JP7049938B2 - Cleaning fee - Google Patents

Description

The present invention is a polyglycerin fatty acid ester in which a polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and capric acid are ester-bonded, and the HLB value is 11 to 14. Containing and thickening the cleaning agent.

The applicant of this journal is a polyglycerin fatty acid ester obtained by ester-bonding polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and caprylic acid, and having an HLB value of 11 to 14. A cosmetic composition containing an ester and a technology for cosmetics are disclosed (Patent Document 1). Further, the applicant has applied polyglycerin having an average degree of polymerization of 10 to 30, a polyglycerin fatty acid ester (A) in which a mixed fatty acid of caprylic acid and caprylic acid is ester-bonded, an oil agent (B), and water ( C) We propose a technique for a cosmetic composition containing 30 to 88% by mass and having a blending ratio of the polyglycerin fatty acid ester (A) and the oil agent (B) of 6: 1 to 2: 1. Then, a thickener to be blended in the cosmetic composition was examined, and it was disclosed that an acrylic acid / methacrylic acid alkyl copolymer and a carboxyvinyl polymer were suitable (Patent Document 2).

The present inventor has been developing a technique for thickening a cleaning agent, and contains a polyglycerin fatty acid ester in which a polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and capric acid are ester-bonded. As a result of examining the cleaning agent to be used, (A) a polyglycerin having an average degree of polymerization of 15 to 30, a polyglycerin fatty acid ester in which a mixed fatty acid of caprylic acid and capric acid is ester-bonded, and (B) a fatty acid alkali metal. It has been found that when a salt and (C) hydroxypropylmethylcellulose are blended in combination, a cleaning agent having an excellent stability can be obtained without thickening and separating at a low temperature. Separation at low temperatures, especially gels, in thickened cleaning agents is often a problem due to the irreversible phenomenon.

Japanese Patent No. 6215435 Japanese Patent Application No. 2017-49932

The present invention is a polyglycerin fatty acid ester in which a polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and capric acid are ester-bonded, and the HLB value is 11 to 14. It is an object of the present invention to provide a thickened cleaning agent containing an ester and having excellent stability.

The present invention has the following configuration.
(1) A cleaning agent containing (A) to (C) and having a total amount of surfactant of 21% by mass or less.
(A) A polyglycerin fatty acid ester in which a mixed fatty acid of polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and caprylic acid is ester-bonded, and having an HLB value of 11 to 14.
(B) Fatty acid alkali metal salt,
(C) The cleaning agent according to (1), wherein the polyglycerin fatty acid ester of hydroxypropylmethyl cellulose (2) (A) is penta (caprylic acid / capric acid) polyglyceryl-20.
(3) The cleaning agent according to (1) or (2), wherein the compounding ratio of (A): (B): (C) is (0.85 to 3) :( 3 to 5): 1.

The cleaning agent of the present invention has a viscosity of 2000 to 4000 mPa · s at 25 ° C., and the gel does not separate at a low temperature and is excellent in stability. Further, the cleaning agent of the present invention is excellent in transparency, detergency, and foaming, and is therefore most suitable as a cleaning agent for cosmetics.

The present invention is (A) a polyglycerin fatty acid ester in which a mixed fatty acid of polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and capric acid is ester-bonded, and the HLB value is 11 to 14. The present invention relates to a cleaning agent containing (B) a fatty acid alkali metal salt and (C) hydroxypropylmethyl cellulose.

(A) A polyglycerin fatty acid ester in which a polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and capric acid are ester-bonded, which is used in the present invention and has an HLB value of 11 to 14. As the glycerin fatty acid ester, any one disclosed in Patent Document 1 can be used. For example, hexa (caprylic acid / capric acid) eikosaglycerin (HLB11.4), penta (caprylic acid / capric acid) eikosaglycerin (HLB12.2), tetra (caprylic acid / capric acid) eikosaglycerin (13. 1) can be exemplified.
These polyglycerin fatty acid esters can be produced according to the method disclosed in Patent Document 1.

