JPS6289646A - Composite body of basic amino acid and fatty acid and additive therefrom for cosmetics - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a complex obtained by the reaction of a basic amino acid such as lysine or arginine with a fatty acid, and an antioxidant and emulsifier for cosmetics made of the complex. Relating to flexibility additives.

Cosmetics are products that are used by rubbing, spraying, or similar methods on a person's body to treat, beautify, and increase attractiveness, and to keep the skin, hair, or teeth healthy.
It also refers to products intended to change one's appearance, such as cosmetic lotions, cosmetic creams, permanent solutions, hair products, cosmetic soaps, shampoos, etc.

(Prior art) It is well known that amino acids include basic amino acids (lysine, arginine, etc.) and acidic amino acids (aspartic acid, etc.), and in recent years, complexes made by reacting the two have been developed and are used as medicines. Among these complexes, lysine and
It has been discovered that an aspartic acid complex has a muscle contraction-relaxing effect, and the present inventor has already proposed a liniment using the same (Japanese Patent Application No. 137824/1982).

Since drugs made from such amino acids are less toxic than other synthetic drugs and are expected to have a variety of efficacy, it has been desired to provide such novel complexes and to develop their uses.

On the other hand, when it comes to cosmetics, ingredients that are irritating to the skin are avoided, although their bases and additives are of course effective. However, many cosmetic bases are susceptible to oxidative deterioration, and once peroxide is formed, it becomes an irritant and has non-negligible toxicity to human skin.

It is also well known that the free radicals formed during peroxide development are antiphysiological substances.

Many authors have also pointed out that this phenomenon plays an important role in the aging process for living organisms.
al Theory of aging-J.

Geront, 1968-23-467, Pro
Longation of Life, Role of
to free radical action
inaging-J, ^mer, Geront,
Soc, 1969-17-721゜110cH8cI
IILD R-Lysosomes membranc
s and aging EXP, Geront, 1
971-6-153゜TAPPLE A L-Free
radical 1ipid peroxidati
ondams and its 1nhibition
by vitamin E and Selenium
-Fed, Proc 1965-24-73,).

Furthermore, it is known that ultraviolet rays lead to the formation of peroxides (SIIERVIN [R-Oxidati
onan antioxidants in fat
and oil processing-J, A,
0. C,S, 1978-55-809-VIG
N [RON M.

Autoxydation, He5ures de
pr6ventio 1956-3oci6t6 dM
dition pharmaceutiques e
tscientifiques, Paris).

This substance causes skin aging, causes the skin to lose its elasticity, and causes wrinkles. therefore,
In order to protect the skin from such peroxidation phenomena (especially in the summer when ionizing rays are strong), it is important to incorporate appropriate agents in cosmetics to prevent these phenomena, and the development of such agents is particularly anticipated. It was.

[Problem that the invention seeks to solve]

Under these circumstances, the present invention was made with the aim of improving the above-mentioned prior art and developing this technology, and particularly to provide a new amino acid-based material of this type and its applicability in the field of cosmetics.

[Means for solving problems]

As a result of intensive studies with the above purpose in mind, the present inventor has produced a new complex by combining basic amino acids such as lysine and arginine with fatty acids, and this has been used in the cosmetics field to emulsify and soften the complex. The present invention was achieved by confirming that it has an antioxidative effect as well as an antioxidant effect.

That is, the present invention relates to a complex of a basic amino acid and a fatty acid represented by the general formula where R is a saturated, unsaturated or branched aliphatic group having 4 to 30 carbon atoms. It provides cosmetic additives consisting of
This complex has emulsifying, softening, and antioxidant effects, and has a skin protective effect that takes advantage of its physiological properties and the ability to suppress the production of peroxides caused by the oxidation of cosmetic bases, especially oils. This type of product is effectively used in the field of cosmetics.

When lysine is used as the basic amino acid, the above formula [
I], R' is -CH2-1Rn is -(CH2)3
- is obtained, and when arginine is used, R'10-NH-1RJJ is H -(CH2)3-.

As the fatty acid, those having a hydrocarbon group having 4 to 24 carbon atoms are particularly preferable, and examples of the fatty acids used include capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, oleic acid, linoleic acid, and linuric acid.

The complex is obtained by neutralizing the above fatty acid with a basic amino acid, and its 10% alcohol aqueous solution has a pH of 6.5 to 7.5.

The reaction temperature is slightly higher than room temperature to avoid coloring, for example, about 50° C. in the case of oleic acid.

The product (complex) is gel-like in the case of unsaturated fatty acids such as oleic acid and linoleic acid, and is in the form of a gel in the case of saturated fatty acids. A 2′-sh solid is obtained. Those derived from unsaturated fatty acids are gel-like when exposed to water, but liquefy when heated. It is soluble in pure ethanol, propylene glycol, chloroform, acetone, and ethyl acetate.

