaning.
Such polyoxyethylene alkyl ether sulfates are not particularly limited as long as they are used in ordinary detergent compositions, but those having an alkyl group or an alkenyl group having 10 to 18 carbon atoms are preferred, and further 12 to 12 carbon atoms are preferred. Those having 14 alkyl groups are preferred. Further, the number of moles of ethylene oxide added is preferably larger than 0 and 5 or less, and more preferably 1 to 4 on average.

  The salt includes alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; ammonium salts; alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine; bases such as arginine and lysine. Amino acid salts and the like.

  As the component (D), one or more kinds can be used, and from the viewpoint of the amount of foam at the time of washing, it is preferably contained as a salt in the total composition in an amount of 1 to 15% by mass, and further 4 to 10% by mass. It is preferable to contain.

  Moreover, in this invention, since the mass ratio of component (A), (B) and (D) can increase the amount of foam and can hold | maintain the water | moisture content of the skin after washing | cleaning, (D) / ((A ) + (B)) = 0.5-3, more preferably 1-2.

The skin cleanser composition of the present invention can further contain (E) a fatty acid having 8 to 18 carbon atoms and a polyglycerin fatty acid ester composed of polyglycerin having an average polymerization degree of 2 to 15, and air is washed during washing. It has the effect of entraining the foam to increase the foam, prevents the foam from being reduced during use, and allows the foam to reach every corner of the fingers, thereby providing sufficient cleaning and a feeling of cleaning.
In addition, the polyglycerin fatty acid ester of component (E) is preferably HLB 12-18, and more preferably HLB 13-16, since excellent foam retention is obtained.

Examples of the polyglycerin fatty acid ester of component (E) include polyglycerin octanoic acid ester, polyglycerin 2-ethylhexanoic acid ester, polyglycerin decanoic acid ester, polyglycerin lauric acid ester, polyglycerin myristic acid ester, polyglycerin palmitic acid. Acid ester, polyglycerol isostearic acid ester, polyglycerin stearic acid ester, polyglycerin oleic acid ester, polyglycerin behenic acid ester and the like can be mentioned.
As a component (E), a C12-C18 fatty acid monoester is preferable. The average degree of polymerization of polyglycerol is preferably 5-10.
Specifically, decaglyceryl monolaurate (Sunsoft M-12J, manufactured by Taiyo Kagaku) and pentaglyceryl monostearate (Sunsoft A-181E, manufactured by Taiyo Chemical) are preferred.

  Component (E) can be used alone or in combination of two or more. From the standpoint of foam, 0.01 to 5 mass%, more preferably 0.1 to 2 mass%, more preferably, It is preferable to contain 0.5-1 mass%.

  The skin cleanser composition of the present invention further comprises components used in ordinary cleanser compositions such as oil components, polyhydric alcohols, bactericides, anti-inflammatory agents, antiseptics, chelating agents, salts, and pearlizing agents. , Scrub agents, fragrances, cooling agents, pigments, UV absorbers, antioxidants, plant extracts and the like.

The skin cleansing composition of the present invention can be produced by heating water to 60 to 80 ° C., sequentially mixing each component, stirring to dissolve, and cooling to 30 ° C.
Moreover, it is preferable that the skin cleansing composition of this invention is pH 3-10, and also 4-7. In addition, the measurement of pH is a value obtained by diluting the skin cleansing composition 20 times with water at 25 ° C.

  The skin cleansing composition of the present invention is preferably transparent. By being transparent, discharge from the former container becomes easy and clogging is difficult. Here, the term “transparent” refers to the transmittance at 550 nm, and the range from 75 to 100 is transparent. The transmittance was measured using a spectrophotometer (UV-160) manufactured by Shimadzu Corporation, and the transmittance of distilled water used as a control was judged as 100. Further, as the cell, (The) Disposer No./REF 67.774 10 × 10 × 45 mm manufactured by Sarstedt, Germany is used.

