JP5891074B2 - Method for producing cleaning composition - Google Patents

Description

  The present invention relates to a method for producing a cleaning composition.

  Fatty acid soap is excellent in foaming and detergency and has been used as a skin cleanser for a long time. However, soap does not have sufficient detergency for strong oily soils such as foundations, and soap reacts with magnesium ions, calcium ions, etc. in hard water to generate water-insoluble scum. There is a strong sense of squeak at times.

  On the other hand, alkyl ether carboxylic acid-based surfactants are known as surfactants that are less irritating to the skin (for example, Patent Document 1), and detergents combined with soaps have also been developed. (For example, patent document 2).

Japanese Patent Laid-Open No. 5-12795 JP 2008-115094 A

However, alkyl ether carboxylic acid-based surfactants have poor foaming properties and do not have sufficient detergency against strong oily soils such as foundations, and water-insoluble scum adheres to toilets and bathrooms. When dried, it becomes difficult to re-dissolve in water, resulting in white spots.
The present invention has a high detergency against oily and strong oil stains, excellent foaming, no stickiness or stickiness after washing, a refreshing feeling is obtained, and it has excellent scum dispersibility, and it can be used in toilets and bathrooms. It is an object of the present invention to provide a cleaning composition that is prevented from being soiled.

  The present inventors have found that when a specific alkyl ether carboxylic acid and a fatty acid that is liquid at 20 ° C. are used in combination at a specific ratio, a cleaning composition that solves the above problems can be obtained.

  The present invention relates to (A) the general formula (1)

(In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, and n represents a number of 0 to 20).
Wherein R ^{1 has} an average carbon number of 10.8 to 12.8, the component of n = 0 exceeds 9.6% by mass and is 27% by mass or less, n = 1 0.1 to 60% by weight of an alkyl ether carboxylic acid containing 21% by weight or more and less than 40% by weight in total and the component of n = 2
(B) 0.1 to 80% by mass of liquid fatty acid at 20 ° C., and (D1) a part of water is heated and mixed, and (D2) the remainder of water and (C) a base are mixed. It provides the manufacturing method of the cleaning composition characterized by adding so that the neutralization rate of component (A) and (B) may be 50-100%.

  According to the present invention, it has a high detergency against oily oily stains, is excellent in foaming, has no stickiness after washing, has no feeling of being sticky after being wiped with a towel, and has a refreshing feeling, and also has a scum dispersion. Therefore, it is possible to obtain a cleaning composition that is excellent in properties and prevents the bathroom and bathroom from being soiled.

The alkyl ether carboxylic acid of component (A) 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) is more than 9.6 mass% and 27 mass% or less, preferably 9.8 to 27 mass%, more preferably 9 in the n = 0 component. It contains 9.9-27 mass%, More preferably, it is 9.9-16 mass%, More preferably, it contains 9.9-15 mass%. By making it within this range, it has excellent foam volume and foam quality, excellent detergency against oily oil stains, excellent foaming, no stickiness after washing, and no sensation after wiping with a towel. A feeling is obtained, and the dispersibility of the scum is excellent, and the bathroom and the bathroom are not soiled.
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 general formula (1), the alkyl ether carboxylic acid of the component (A) is an alkyl chain length component having a 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 (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, compatibility of foamability, detergency, and squeaky feeling during rinsing From this point, 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 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. 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. By doing in this way, foam quality and the amount of foam can be improved.

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. 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. 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 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 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 component (A) alkyl ether carboxylic acid has the composition as described above, is gentle to the skin, and is contained in an amount of 0.1 to 60% by mass, preferably 0, in terms of obtaining high cleaning performance. 25 to 50% by mass, more preferably 0.5 to 20% by mass.

  The fatty acid of component (B) used in the present invention is liquid at 20 ° C. For example, it is a C12-22 fatty acid having an unsaturated bond or a branched chain. More specifically, unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid and erucic acid; branched saturated fatty acids such as isomyristic acid, isopalmitic acid and isostearic acid. Preferably, from the viewpoint of detergency against oily strong oil stains, palmitoleic acid, oleic acid, linoleic acid, isopalmitic acid, isostearic acid, more preferably oleic acid, linoleic acid, isostearic acid, More preferably, isostearic acid is used.

