JPS6046085B2 - cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a stable and skin-friendly ester comprising a polyglycerin fatty acid ester and a polybasic acid, that is, a fatty acid polybasic acid polyglycerin ester and/or a salt thereof. There is something about safe cosmetics.

Fatty acid polyglycerol esters, which are useful as surfactants for medical products, cosmetics, and foods, are obtained by esterifying fatty acids and polyglycerin.
The core polyglycerol is obtained by condensing glycerin or by reacting glycerin with glycidol, and is generally obtained by condensing glycerin.

In this way, fatty acid polyglycerin ester uses glycerin as a starting material, so it has low irritation to the skin, etc.
Emulsifiers have good safety, and the hydrophilic-lipophilic balance (hereinafter abbreviated as HLB) can be changed by changing the type of fatty acid, the degree of polymerization of glycerin, and the degree of esterification. It has been considered useful as a solubilizer.

Therefore, the application to cosmetics has been particularly studied, and several fatty acid polyglycerol esters including fatty acid diglycerol esters are already in use.

However, while fatty acid polyglycerol esters have good skin safety, which is an essential condition for cosmetic surfactants, as mentioned above, they are not as good as conventional surfactants in terms of surfactant ability. In reality, however, it has the following drawbacks, and improvement thereof has been highly desired.

(1) High ■, B is difficult to obtain. In other words, the conventional method for increasing the hydrophilicity of fatty acid polyglycerol esters during synthesis is to increase the degree of polymerization and increase the number of hydroxyl groups, but increasing the degree of polymerization causes an extreme increase in viscosity, making synthesis difficult. In addition, the usability of the synthesized fatty acid polyglycerin ester is not good because it is highly sticky. On the contrary, in the case of the fatty acid polybasic acid polyglycerin ester according to the present invention, the viscosity can be freely adjusted to high (1) and B (high B) without any increase in viscosity. (
2) Poor compatibility with the skin.

In general, when cosmetics containing nonionic surfactants are used on the skin, they tend to have a thicker feel when used, compared to cosmetics containing anionic surfactants. In many cases, it does not have a range of use where it can be quickly adapted and integrated. Fatty acid polyglycerin is no exception, and has an unpleasant feeling when used, as if a layer of skin remains on the skin. In comparison, the fatty acid polybasic acid polyglycerin ester and/or its salt of the present invention has both the familiar feeling of use and the powdery and crisp feel of fatty acid polyglycerin. ing. In view of the current situation, the present inventors investigated improvements such as improving the performance of fatty acid polyglycerol esters, and as a result, they obtained fatty acid polybasic acid polyglycerol esters and/or salts thereof.

Like fatty acid polyglycerin esters, this product has good skin safety, and allows for free adjustment of HL, which was not possible with fatty acid polyglycerin esters.
Furthermore, it was found that it felt good on the skin and was found to be an ideal cosmetic surfactant. and,
The present inventors blended the fatty acid polybasic acid polyglycerin into various cosmetics to create a new product that has excellent safety, stable emulsifying properties, and good feeling of use, which are not found in conventional cosmetics. This led to the development of cosmetics. That is, the present invention uses polyglycerin with a degree of polymerization of 2 to 20 and a carbon number of 8 to 3.
A fatty acid polyglycerol ester consisting of 0 fatty acids and a polybasic acid are reacted so that at least one acid group of the polybasic acid remains free. The purpose is to provide cosmetics with special characteristics.

Here, for the purpose of understanding the fatty acid polybasic acid polyglycerol ester of the present invention, it is assumed that all the polyglycerol cores are α
The general formula for a linear polyglycerin ester polymerized at this position is as follows.

In the above general formula, n=2 to 20, R1, R2・
...Rn+1 represents hydrogen, a fatty acid residue having 8 to 30 carbon atoms, a polybasic acid residue, or a polybasic acid salt residue, and at least one of R1, R2, ...Rn+1 is carbon Among the number of 8 to 30 fatty acid residues, at least one other is a polybasic acid residue or a polybasic acid salt residue.

Hereinafter, the configuration of the present invention will be explained in detail.