Derivatives from saturated fatty acids are powder-like, soluble in propylene glycol and glycerol when heated, and form a gel when mixed with water.

It is partially soluble in chloroform and sparingly soluble in stearin polyoxyethylene alcohol, oil, and cetyl alcohol.

Table 1 shows the relationship between the theoretical and actual fatty acid-amino acid values and the total nitrogen percentage indicating the purity of the obtained substance.

Next, identification data for the complex of the present invention will be shown.

(it melting point (BLoko Flcytu;btvn
h i@)CH3-(CH12), -CH=CH-(C
I-12) 7-COO lysine oleate 150
°±5℃ CH3-(CH2), 4-COoH-H2N-(CH2
) 4-Lysine Balmitate 185°±5°CCH3-
(CH2)16-COOH-H2N-(CH2)4-lysine stearate 190°±5℃CH3-(CH2
)12-COOH-H2N-(CH2>4-lysine myristic acid 1iso°±5℃ C113-(CH2)4-CH=CH-CH2-C)l
=cH (lysine linoleate 180°±5°C H・82N-(CI-12) 4-CH-COOH■ NH2 C1l-COOH NH2 CI-(-Cool-1 NH2 Cl-1-COOH NH2 CH2), - CooH-82N-(CH2)4-0H-
COoH sign NH2 CH3-(CH2) 7-CH=CH-(CH2) 7
-C0OH・Arginine oleate 170°±5℃
CH3-(CH2) 14-COoH-H2N-C-N
H-(CH2) 3NH-1 Arginine palmitate 135°±5℃CH3-(C
I-(2) 16-Cool-1-H2N-C-NH-
(CH2) 3NH Arginine stearate 170°±5°CCH3-(
C112)4-CH=CH-CH2-CH=CH7(C
H2 arginine linoleate 140'±5℃NHN+
4゜-CH-C0OH NH2 -CI-1-COOH NH2) 7-COoH-H2N-C-NH-(Ca12)3
-CH-COOHNHNH (11) Color reaction ■ Adding a few drops of ninhydrin to the aqueous alcohol solution of 2d and soaking it in boiling water for a few minutes always accelerates the purple-brown color.

A thick precipitate forms. When B and M are added, the precipitate disappears and the solution takes on a pink color.

fiiiil Chromatography test (Table ■,
Table ■) For comparison with amino acids, use the following mobile phase solutions: Chloroform, methanol, ammonia 20/20/10 Transfer time: Approximately 30 minutes Detection solution: Scarlet (purple) ninhydrin, methyl red or bromocresol Red) Table ■ R, R.

Lysine 0.35 Arginine
0.36 Lysine oleate 0.24
Arginine oleate 0.33 Lysine palmitin MjW 0.23 Arginine palmitin M salt 0.33 Lysine stearin MFA 0.23
Arginine Stearin MW 0.33 Lysine Linoleate 0.23 Lysine Caprylate 0.23 Use the following transfer solution to draw out the characteristics compared to fatty acids: Petroleum Ether Ethyl Ether = Detection Solution = 2-
After evaporation with 7 dichlorofluorescein or methyl red solution, the pre-heated plaques are exposed to ammonia vapor.

Fatty acids and their amino acid derivatives remain red, but their R front, where the solvent diffuses over the plaque, becomes yellow. Ultraviolet light (3
66r++++).

Table■ Stearin M O,66 Arginine Palmitin lH0,61 Palmitic acid 0.63
Fulginine Stearin Wtm0.52 Linole PIi
o, s.

Lysine Balmitate 0.61 Lysine Oleate 0.72 Lysine Stearate 0.55 Lysine Linol Pa Salt 0.73 1M Measurement of M When acidified, it can be easily separated into fatty acids and amino acids. At this time, the amino acid remains in the aqueous solution as a hydrochloride. To find out the identity of a fatty acid, measure its acid value. For amino acids, either measure the nitrogen value or use the small lumole titration method.

This novel complex of the invention is now particularly advantageously used in cosmetic emulsions. It can be used alone as an emulsifier or softener, or in combination with other ionic or nonionic emulsifiers. This substance is also effective when used on the skin by replenishing it with oil and water, and its feel is very smooth without any "greasiness".

Incidentally, apart from such emulsifying and softening effects, the most noteworthy feature of this substance is its antioxidant properties. That is, by incorporating this complex into cosmetics in advance, it is possible to prevent the peroxidation phenomenon.

Although fatty acids such as oleic acid and oleic acid are self-oxidizing in themselves, they exhibit the unexpected property of inhibiting peroxidation phenomena, especially when combined with amino acids.

This is a particularly interesting aspect of the invention.

In order to investigate these characteristics, an experiment was conducted to measure the degradation of peroxide after mixing with air and oxygen, and especially after exposure to ultraviolet light. The results are shown in Table 2.