  The fatty acid of a component (B) can use 1 type (s) or 2 or more types, and 0.1-80 mass% is contained in the whole composition from the point of the detergency with respect to sebum, a foundation, etc., Preferably it is 0.25. -70 mass%, More preferably, 0.5-60 mass% is contained.

  In the cleaning composition of the present invention, the mass proportions of the components (A) and (B) are (A) / (B) = 0.05 to 20, more preferably 0.07 from the viewpoint that the scum dispersibility becomes higher. -10, more preferably 0.1-5.

  The base of component (C) used in the present invention is used to neutralize components (A) and (B). For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia; Examples include organic amine compounds such as ethanolamine. Of these, alkali metal hydroxides are preferred in terms of foamability, low temperature stability, and lack of coloration over time.

  Component (C) can be used singly or in combination of two or more, and preferably has a neutralization rate of components (A) and (B) from the viewpoint of bubbling and detergency against oily strong oil stains. It is used so that it may be 50 to 100%, preferably 70 to 98%, more preferably 70 to 93%.

  The water of the component (D) used by this invention is used as a solvent, and is 1-99 mass% in the whole composition, Preferably it is 2.5-90 mass%, More preferably, it contains 5-80 mass%.

The detergent composition obtained in the present invention can further contain (E) a fatty acid or a salt thereof that is solid at 20 ° C., can improve foaming and refreshing feeling, and foam is generated during washing. It can suppress dripping.
Such fatty acid is preferably a linear saturated fatty acid having 12 to 22 carbon atoms, and examples thereof include lauric acid, myristic acid, palmitic acid, and stearic acid.

Examples of the fatty acid salt include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. .
As the component (E), lauric acid, myristic acid, palmitic acid, stearic acid or a sodium salt or potassium salt thereof is preferable, and lauric acid, myristic acid or a sodium salt or potassium salt thereof is more preferable.

Component (E) fatty acid or a salt thereof can be used alone or in combination of two or more thereof.
From the viewpoint of foamability, the acid is contained in the total composition in an amount of 0.1 to 60% by mass, preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass.

  The cleaning composition of the present invention further comprises components used in ordinary cleaning agents, such as surfactants other than those described above, moisturizing agents, oily components, bactericides, anti-inflammatory agents, antiseptics, chelating agents, thickening agents. Agents, pearlizing agents, fragrances, cooling agents, pigments, ultraviolet absorbers, antioxidants, plant extracts and the like.

In the present invention, components (A), (B) and (D1) a part of water is heated and mixed, and (D2) the remainder of water and (C) the base are mixed together to obtain component (A). And it adds so that the neutralization rate of (B) may be 50-100%, and manufactures a cleaning composition.
The heat mixing is preferably performed at 50 to 90 ° C.
Moreover, although the water of a component (D) is divided and mixed into a part of (D1) water and the remainder of (D2) water, it is preferable that these total amounts are in the said range. Moreover, it is preferable that the ratio of the base of (D2) and (C) is 1: 4-20: 1.
Moreover, when mix | blending a component (E) and another component, it can add, when heat-mixing a part of component (A), (B) and (D1) water. Furthermore, after neutralization, a fragrance | flavor and another water-soluble component can be added, and it can cool after that and can obtain a cleaning composition.

  The resulting cleaning 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 5 to 80000 mPa · s. It is preferable that it can be adjusted by appropriately selecting the blending components.

  The detergent composition obtained in the present invention may be, for example, hand soap, hand wash, face wash, face washing foam, cleansing foam, solid soap, cleansing agent, body soap, body washing foam, hair washing agent, etc. it can. Among them, it is suitable as a skin cleanser composition such as a facial cleanser, solid soap, cleansing agent, body soap and the like.

  A method for cleaning the skin using the cleaning composition obtained in the present invention is, for example, as follows. That is, the cleaning composition obtained in 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 hot 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 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 alkyl ether carboxylic acid of the component (A) used for the cleaning 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), 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), R ¹ is a decyl group, the average value of n is 3.1, n = 0 contains 16% by mass, n = 1 and n = 2 The total amount of the components was 37% by mass.