  The skin cleansing composition of the present invention preferably has a viscosity of 1 to 1000 mPa · s at 30 ° C., and further has a viscosity of 1 to 30 mPa · s when used in a foam discharge container. Is preferred. By doing in this way, discharge from a former container becomes easy and fine foam can be discharged.

The skin cleansing composition of the present invention can be used as a skin cleansing composition as it is, and is preferably used as a skin cleansing composition filled in a foam discharge container.
The foam discharge container is not particularly limited as long as the skin cleanser composition can be mixed with air and discharged in a foamed state. For example, a squeeze foamer type that presses and discharges the body of a soft container, press A pump former type discharged from a pump can be used. Among them, those having a porous film body in the foaming mechanism are preferable, and a single layer of a porous film body such as a sponge, a sintered body, or a net having a thickness of about 0.1 to 2 mm through which the cleaning composition passes. Alternatively, it can be provided in a plurality of layers or in a plurality of locations (for example, Japanese Patent Publication No. 52-16567, Japanese Utility Model Publication 58-174272, Japanese Utility Model Publication 3-7963, Japanese Utility Model Publication No. 6-32346, Japanese Patent Publication No. (Kaihei 7-215352, JP-A-9-118352, etc.). The mesh size of the porous membrane is preferably 50 to 500 mesh, particularly 150 to 400 mesh. Moreover, as a material of such a porous film body, a plastic material such as nylon, polyester, or polyolefin is preferable.

  The skin cleansing composition of the present invention can be applied as a hand washing cleanser, facial cleanser, face wash foam, cleansing foam, body soap, body wash foam, and the like. In particular, it is suitable as a detergent composition for hand washing. Moreover, it can also wash | clean and remove stain | pollution | contamination fully by apply | coating a skin cleansing composition directly to a hand, without massaging a hand with water, and massaging and washing away.

<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 receivers and the second and third receivers 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>
The component (B) alkyl ether carboxylic acid used in the frame kneaded soap 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 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 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
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 (1), M = H, R1 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.
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: 1.19: 1.13: 0.94: 1.

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 composition of R1, (n = 0 component mass): (n = 1 component mass): (n = Mass of 2 components) :( mass of n = 3 components) :( mass of n = 4 components) = 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.

The composition of the component (A) used in the examples is as shown in Tables 1 and 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 1-11, Comparative Examples 1-5
The skin cleansing composition having the composition shown in Table 3 was prepared by mixing each component in 60 ° C. water to make the solution uniform, and then cooling to 30 ° C. to remove soil dirt on the hands and foam during washing. The feeling of thickness, the amount of foam, the moisture content of the skin and the foam retention were evaluated. Further, the transmittance was measured. The results are also shown in Table 3.

(Evaluation method)
(1) Hand dirt removal:
As a soil, a soil of a foliage plant (A-49) manufactured by Daiso Sangyo Co., Ltd. was used. This soil is mainly composed of bark compost, pumice, peat moss and vermiculite.
500 g of this soil was filled in a polyethylene bag (Unipack L-4, produced by Nippon Nihonsha). Wet both hands well with water, wipe well with Eliere Pro Wipe Soft Towel White 4fold (dimensions: 405mm, width 315mm) (manufactured by Daio Paper Co., Ltd.), dry for 1 minute, and put it in a bag containing the soil When both hands were put in and the hand was grasped, the opening operation was repeated for 1 minute to allow soil to adhere to the hand. Thereafter, the hand was taken out of the bag and left for 15 minutes.
Each skin cleansing composition was filled into a pump former container (160 mL [YF-9413] manufactured by Yoshino Kogyo Co., Ltd.). Ten women (special panelists), for each of the skin cleansing compositions, pressed the pump once to discharge foam on the palm. Rub it with your left and right hands for 10 seconds, then rub with running water for 10 seconds with your left and right hands to wash away the foam, and then fold the erière pro wipe soft towel white into four (dimensions: 405 mm long, 315 mm wide) The water was thoroughly wiped off (made by Daio Paper Co., Ltd.). The soil dirt on the hands was visually evaluated according to the following criteria. The result was shown by the average value of 10 persons.
1; No dirt remains.
2; Slight dirt remains on the fingertip.
3; Most dirt remains on the fingertip.