The core polyglycerin of the fatty acid polybasic acid polyglycerin ester according to the present invention has a degree of polymerization of 2 to . 20, preferably 3 to 15.

Furthermore, those with a high degree of polymerization are considered to have good surface activity, but there is a problem that the viscosity of the system increases during synthesis, making it difficult for the reaction to proceed. In addition, the above polyglycerin has α. Generally, it is a polyglycerol condensed at the β position, but it may also be a branched polyglycerin condensed at the β position.

Next, the fatty acids constituting the fatty acid polybasic acid polyglycerol ester according to the present invention are linear saturated and unsaturated fatty acids having 8 to 30 carbon atoms, and saturated and unsaturated fatty acids having side chains, For example, puric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, palmitoleic acid, oleic acid,
Isopalmitic acid, isostearic acid, hydroxystearic acid, linoleic acid, linoleic acid, ricinoleic acid,
These include ricinoleic acid and abietic acid.

The number of moles of fatty acid added to polyglycerin can be arbitrarily selected taking into consideration the number of hydroxyl groups, polybasic acid residues and polybasic acid salt residues of polyglycerin, but at least 1 mole should be added. and 1 molar addition is most preferred. Polybasic acids constituting the fatty acid polybasic acid polyglycerol ester according to the present invention include succinic acid, glutaric acid, adipic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, and the like.

The number of moles of the polybasic acid added can also be arbitrarily selected while taking into account the number of hydroxyl groups and the number of fatty acid residues in the polyglycerin, but at least 1 mole or more must be added.

The fatty acid polybasic acid polyglycerol ester of the present invention can be blended into cosmetics as it is, but it can also be used by neutralizing the polybasic acid residues with a basic substance to further increase HL and B.

Basic substances that neutralize polybasic acid residues include metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, organic amines such as triethanolamine and isopropanolamine, and bases such as arginine and lysine. It is a sexual amino acid.

Neutralization of polybasic acid residues with a basic substance may be partial neutralization or complete neutralization. Alternatively, neutralization may be performed in advance to form a fatty acid polybasic acid polyglycerin ester salt, which can then be blended into cosmetics, or fatty acid polybasic acid polyglycerin may be blended into the oil phase and a basic substance may be blended into the aqueous phase. Neutralization may be carried out during the manufacturing process of cosmetics, such as during emulsification. The above fatty acid polybasic acid polyglycerin ester is generally synthesized by the following method.

That is, polyglycerin is heated at about 80°C under an alkali catalyst.
Convert to fatty acid ester at ~250°C (preferably 180°C to 230°C). Next, add this material to an acid anhydride and
℃~250℃ (preferably 180℃~2300℃)
The mixture is esterified with a polybasic acid to obtain the target fatty acid polybasic acid polyglycerin ester. Furthermore, if this product is neutralized or partially neutralized with a basic substance, a fatty acid polybasic acid polyglycerin ester salt can be obtained. In order to explain the above synthesis method in more detail, specific synthesis examples are given below.

The present invention is not limited thereby. Synthesis example-
1 Monolauric acid disuccinic acid decaglycerin ester Add 152 g of decaglycerin 1 40.5 g of lauric acid and 0.3 g of sodium hydroxide to a Mitsuro flask (1e) equipped with a stirring device and a water sampling tube, and add 200 to 200 g of sodium hydroxide while blowing nitrogen gas. Heat and stir at 230°C.

When the amount of water distilled reaches approximately 3.3 ml, the reaction is stopped by cooling to room temperature. Then, succinic anhydride 40.0
g and heated to 80-110℃ while blowing nitrogen gas.
The mixture was stirred for about 2 hours to obtain monolaurate disuccinate decaglycerin ester.

This product is a waxy substance at room temperature and has an acid value of 105.
It was 4.

This product can be used as is or partially neutralized with alkali.
Alternatively, it can be used after being completely neutralized.

Synthesis Example-2 Monolauric acid tetrasuccinic acid decaglycerin ester In a 1' three-meter flask equipped with a stirring device and a water sampling tube, 152 g of decaglycerin, 40.5 g of lauric acid, and 0.4 g of sodium hydroxide were added, and nitrogen gas was blown into the flask. While stirring, heat and stir at 200 to 230°C.