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

Production Example 7
Following Production Example 1, EO was added to a raw material in which lauryl alcohol and cetyl alcohol were mixed at a mass ratio of 20/80 to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in the general formula (1), R ¹ includes lauryl group / palmityl group = 20/80, n has an average value of 3.1, and n = 0 contains 16% by mass. The total amount of the component 1 and the component n = 2 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), R ¹ is a lauryl group, the average value of n is 3.5, and n = 0 contains 11.4% by mass, and n = 1 and n The total amount of the components of = 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), R ¹ is a component of lauryl group / myristyl group = 94/6, average carbon number is 12.1, n average value is 3.1, and n = 0 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 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.

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 Corporation) and Nikkor ECTD-3NEX (made by Nikko Chemical Co., Ltd.) used in the examples is published on the catalog value of each company's vendor and on the website. The unknown alkyl composition, the amount of the component 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 1-7, Comparative Examples 1-4
Manufactures a detergent composition having the composition shown in Table 3 and has a detergency (sebum, sunscreen, foundation), foaming, foam that does not flow down from the skin, no stickiness immediately after rinsing, a refreshing feeling, no feeling of feeling The absence of soap stains was evaluated. The results are also shown in Table 3.

(Production method)
A part of component (D) and glycerin were mixed, and components (A), (B), and (E) were sequentially mixed. The mixture was warmed to 50 ° C. and stirred well to make it uniform. Further, (D2) a mixture of the remaining water and (C) the base was added and stirred to make it uniform. Then, it cooled to 30 degreeC and obtained the cleaning composition.

(Evaluation method)
(1) Detergency (sebum):
The skin color E0 (L0, a0, b0) of the test site (the inner side of the forearm) before the test was measured (color difference meter: MINOLTA DP300). Thereafter, model sebum (composition: see Table 4; colored by mixing 2% by mass of carbon black with 100% by mass of model sebum) was uniformly applied to a test site in a circular size of 20 mg / 5 cm ² , and 30 After drying for a minute, skin color E1 (L1, a1, b1) in a state where model sebum was applied was measured. Next, the detergent composition is diluted 5 times with ion-exchanged water and put into a pump former (160 mL; YF-9413, manufactured by Yoshino Kogyo Co., Ltd.). One push of foam (0.85-0.95 g) Placed on the test site. The index finger was massaged 5 times on the left and right (10 times in total) and rinsed lightly with 20 mL of 30 ° C. tap water. The skin color E2 (L2, a2, b2) after the washing treatment was measured, and the washing rate was calculated from the following formula.
ΔE01 = √ [(L0−L1) ² + (a0−a1) ² + (b0−b1) ² ]
ΔE02 = √ [(L0−L2) ² + (a0−a2) ² + (b0−b2) ² ]
Cleaning rate (%) = (1−ΔE02 / ΔE01) × 100

The evaluation results are shown by the following criteria depending on the cleaning rate.
(Similar standards are also shown for the cleaning rate for sunscreen and foundation)
5: Cleaning rate of 80% or more.
4: The cleaning rate is 60% or more and less than 80%.
3: The cleaning rate is 40% or more and less than 60%.
2: The cleaning rate is 20% or more and less than 40%.
1: The cleaning rate is less than 20%.

(2) Detergency (sunscreen):
The skin color E0 (L0, a0, b0) of the test site (the inner side of the forearm) before the test was measured (color difference meter: MINOLTA DP300). Thereafter, sunscreens (manufactured by Kao Corporation, against Biore smooth UV Perfect Milk 100 wt%, colored by mixing carbon black 2% by weight) to the test site, applied to a circular size of 20 mg / 5 cm ² uniformly Then, after drying for 60 minutes, the skin color E3 (L3, a3, b3) in a state where a sunscreen was applied was measured. Next, the detergent composition is diluted 5 times with ion-exchanged water and put into a pump former (160 mL; YF-9413, manufactured by Yoshino Kogyo Co., Ltd.). One push of foam (0.85-0.95 g) Placed on the test site. The index finger was massaged 5 times on the left and right (10 times in total) and rinsed lightly with 20 mL of 30 ° C. tap water. The skin color E4 (L4, a4, b4) after the washing treatment was measured, and the washing rate was calculated from the following formula.
ΔE03 = √ [(L0−L3) ² + (a0−a3) ² + (b0−b3) ² ]
ΔE04 = √ [(L0−L4) ² + (a0−a4) ² + (b0−b4) ² ]
Cleaning rate (%) = (1−ΔE04 / ΔE03) × 100