(2) Thickness of foam at the time of washing:
Each skin cleansing composition was filled into a pump former container (160 mL [YF-9413] manufactured by Yoshino Kogyo Co., Ltd.). 10 females (special panelists), for each skin cleanser composition, press the pump twice to discharge the foam on the palm and rub it with the left and right hands for 10 seconds. It was evaluated sensuously on the basis of The result was shown by the average value of 10 persons.
1; I feel that there is a bubble thickness.
2; I feel that the thickness of the foam is slightly.
3; Bubble thickness is not felt at all.

(3) Foam amount:
Ten women (special panelists) applied 1 g of each skin cleansing composition to the palm and rubbed it with their left and right hands for 10 seconds, and evaluated the amount of foam organoleptically according to the following criteria. . The result was shown by the average value of 10 persons.
1; I feel a lot of foam.
2; Neither can be said.
3; I feel the amount of foam is small.

(4) Skin moisture (keratin moisture):
The capacitance value was measured by the following method to determine the moisture content of the skin.
(a) Wash the back with water.
(b) After resting in a temperature-controlled room (20 ° C., 40% RH) for 10 minutes, the capacitance before washing is measured by a model of Courage + Khazaka electronic GmbH (made in Germany): Corneometer CM825RC. The measurement was performed at five locations on the entire back and the average value was determined.
(c) Each skin cleansing composition is filled in a pump former container (160 mL [YF-9413] manufactured by Yoshino Kogyo Co., Ltd.) and pressed twice to take about 2 mL in the palm of the hand. Rinse the left and right hands for 10 seconds from the wrist to the hands, thoroughly massage the detergent, and then rinse with running water for 10 seconds. These are performed 10 times. After washing, after about 30 minutes in a temperature-controlled room (20 ° C., 40% RH), the capacitance after washing is measured. The capacitance was measured at five locations on the entire back and the average value was obtained.
As a result, the capacitance value before washing was set to 1, and the capacitance value after washing was shown as a relative ratio.

(5) Foam retention:
Each skin cleansing composition was filled into a pump former container (160 mL [YF-9413] manufactured by Yoshino Kogyo Co., Ltd.). 10 women (special panelists), for each skin cleanser composition, press the pump twice to eject the foam on the palm, and rub this with the left and right hands for 10 seconds, The following criteria were used for visual evaluation. The result was shown by the average value of 10 persons.
1; Bubbles increase.
2; Foam is maintained.
3; Bubbles decrease.

(6) Transmittance:
Using a spectrophotometer (UV-160) manufactured by Shimadzu Corporation, the transmittance was measured at 550 nm, and the transmittance of distilled water used as a control was shown as 100. As the cell, (The) Disposer No./REF 67.741 10 × 10 × 45 mm manufactured by Sarstedt, Germany was used.

Examples 12-16
A skin cleanser composition was produced in the same manner as in Examples 1 to 11 using EC2 to EC5.
Each of the obtained skin cleanser compositions has a transmittance of 550 nm of 100, and is excellent in removing soil dirt on the hands, foam thickness feeling, foam amount, skin moisture content and foam retention at the time of washing. confirmed.