The method for calculating the average degree of polymerization of polyglycerin is not particularly limited, but for example, a method for calculating from hydroxyl value, gas chromatography, liquid chromatography, thin layer chromatography, gas chromatograph mass spectrometry or liquid chromatograph mass spectrometry. A method of determining the composition of polyglycerin from the above and calculating the average degree of polymerization can be mentioned. In the present specification, the average degree of polymerization in the examples described later is determined from the hydroxyl value based on the following formula, but is not limited to this calculation method.
OHV = 56110 (n + 2) / (74n + 18)
OHV: Hydroxyl value of polyglycerin n: Average degree of polymerization of polyglycerin

The degree of esterification may be adjusted so that the HLB value of the polyglycerin fatty acid ester used in the present invention is 11 to 14, and more preferably the HLB value is 12 to 13. When a mixed fatty acid is ester-bonded to 1 mol of polyglycerin having an average degree of polymerization of 20 so as to be 4 to 7 mol, a polyglycerin fatty acid ester having an HLB value in the range of 11 to 14 can be obtained. Here, the mixed fatty acid used means a mixture of caprylic acid and capric acid. The ratio of caprylic acid to caprylic acid is preferably 10:90 to 90:10 by mass ratio, and more preferably 10:90 to 50:50 by mass ratio.

The polyglycerin fatty acid ester used in the present invention can be produced, for example, by esterifying polyglycerin and a mixed fatty acid (caprylic acid / capric acid) by a conventional method. That is, the polyglycerin and the mixed fatty acid are preferably removed from water at 100 to 300 ° C. in the presence of an acid catalyst (phosphoric acid, p-toluenesulfonic acid, etc.) or an alkaline catalyst (caustic soda, etc.) or without a catalyst. It is preferably carried out by heating in the range of 120 to 260 ° C. Moreover, the reaction may be carried out in the presence of an inert gas. The polyglycerin fatty acid ester thus obtained may be purified depending on the intended purpose. For purification, in addition to techniques such as molecular distillation under reduced pressure, extraction with an organic solvent, chromatographic separation using a column packed with a fractionation or synthetic adsorbent, and a gel filter can also be used. The polyglycerin fatty acid ester used in the present invention can also be obtained by transesterifying with polyglycerin using an ester of caprylic acid or caprylic acid instead of the mixed fatty acid.
The blending amount of the polyglycerin fatty acid ester used in the present invention is preferably 0.1 to 2.5% by mass, more preferably 1 to 2.5% by mass, based on the total amount of the cleaning agent.
The polyglycerin fatty acid ester of (A) of the present invention is a component that enhances detergency, but it contributes to the stability of the detergency by suppressing white turbidity of the component (B) at low temperature, generation of haze, and precipitation of soap grains. do.

The (B) fatty acid alkali metal salt used in the present invention contributes to the stability of the cleaning agent by coexisting with the polyglycerin fatty acid ester of (A). As a secondary effect, it exerts the effects of foaming and detergency. Examples of the fatty acid alkali metal salt include sodium laurate, potassium laurate, sodium myristate, potassium myristate, sodium palmitate, potassium palmitate and the like. The type of salt may be triethanolamine.
The blending amount of the (B) fatty acid alkali metal salt in the present invention is preferably 1 to 7% by mass, particularly preferably 1 to 5% by mass, based on the total amount of the cleaning agent. If it exceeds this range, the risk of white turbidity and haze will increase during low-temperature storage, and if the temperature is returned to room temperature, this white turbidity and haze will disappear and transparency will be obtained, but prescription design for cosmetics that emphasize aesthetics. Then you need to be careful. In the specification, (B) fatty acid alkali metal salt may be referred to as soap.