(3) Detergency (foundation):
The skin color E0 (L0, a0, b0) of the test site (the inner side of the forearm) before the test was measured (color difference meter: MINOLTA DP300). Thereafter, a foundation (colored by mixing 2% by mass of carbon black with 100% by mass of Kao Sofina Prima Vista Liquid Foundation (Ocher 07)) was uniformly applied to the test site in a circular size of 3.25 mg / 5 cm ^2. After apply | coating and drying for 60 minutes, the skin color E5 (L5, a5, b5) of the state which apply | coated the foundation was measured. Next, the detergent composition is diluted 5 times with ion-exchanged water and put into a pump former (160 mL; YF-9413, manufactured by Yoshino Kogyo Co., Ltd.). One push of foam (0.85-0.95 g) Placed on the test site. The index finger was massaged 5 times on the left and right (10 times in total) and rinsed lightly with 20 mL of 30 ° C. tap water. The skin color E6 (L6, a6, b6) after the washing treatment was measured, and the washing rate was calculated from the following formula.
ΔE05 = √ [(L0−L5) ² + (a0−a5) ² + (b0−b5) ² ]
ΔE06 = √ [(L0−L6) ² + (a0−a6) ² + (b0−b6) ² ]
Cleaning rate (%) = (1−ΔE06 / ΔE05) × 100

(4) Foaming:
One expert evaluator took 1 g of each detergent composition in one hand, diluted about 5 times with 30 ° C. tap water, and bubbled for about 30 seconds. The ease of foaming at that time was evaluated according to the following criteria.
5: Easy to foam.
4: Slightly easy to foam.
3: Neither can be said.
2: Slightly difficult to foam.
1: Difficult to foam.

(5) Foam that does not flow down from the skin:
One expert evaluator took 1 g of each detergent composition in one hand, diluted about 5 times with 30 ° C. tap water, and bubbled for about 30 seconds. Thereafter, the foam was collected on one palm, spread on one horizontally stretched arm (from elbow to wrist), and after 5 seconds, the condition of the foam flowing down from the skin was observed and evaluated according to the following criteria.
5: It does not flow down.
4: Almost no flow down.
3: Slightly flows down.
2: Slightly falls.
1: It flows down immediately.

(6) No stickiness immediately after rinsing:
One expert evaluator took 1 g of each detergent composition in one hand, diluted about 5 times with 30 ° C. tap water, and bubbled for about 30 seconds. After that, the foam was collected in one palm, one arm (from elbow to wrist) was washed with the foamed foam, rinsed with tap water and rinsed. Immediately after that, the non-stickiness of wet skin was evaluated according to the following criteria.
5: No stickiness.
4: Almost no stickiness.
3: Neither can be said.
2: Slightly sticky.
1: There is stickiness.

(7) Refreshing feeling:
One expert evaluator took 1 g of each cleaning composition in one hand, diluted about 5 times with 30 ° C. tap water, foamed for about 30 seconds, applied to the face and washed. Next, when the face was washed away with tap water and the face was wiped with a towel, the freshness of the skin was evaluated according to the following criteria.
5: A refreshing feeling is strong.
4: A slight refreshing feeling is strong.
3: Neither can be said.
2: Slightly refreshing feeling is weak.
1: A refreshing feeling is weak.

(8) No sense of tension:
One expert evaluator took 1 g of each cleaning composition in one hand, diluted about 5 times with 30 ° C. tap water, foamed for about 30 seconds, applied to the face and washed. Then rinsed with tap water and wiped his face with a towel. The feeling of tightness of the face after about 10 minutes was evaluated according to the following criteria.
5: There is no sense of tension.
4: There is almost no sense of tension.
3: There is a slight feeling of tension.
2: There is a sense of tension.
1: Strong feeling.

(9) No soap stains:
Each cleaning composition was adjusted to a 5% aqueous solution using 20 HD hard water. The adjusted aqueous solution (40 ° C.) is put into a pump former (160 mL; YF-9413, manufactured by Yoshino Kogyo Co., Ltd.) and placed on the skin model (skin model No. 10A (40 generations) #BLACK, surface normal, manufactured by Beaulux). 1 push (0.85-0.95 g), foam was applied, and left in a dryer at 50 ° C. for 1 hour. The dried skin model was taken out and rinsed with 2 mL of 20 HD hard water with a dropper. After rinsing three times in total, the surface was lightly pressed with a tissue to wipe off moisture. After naturally drying it for 5 minutes, the skin model was visually observed. The degree of soap stain adhesion was evaluated according to the following criteria. The less soap dirt is attached, the harder it is to get in the bathroom and bathroom.
5: No adhesion.
4: Almost no adhesion.
3: Slightly attached.
2: Slightly adhered.
1: There is much adhesion.