When the water distillation amount reaches approximately 3.3 mL, the reaction is stopped by cooling to room temperature. Then, succinic anhydride 80.
Add 1g and heat to 80-110 while blowing in nitrogen gas.
Stirring was carried out at °C for about 2 hours to obtain monolauric acid tetrasuccinic acid decaglycerin ester.

This product is a waxy substance at room temperature and has an acid value of 172.
．． It was 3. This product can be used as it is, or after being partially or completely neutralized with an alkali. Synthesis Example-3 Monolauric acid disuccinic acid hexaglycerin ester Using the same apparatus as in Synthesis Example 1, hexaglycerin 138
．． 6g1 lauric acid 60.1g1 and sodium hydroxide 0.12g were added, and while blowing nitrogen gas, 20
Heat and stir at 0 to 230°C.

When the amount of water distilled reaches approximately 5.0 ml, the reaction is stopped by cooling to room temperature. Then, succinic anhydride 60
．． Add 1g and blow nitrogen gas until it reaches 80~11.
Stirring was performed at 0° C. for about 2 hours to obtain monolauric acid disuccinic acid hexaglycerin ester.

This product is a colorless and transparent liquid substance at room temperature, and its acid value is 138.
．． It was 1. This product can be used as is, or partially or completely neutralized with an alkali.
Synthesis Example-4 Monolauric Acid Monoglutaric Acid Decaglycerin Ester Using the same reaction apparatus as in Synthesis Example-1, 227.4 g of decaglycerin, 64.1 g of lauric acid, and 0.6 g of sodium hydroxide were added, and nitrogen gas was blown into the mixture. While heating and stirring at 200 to 230°C.

When the water distillation amount reaches approximately 5.5 WLt, the reaction is stopped by cooling to room temperature. Next, 34.2 g of glutaric anhydride was added, and the mixture was heated to 80 g while blowing nitrogen gas.
Stirring was performed at ~110°C for about 3 hours to obtain monolauric acid monoglutaric acid decaglycerin ester.

This product is a colorless and transparent liquid substance at room temperature, and has an acid value of 57.8.
It was hot. This product can be used as is, or partially or completely neutralized with an alkali. Synthesis Example-5 Monoisostearic acid monoglutaric acid hexaglycerin ester Using the same apparatus as in Synthesis Example-1, 138.6 g of hexaglycerin 1 93.9 g of isostearic acid
Add 0.8 g of sodium hydroxide, and heat and stir at 200 to 230°C while blowing nitrogen gas.

When the water distillation amount reaches approximately 5.2 mt, the reaction is stopped by cooling to room temperature. Then, glutaric anhydride 35
．． 80-11 while adding 4g and blowing in nitrogen gas.
Stirring was performed at 0° C. for about 2 hours to obtain monoisostearic acid monoglutaric acid hexaglycerin ester.

This product is an almost colorless viscous substance at room temperature, and its acid value is 69.
．． It was 8. This product can be used as is, or partially or completely neutralized with an alkali.

Synthesis Example-6 Monoisostearic acid monoadipate decaglycerin ester Using the same equipment as in Synthesis Example-1, 227.4 g of decaglycerin 93.9 g of isostearic acid
g1 and 1.0 g of sodium hydroxide are added, and the mixture is heated and stirred at 200 to 230°C while blowing nitrogen gas.

When the amount of distilled water reaches about 5.5 ml, the reaction is stopped by cooling to room temperature. Next, 43.8g of adipic acid
1 and sodium hydroxide, and heated and stirred at 200 to 220°C while blowing nitrogen gas.

When the amount of distilled water reached about 5 ml, the reaction mixture was cooled to room temperature and the reaction was stopped to obtain monoisostearic acid adipic acid decaglycerol ester. The acid value of this product was 56.5.

In addition, this product can be used as it is, or after being partially or completely neutralized with an alkali.

In the present invention, by blending the fatty acid polybasic acid polyglycerol ester and/or its salt into cosmetics, it is possible to obtain cosmetics that are safe for the skin, have good emulsification, and are excellent in usability. can.