As the (C) hydroxypropylmethyl cellulose used in the present invention, a commercially available product may be used, and examples thereof include Metrose 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.).
The blending amount of (C) hydroxypropylmethylcellulose is preferably 0.5 to 1.5% by mass, more preferably 0.5 to 1.2% by mass, and particularly preferably 0.7 to 0.7 to the total amount of the cleaning agent. It is preferably 1% by mass.

In the present invention, (C) hydroxypropylmethylcellulose is the main component that thickens the cleaning agent. (C) Hydroxypropylmethylcellulose is a general-purpose ingredient that thickens cosmetics, but with a composition that does not cause precipitation of hydroxypropylmethylcellulose (gel separation) at low temperatures in the cleaning agent, the viscosity is 1000 to 1500 mPa · s (25 ° C). The composition can only be thickened to a certain extent. If the viscosity is as high as 2000 mPa · s, the hydroxypropylmethylcellulose gel may precipitate (separate) at a low temperature (-5 ° C, 5 ° C), which is not preferable in terms of quality design.
(A) A cleaning agent containing a polyglycerin fatty acid ester in which a mixed fatty acid of polyglycerin having an average degree of polymerization of 15 to 30 and a mixed fatty acid of caprylic acid and caprylic acid is ester-bonded is thickened to a viscosity of 2000 mPa · s or more, and In order to be stable even when stored in a wide temperature range (-5 ° C, 5 ° C, 25 ° C, 40 ° C) required for quality design, it is essential to add (B) fatty acid alkali metal salt. However, if a large amount of (B) fatty acid alkali metal salt is blended, the risk of precipitation at low temperature and white turbidity increases. Soap precipitation at a low temperature of the cleaning agent is a reversible phenomenon that disappears when heated to about room temperature (25 ° C.), so it is unlikely to be a big problem, but caution is required in cold regions. In the present invention, the component (A) acts to suppress the precipitation of soap at a low temperature, so that the three components (A + B + C) of the present invention may be blended in order to achieve excellent low temperature stability. It is indispensable, and by adopting this configuration, high quality can be guaranteed even in cold regions.
In the present invention, in particular, when the compounding of (C) hydroxypropylmethylcellulose is 1, (A) a poly obtained by ester-bonding a mixed fatty acid of polyglycerin, capricyl and capric acid having an average degree of polymerization of 15 to 30. The preferable blending ratio of the polyglycerin fatty acid ester having an HLB value of 11 to 14 and the (B) fatty acid alkali metal salt, which is a glycerin fatty acid ester, is preferably as follows.
The blending ratio of (A): (B): (C) is (0.85 to 3) :( 3 to 5): 1.
If it is out of this range, there is a high risk that a stable cleaning agent cannot be obtained at low temperatures.

In the present invention, an anionic surfactant, an amphoteric surfactant, a polyhydric alcohol, or the like, which is effective for good foaming (foam amount and retention of foam), may be blended as an optional component. Further, a pH adjuster (potassium hydroxide or the like) may be blended.
Examples of the anionic surfactant include amino acid-based surfactants.
Examples of commercially available products include Amylite ACS-12K (30% aqueous solution of cocoylalanine Na, manufactured by Ajinomoto Healthy Supply Co., Ltd.) and Amylite GCK-12K (30% aqueous solution of cocoylglycine K, manufactured by Ajinomoto Healthy Supply Co., Ltd.).
For example, the blending amount of the amino acid-based surfactant is preferably 5 to 12% by mass with respect to the total amount of the cleaning agent.

Examples of the amphoteric tenside include amidoamine oxide, imidazoline type betaine, and amide sulfobetaine type. Commercially available products of amidoamine oxide include, for example, the label name lauramidopropylamine oxide (compound name: lauric acid amidopropyldimethylamine oxide: trade name: "softazoline LAO-C" manufactured by Kawaken Fine Chemicals Co., Ltd.), and the label name myristamide. Propylamine oxide (compound name: myristic acid amidopropyldimethylamine oxide), mixture of lauramidopropylamine oxide and myristamidepropylamine oxide (trade name: "AMMONYX LMDO" manufactured by Stepan), display name cocamidopropylamine oxide (compound) Name: Palm oil fatty acid amidopropyldimethylamine oxide: Trade name: "AMMONYX CDOSPECIAL" manufactured by Stepan) can be exemplified.
For example, the blending amount of amidoamine oxide is preferably 0.6 to 6% by mass with respect to the total amount of the cleaning agent.