Examples 8-14
A cleaning composition having the following composition is produced in the same manner as in Examples 1-7.
Each of the resulting detergent compositions is excellent in detergency and foaming, has no stickiness immediately after rinsing, does not feel sticky after wiping with a towel, has a refreshing feeling, and has no soap stains. is there.

Example 8 (Pump former face wash)
(component)
EC1 2.0 (mass%)
Oleic acid 2.0
Lauric acid 1.0
Myristic acid 1.0
Alkyl (C8-14) glucoside 1.0
Lauryl hydroxysulfobetaine 0.3
Glycerin 5.0
Potassium hydroxide appropriate amount
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.95)

Example 9 (Paste face wash)
(component)
EC1 7.5 (mass%)
Oleic acid 3.5
Lauric acid 2.0
Myristic acid 1.75
Lauryl hydroxysulfobetaine 4.0
Acrylic acid / alkyl methacrylate copolymer * 3 0.2
Glycerin 5.0
Potassium hydroxide appropriate amount
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.95)
* 3: Carbopol ETD2020 (Lubrizol Advanced Material, Inc.)

Example 10 (Soap)
(component)
EC2 5.0 (mass%)
Oleic acid 50.0
Lauric acid 7.5
Myristic acid 7.5
Glycerin 5.0
Sodium hydroxide
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.90)

Example 11 (Soap)
(component)
EC3 5.0 (mass%)
Oleic acid 50.0
Lauric acid 7.5
Myristic acid 7.5
Glycerin 5.0
Sodium hydroxide
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.90)

Example 12 (Soap)
(component)
EC4 5.0 (mass%)
Oleic acid 50.0
Lauric acid 7.5
Myristic acid 7.5
Glycerin 5.0
Sodium hydroxide
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.90)

Example 13 (Soap)
(component)
EC5 5.0 (mass%)
Oleic acid 50.0
Lauric acid 7.5
Myristic acid 7.5
Glycerin 5.0
Sodium hydroxide
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.90)

Example 14 (Soap)
(component)
EC6 5.0 (mass%)
Oleic acid 50.0
Lauric acid 7.5
Myristic acid 7.5
Glycerin 5.0
Sodium hydroxide
Ion exchange water balance
Total 100
(Neutralization rate of components (A) and (B): 0.90)

Claims (8)

(A) General formula (1)

(In the formula, R ¹ represents an alkyl group having 10 to 16 carbon atoms, and n represents a number of 0 to 20)
Wherein R ^{1 has} an average carbon number of 10.8 to 12.5 , n has an average value of 2.8 to 3.4, and n = 0 9.9 to 27% by mass , alkyl ether carboxylic acid 0.1 to 60% by mass containing 27 to 36.1% by mass in total of n = 1 component and n = 2 component,
(B) 0.1 to 80% by mass of liquid fatty acid at 20 ° C., and (D1) a part of water is heated and mixed, and (D2) the remainder of water and (C) a base are mixed. A method for producing a detergent composition, wherein the neutralization rate of components (A) and (B) is 50 to 100%.   The manufacturing method of the cleaning composition of Claim 1 whose mass ratio of a component (A) and (B) is (A) / (B) = 0.05-20.   3. When mixing (A), (B) and (D1) by heating, (E) 0.1 to 60% by mass of a solid fatty acid or a salt thereof at 20 ° C. is added as an acid. The manufacturing method of the cleaning composition of this. 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 36.1 mass% in total of the component of n = 1, and the component of n = 2 is any one of Claims 1-3 A method for producing the cleaning composition according to claim 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 process according to claim 1 detergent composition according to any one of 4 to be 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 manufacturing method of the cleaning composition of any one of 1-5 . 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 = 4 weight component) = 1: 0.99 to 1.34: 0.89 to 1.40: 0.76 to 1.23: 0.63 to 1 and consisting claim 1-6 either 1 Method for producing a detergent composition. A method for rinsing the skin after applying the cleaning composition obtained by the production method according to any one of claims 1 to 7 to a body skin part and cleaning it.