The resulting cosmetics may be of any type, including basic cosmetics, makeup cosmetics, hair cosmetics, and body cosmetics.
It is blended as one of the cosmetic ingredients, for example, in the same manner as conventional surfactants. The blending amount can be selected arbitrarily like conventional surfactants, but generally it is 0.
．． It is 1 to 95% by weight. Of course, the fatty acid polybasic acid polyglycerin ester and/or its salt may be blended in combination of two or more types with different structures, and in that case, the total blended amount is also 0.1 to 95% by weight. . As detailed above, the present invention relates to a cosmetic containing a novel surfactant, fatty acid polybasic acid polyglycerol ester and/or its salt, as an emulsifier or solubilizer. Conventional polyoxyethylene-based polyoxyethylene-based Compared to nonionic surfactants, anionic surfactants, and cationic surfactants, it is safer and it is possible to create many types of distinctive cosmetics. Basic acid polyglycerol esters are also useful as surfactants for pharmaceuticals because they have good safety.Hereinafter, in order to explain the present invention in more detail,
Although test examples and examples are given, the present invention is not limited thereto.

Test Example The tripotassium salt of monolaurate trisuccinate decaglycerin used in the present invention (PH=7) and the Journal of Pharmaceutical Science No. 5? SOdi described on page 1164 of the first trowel, 196 tsubo
unllaljrylethersulfate,SO
The following safety tests were conducted on diumlauryIsulfate.

1 Animal test 1.1 Examination of primary skin irritation (test according to FDA method)
Test method: Japanese white rabbits weighing 2.3k9 to 3k9 are used.

Eight rabbits whose back hair was trimmed with electric clippers were divided into two groups of four rabbits each, and one group was left alone (IntactSki
n), and the other group had an abrasion on the test site (, Abra
dedSkin) and fixed in a fixator. The test substance was 0.
Apply to the skin using an animal test bandage with a lint cloth of 3m11 diameter 2.5cm. After 24 hours, the bandage is removed, and the degree of erythema and edema is recorded according to the skin reaction criteria.

The determination is made again after n hours. Judgment: (1) Formation of erythema and derma. No erythema at all ... 0 Slight erythema ... 1 Clear erythema ... 2 Those with strong erythema...3 Those with strong erythema and slight derma...4 (2) Formation of edema Those with no edema...
0 Very slight edema is observed...1
Slight edema...2 Moderate edema...3 (approximately 1W0rL) Strong edema
...4 (1wr1 or more and protruding outside the patch area) 24, n for each 4 birds with intact skin (IntactSkjn) and damaged skin (AbradedSkin)
Add the average value of the judgment of the formation of erythema and edema after hours,
The average value obtained by dividing this by the number of animal specimens (4) represents the price of primary animal skin irritation.

Evaluation of test substance; (average sum of judgment criteria) Average value less than 2 Slight irritation or almost no irritation 2-5
Moderate irritation 5 or higher Strong irritation Table 1 shows the results of primary irritation to the animal skin layer of each test substance.

1.2 Test method for examining cumulative skin irritation; Hartley white guinea pigs weighing 400 to 500 g are used.

0.3 mt of the test substance is evenly applied to the skin of three guinea pigs whose back hair has been shaved with electric clippers in an area of 3 x 4 cm. After application 2, the skin reaction is determined according to the criteria. After the determination, apply 2 in the same area in the same way as the previous day.
Apply the second application.

After 2 coats, the skin reaction is assessed and a third application is made.

After two seconds, a final judgment will be made.

Judgment: No change at all ... 0 Slight erythema ... 1 Obviously erythema ... 2 Strong erythema, slight edema, or dermoid skin thing
3. Those with obvious edema, dementia, or worse changes 4. Evaluation of cumulative animal skin irritation: 48. It is expressed as the average value obtained by dividing the sum of judgments after n hours by 9.

Evaluation average value of test substance Evaluation Less than 2 Slight irritation or almost no irritation.

2 or more Irritating.

1.3 Examination of eyelid irritation (test method according to Draiz method) Test method: Japanese white rabbits weighing 2.0 kg to 3.5 kg are used.