Example 12
(Ingredient) (mass%)
EC2 2
Polyoxyethylene (21) lauryl ether (HLB14) * 2 3
Polyoxyethylene (2) sodium lauryl ether sulfate * 6 8
Decaglyceryl monolaurate (HLB15.5) * 7 3
Glycerin 0.16
Citric acid appropriate amount
Ion exchange water balance
Total 100
pH 5.5

Example 13
(Ingredient) (mass%)
EC3 2
Polyoxyethylene (21) lauryl ether (HLB14) * 2 3
Polyoxyethylene (2) sodium lauryl ether sulfate * 6 8
Decaglyceryl monolaurate (HLB15.5) * 7 3
Glycerin 0.16
Citric acid appropriate amount
Ion exchange water balance
Total 100
pH 5.5

Example 14
(Ingredient) (mass%)
EC4 2
Polyoxyethylene (21) lauryl ether (HLB14) * 2 3
Polyoxyethylene (2) sodium lauryl ether sulfate * 6 8
Decaglyceryl monolaurate (HLB15.5) * 7 3
Glycerin 0.16
Citric acid appropriate amount
Ion exchange water balance
Total 100
pH 5.5

Example 15
(Ingredient) (mass%)
EC5 2
Polyoxyethylene (21) lauryl ether (HLB14) * 2 3
Polyoxyethylene (2) sodium lauryl ether sulfate * 6 8
Decaglyceryl monolaurate (HLB15.5) * 7 3
Glycerin 0.16
Citric acid appropriate amount
Ion exchange water balance
Total 100
pH 5.5

Claims (12)

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

(In the formula, R ¹ represents an alkyl group having 10 to 16 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)
Wherein R ^{1 has} an average carbon number of 10.8 to 12.8, an average value of n is 2.5 to 3.7, and n = 0 An alkyl ether carboxylic acid or a salt thereof containing 9.9 to 27% by mass of a component of n = 2 and a component of n = 1 and a component of n = 2 in total of 21% by mass or more and less than 40% by mass
(B) HLB 10 or more Porioki Shiechi alkylene alkyl ether nonionic surfactant,
(C) A skin cleanser composition containing water and having a total content of components (A) and (B) of 2 to 20% by mass.   The skin cleanser composition according to claim 1, further comprising (D) polyoxyethylene alkyl ether sulfate.   The skin cleansing composition according to claim 1 or 2, wherein the mass ratio of the components (A) and (B) is (A) / (B) = 0.5-10.   The mass ratio of components (A), (B), and (D) is (D) / ((A) + (B)) = 0.5-3. Skin cleansing composition.   The skin cleanser composition according to any one of claims 1 to 4, further comprising (E) a polyglycerol fatty acid ester comprising a fatty acid having 8 to 18 carbon atoms and a polyglycerol having an average degree of polymerization of 2 to 15. In the component (A), in the general formula (1), R ¹ is an alkyl group having 10 to 16 carbon atoms, an average carbon number is 10.8 to 12.5, and an average value of n is 2.8 to It is 3.4, 9.9-16 mass% of the component of n = 0, 27 to 36.5 mass% in total of the component of n = 1 and the component of n = 2 is included, The any one of Claims 1-5 2. A skin cleanser composition according to item 1. In the component (A), in the general formula (1), in the alkyl chain length component having the maximum content in the composition of R ¹ , (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 0.99 to 3.50: 0.89 to 3.00: 0.76 to 3.00: The skin cleansing composition according to any one of claims 1 to 6, which is 0.63 to 1.52. 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 cleanser composition of any one of 1-7. In the component (A), in the general formula (1), the component of n = 0 is contained in an amount of 9.9% by mass or more and less than 12% by mass, and the maximum content of the alkyl chain length component in the composition of R ¹ is (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 to 2.25: 1.33 to 2.16: 1.14 to 1.52, or 12 to 17% by mass of n = 0, and R ¹ In the composition having the maximum alkyl chain length in the composition, (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 1.34: 0.89 to 1.40: 0.76 to 1.23: 0.63 to 1 Term The skin cleansing composition as described.   The skin cleansing composition according to any one of claims 1 to 9, which is used by being filled in a foam discharge container.   The skin cleansing composition according to any one of claims 1 to 10, which is for hand washing.   A method for rinsing the skin after applying the skin cleansing composition according to any one of claims 1 to 11 to a skin portion and washing the skin portion.