As the imidazoline type betaine, sodium cocoamphoacetate can be exemplified. Examples of commercially available products include NIKKOL AM-101 (manufactured by Nikko Chemicals Co., Ltd.) and Softazoline CL-R (manufactured by Kawaken Fine Chemicals Co., Ltd.).
For example, the blending amount of sodium cocoamphoacetate is preferably 0.6 to 7% by mass with respect to the total amount of the cleaning agent.

As the amide sulfobetaine type, lauramidopropyl hydroxysultaine can be exemplified. As a commercially available product, for example, Softazoline LSB-R (manufactured by Kawaken Fine Chemical Co., Ltd.) can be exemplified.
For example, the blending amount of lauramidopropyl hydroxysultaine is preferably 0.3 to 1.5% by mass with respect to the total amount of the cleaning agent.

In the present invention, the amount of the total surfactant in the cleaning agent is preferably 17 to 21% by mass with respect to the total amount of the cleaning agent. If it exceeds 21% by mass, the risk of precipitating hydroxypropylmethylcellulose at low temperature increases. If it is less than 17% by mass, the function as a cleaning agent may not be sufficient.

Examples of the polyhydric alcohol include glycerin, diglycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, 1,2-pentanediol and the like.

The present invention will be further described below by showing tests using Examples and Comparative Examples.
(1) Preparation of test sample The cleaning agents of Examples 1 to 4 and Comparative Examples 1 to 6 having the compositions shown in the table were prepared by a conventional method.

(2) Viscosity measurement A cleaning agent was placed in a glass bottle with a cap of No. 6 and measured with a B-type viscometer (25 ° C, No. 2 rotor, 12 rotations, 30 seconds). After storing in each temperature range (-5 ° C, 5 ° C, 25 ° C, 40 ° C), the temperature was returned to 25 ° C at the time of measurement before measurement.

In addition, the cleaning agent of the present invention was evaluated by the following tests for three items of appearance observation, detergency, and foaming.
(3) Appearance observation (stability)
A cleaning agent was placed in a glass bottle with a cap of No. 6, and the appearance (presence or absence of gel precipitation, presence or absence of soap particles) was visually observed.
The observations are listed in the table. In addition, the stability was judged according to the following criteria.
◯: There is no precipitation of gel and soap grains.
Δ: Gel or soap particles are precipitated at −5 ° C., but not at 5 ° C.
X: There is precipitation of gel or soap grains at -5 ° C and 5 ° C.
If the gel precipitates slightly after storage at -5 ° C for 1 month, it is judged that there is no effect in actual use, and it is marked with ◯ in the stability column of the table.

(4) Detergency and Foaming Evaluation Method A sunscreen cosmetic containing a high amount of a hydrophobized inorganic ultraviolet scattering agent was applied to a 3 × 3 cm area of the upper arm and dried for 30 minutes.
The sunscreen cosmetic contains 22% by mass of the hydrophobized fine particle titanium oxide and fine particle zinc oxide in a total amount. After applying 0.2 g of the cleaning agent, it was rubbed by hand 30 times, and further rubbed 3 times with warm water to wash it off. Moisture was wiped off with a towel, and evaluation was performed after washing.
In the evaluation, foaming during cleaning and stain removal after cleaning were visually confirmed.