0.1 ml of the test substance is applied to the conjunctival sac of the right eye of three rabbits. 1 hour, 4 hours, 1 day, 2 days, 3 days after application.
After 4, 5, 6, and 7 days, the cornea, iris, and conjunctiva are observed, and judgments are made according to the following scoring method. Scoring method: I Corneal A opacity Transparent ・・・0 Weak opacity ・・・1 Obvious opacity ・・・2 Milky opacity ・・・3 Opaque ・・・4 B Corneal opacity C Total ( A + B) × 5 Maximum theoretical value = 80 ■Iris Δ Officially normal ...0 Slight hyperemia ...1 No reaction to light ...2 Total B total A × 5 Maximum theoretical value = 10 ■Conjunctival A normal redness...0 Obvious hyperemia...1 Deep red hyperemia...2 Beef-like hyperemia...3 B edema normal...0 Slight edema ...1 Obvious edema ...2 Edema in which the eyelids are approximately half closed ...3 Edema in which the eyelids are approximately half closed ...4 C Outflow is normal ...0 Slight Spillage...1 Obvious spillage...2 Very obvious spillage...3 D total (A+B+C)X2 Example 1 Lotion (1) Monolauric acid disuccinate hexa 8 Maximum Theoretical value = 20 The evaluation of eyelid irritation is expressed by the total average value of the cornea, iris, and conjunctiva.

Evaluation of the test substance 5 Average value 1 Very little irritation, almost no irritation 1
0 or more: Irritating.

2 human body occlusion batch test Use your forearm.

0.05 ml of the test substance is applied to the skin using a Nochitest bandage manufactured by Torii Pharmaceutical Co., Ltd. with a lint cloth having a diameter of 1.1゛O. Reaction judgment time: Judgment is performed 2 to 3 hours after the occlusion and the person performing the reaction;
Healthy female 5-5 reaction criteria; No change...- Faint erythema...± Erythema...+ Erythema, edema, or erythema...+++ θ Erythema, edema, vesicles... ... +++ Below, the animal and human safety test results are shown in Table HZ25.

Disodium salt of glycerin (2) Glycerin 5 (3) Propylene glycol 4 (4) Ethanol
10(5) Oleyl alcohol
0.1(6) Fragrance 0.1(7)
Methyl roseoxybenzoate 0.2 (8) Ultraviolet absorber Appropriate amount (9) Sequestering agent Appropriate amount (1a) Purified water
78.1 (Production method) (10 (1),
Dissolve (2), (3), (8), and (9).

Next, (5), (6), and (7) were dissolved in (4) and added to the aqueous solution with stirring to obtain a lotion. Example 2
Lotion-like emulsion [weight%] (1)
Dipropylene glycol 3.0 (2) 1,
3-Butylene glycol 2.0 (3) Monolauric acid diglutaric acid 0.8 Monopotassium salt of decaglycerin (4) Silicon Xiang-56 (manufactured by Shin-Etsu Chemical)
2.0(5) Squalane 0.5
(6) Ethanol 10.0 (7
) Fragrance 0.1 (8) Purified water
81.6 (Production method) (8) (1), (2)
) and (6) and heated to 70°C.

Separately, mix (3), (4), (5), and (7) at 70°C.
Dissolve it by heating and add it to the aqueous solution while stirring.
After thorough emulsification with a homomixer, the mixture was cooled to room temperature to obtain a lotion-like emulsion. Example 3 Emulsion [wt%] (1)
Dipropylene glycol 5.0 (2) Monoadipi monoisostearate 1.0 Ditriethanolamine salt of dodecaglycerin monotartrate (3) Glycerin monostearate 1.0 (4
) Setanol 0.5 (5) Squalane 10.0 (6) Ethyl roseoxybenzoate 0.3 (7) Fragrance
0.15 (8) Purified water
82.05 (Production method) According to Example 2.

Example 4 0/W type cream [wt%] (
1) Dioleic acid trisuccinic acid deca 2 glycerin (
2) Glycerin monooleate 1.5 (3)
Glycerin 5(4)L. 3-Butylene glycol 4(5) Batyl alcohol
5(6) Squalane 1
2 (7) Olive oil 8 (8) Vaseline 4 (9) Solid paraffin 3 [Phase] Methyl rose oxybenzoate 0.1 (11) Butyl rose oxybenzoate 0.1 (12) Fragrance 0.2 (1
3) Sodium hydroxide 0.1 (Production method) Same as Example 2.

Example 5 W/0 type night cream (weight%) (1
) dioleic acid monosuccinic acid hexaglycerin
3.5 monopotassium salt. (2) Diglyceryl diisostearate 1 (3)
) Beeswax 5 (4) Solid paraffin 605 (5) Microcrystalline wax 10 (6) Vaseline 10J (7) Squalane 35 (8) Butyl roseoxybenzoate 0.1 (9) Hibitengluconate liquid 0.1 (1CjiEDTA -3Na0.0
1 (11) Flavoring Appropriate amount (
12) Purified water 30.29 (
Manufacturing method) (1), (2), (3), (4), (5), (
6), (7), and (10) are mixed and heated (70°C) to dissolve.

Separately, mix and dissolve (8), (9), and (11゛) for 70 minutes.
℃ and stirred (added to the oil phase components). After emulsifying with a homomixer, the mixture was cooled to room temperature to obtain a W/O type night cream. Example 6 Emulsified foundation (wt%) (1
) monopalmitic acid monostearic acid monosuccinic acid

Monosodium salt of hexaglycerin diacid (2) Stearic acid 2 (3) Cetostearyl alcohol 1.2 (4) Vaseline
2(5) Lanolin
0.5(6) Glycerol tri2-ethylhexanoate 10(7)
Vitamin E Acetate 0.1 (8) Butyl Baroxybenzoate 0.2 (9) Propylene Glycol 7 (1a) Polyethylene Glycol 60006 (11) Sodium Carboxymethyl Cellulose 1 (
12) Bentonite 0.1 (1
3) Triethanolamine 1 (10 titanium oxide 9 (15) talc
6 (16) Colored pigment 1 (17)
Fragrance 0.5 (18) Purified water
50.37 (Production method) (9), (1CjI
, (11) is dissolved in (18), then (12), (1
4), (15), and (16) are added to this and uniformly dispersed using a homomixer.

Thereafter, (13) is added and dissolved to form a powder/water phase component phase. Separately (1), (2), (3), (4), (5
), (6), (7), (8), (17) and mix 70
'C to form an oil phase.

The powder/aqueous component phase is also heated to 70'C, and the oil phase is added thereto and mixed and emulsified using a homomixer. An emulsified foundation was obtained by cooling to room temperature. Example 7 Nogutsuku (weight%) (1
) Monoisopropanolamine salt of monoisostearate monoglutarate 2 hexaglycerin 1 (2) Denatured alcohol 9 (3) Polyethylene glycol 40003 (4) Olive oil
4(5) Vinyl acetate resin emulsion 10(6) Polyvinyl alcohol
10(7) Sodium bicarbonate 0.
05(8) Titanium oxide 13(9)
) Methyl roseoxybenzoate 0.2 [phase] Flavor Appropriate amount (11) Purified water
48.75 (manufacturing method) (1
Add (8) to a portion of 1) and uniformly disperse with a homomixer to form a powder dispersed phase.

Separately, (6) and (7) were dissolved in (11), then heated and dissolved (3) and (7) were added and dissolved, and finally (5)
Add and stir evenly to form the aqueous phase. The aqueous phase and powder dispersed phase were mixed, and (2) was dissolved in (1), (
Add 4), (9), and (10) and stir evenly.The resulting bag is in the form of an opaque gel, and has a mild feel on the skin.
Both stability over time was good.

Claims (1)

[Claims] 1 Polyglycerin with a degree of polymerization of 2 to 20 and carbon number of 8 to 30
It is characterized by blending an ester and/or a salt thereof obtained by reacting a fatty acid polyglycerol ester consisting of a fatty acid with a polybasic acid so that at least one acid group of the polybasic acid remains free. cosmetics.