(4-1) Evaluation criteria for foaming The evaluation criteria are as follows.
○: Good foaming
△: Foaming is a little bad
×: Poor foaming

(4-2) Evaluation criteria for cleansing power (presence or absence of white residue on the skin) ○: No white residue
△: You can see the white residue.
×: White residue is clearly visible

(3) Results The evaluation results are shown in the lower part of Table 1.

(result)
When the total amount of the surfactant is small, the stability is excellent, but the detergency and foaming are not good (Comparative Example 1). If the total amount of the surfactant is increased and the thickener is cellulose gum, the gel does not precipitate, but the viscosity is very low, and the detergency and foaming are not good (Comparative Example 2). Although the composition of the cleaning agent having a viscosity of 2000 mPa · s or more was assembled, the gel was precipitated at a low temperature, foamed, and the cleaning power was not good (Comparative Examples 3 and 4). When soap was added, the composition of a cleaning agent having a viscosity of 2000 mPa · s or more was obtained, foaming was improved, and gel did not precipitate at a low temperature, but soap particles were slightly precipitated (Comparative Example 5).
On the other hand, by combining (A), (B) and (C), the target viscosity is 2000 mPa · s or more, and the stability is excellent without gel precipitation or soap grain precipitation at low temperature. A cleaning agent was obtained, and an excellent cleaning agent (foaming, detergency) was also obtained (Examples 1 to 4). In Comparative Example 6, (A), (B) and (C) were blended in combination, and gel precipitation was observed at a low temperature. It is considered that this is because the total amount of the surfactant exceeds 21% by mass, the various components dissolved in water increase and the water is exchanged, so that the hydroxypropylmethyl cellulose is not in a stable state and precipitates. The total amount of the surfactants in Comparative Examples 3 and 4 was 17.9% by mass, and gel precipitation was observed, whereas the total amount of the surfactants in Examples 1 to 4 was 19.26 to 20.26. Despite the increase in mass%, the precipitation of gel was suppressed, and the function as a cleaning agent (foaming, detergency) could be enhanced. It was found that by combining (A), (B) and (C), a thickened cleaning agent having excellent functionality and stability can be obtained. In particular, when the compounding ratio of (C) hydroxypropylmethyl cellulose is 1, the preferable compounding ratio of (A) and (B) is (A) :( B) :( C) (0.85 to 3) :. It was found that (3 to 5): 1 was preferable.
Next, a prescription example of the present invention will be shown.

Prescription example 1 (cleaning agent for body)% by mass
1. 1. Potassium laurate 2
2. 2. Potassium myristate 0.3
3. 3. Potassium palmitate 0.3
4. Cocoyl alanine sodium 1.5
5. Cocoyl glycine potassium 6
6. Triethanolamine cocoyl glutamate 3
7. Penta (caprylic acid / caprylic acid) polyglyceryl-20 1.5
8. Lauramide propylamine oxide 1.5
9. Sodium cocoamphoacetate 3
10. Lauramide Propyl hydroxysultaine 1.5
11. Glycerin 7
12.1,2-Pentanediol 2
13 Hydroxypropyl Methyl Cellulose 0.85
14. The residual water components 1 to 14 were mixed by a conventional method to obtain a cleaning agent for a body.
The body cleanser of Formulation Example 1 had good foaming, and the sunscreen cosmetic of SPF50 (containing 25% by mass of a hydrophobically treated inorganic ultraviolet scattering agent) was washed cleanly without leaving white residue on the skin. The viscosity was 2500 mPa · s, and even after storage in a wide temperature range (5 ° C, 25 ° C, 40 ° C) for 1 month, no gel or soap particles were deposited and the stability was excellent.

Claims (1)

It contains (A) to (C), the total amount of the surfactant is 21% by mass or less , and the blending ratio of (A) :( B): (C) is (0.85 to 3) :( 3). ~ 5): 1 cleaning charge.
(A) Penta (caprylic acid / capric acid) polyglyceryl-20
(B) Fatty acid alkali metal salt,
(C) Hydroxypropyl Methyl Cellulose