Since most cosmetic products are in the form of emulsions, experiments were also conducted with emulsions containing the substances of the present invention. The control substance (T5moin) was made of only oil and polyoxyethylene aliphatic alcohol. In addition, the control object is neutral (TI3m
oin neutrc) contains no antioxidants, and the control BHT (T5moin BIIT) contains 88 teeth.

Between 2% and 4% lysine oleate and B HTO,
The oxidation at 50°C was compared under the following conditions for Ura to which 1% was added.
21 days later - CXJ exposure
It corresponds to the d number of ium). In addition, all the numerical values in all the following tables (V-X) are also the same as this.

Table V shows the results of examining the oxidation of oil when the oil is bubbled at 50°C for 1 hour (through oxygen).The only value is immediately after treatment, and the control neutrality (T6moinneutre) is the one that does not pass through 02. Oxidation at 50°C under ultraviolet light is shown in Table 3. -However, (~8
(B) 12-hour exposure with 2% lysine oleate and B)-I TO91%
Table 3 shows the oxidation of oil under ultraviolet irradiation for 10 hours.

-However, in the case of lysine stearate (4%) and Bl-
Comparison table with IT < 0.1%) I Comparison of antioxidant properties (Table ■): BHT (0.1%)
, lysine oleate, lysine stearate (5%) - Oleate, stearin 1 stone 5%, des 1 ~ oil 5
% Table ■ Comparison of antioxidant properties of various lysine and arginine derivatives with BHT in various emulsified oils (Table IX) Control: Polyoxyethylene alcohol: 5% - oil 5%
- Water - 90% BHT: 0.1% Amino acid derivative = 5% - Oil 5% - Water 90% UV irradiation gA
: 12 hours at 50°C Table IX Comparison of antioxidant properties of various compounds in the oil or water layer, B HT and amino acid salts (Table X): UV irradiation at 22°C for 18 hours Water layer (1), oil layer (2 ), BHT is mixed only in the oil layer.

Table The following are the steps to play.

When mixed with air or oxygen for 1 hour at +1150°C, lysine oleate has an antioxidant activity close to or better than that of B l-I T (Table ■ or Table V), and the composites of the present invention The body has shown that it is not only a safe emulsifier and softener, but also an antioxidant.

(2) Even when irradiated with ultraviolet light for 8 to 18 hours, the results in Tables 1 and 2 indicate that both lysine oleate and lysine stearate have excellent antioxidant properties.

(3) In the case of emulsions containing various oils, when exposed to UV light for 18 hours, lysine stearate has a better effect than lysine oleate when compared among the complexes of the present invention. have

(4) Compounds of fatty acids and lysine or arginine, ie, the complexes of the present invention, regardless of whether they are saturated or unsaturated, can generally be said to have antioxidant properties.

(5) This antioxidant effect is more effective when the amino acid derivative (complex) is mixed into the oil layer of the emulsion than when it is mixed into the water layer.

As can be seen from the above explanation, the compound (complex) of the present invention has the ability to contain conventional antioxidant chemicals (Bl-(T, BHA).
etc.), so in the strict sense it should not be considered an antioxidant, but rather an emulsifier or softener that also has antioxidant properties. And it should be said that there is no need to use other antioxidant chemicals in combination.

Furthermore, it can be said that the use of the complexes according to the invention is extremely effective, since they have a protective effect against ultraviolet radiation.

Moreover, since the complex of the present invention has biological properties similar to those of free or complex fatty acids, lysine or arginine, and since these are normally found in the stratum corneum of the skin, The composite of the invention is revolutionary because it can prevent oxidation and protect the skin from ultraviolet rays without being incompatible with the skin.

Due to the excellent properties described above, it is desirable that the complex of the present invention be blended to protect the oil content of the emulsion from self-oxidation. Since it is difficult to obtain a clear homogeneous composition without color change, it is desirable to dissolve it in a polyhydric alcohol such as propylene glycol or glycerol. Water is then added to obtain the desired emulsion.

The emulsion thus obtained has a pH close to 7 and has an excellent softening effect.

Furthermore, similar or better effects can be obtained by mixing the composite of the present invention into sanitary products such as soaps and jump products or permanent fluids. Particularly in the case of permanent fluids, it is desirable to incorporate this complex, since it increases the action of the reducing agent due to its surfactant effect or biological properties.

〔Example〕

Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 (Production Example of Lysine Oleate) 282 g of oleic acid was dissolved in 500 to 750 d of ethanol while stirring at 50° C., and 146 g of lysine was slowly added thereto. To avoid coloring, do not exceed 55℃.
First, the alcohol and then the JTA-based water were removed in a vacuum to obtain a gel-like product (complex). Its melting point was 151°C, and the analytical values and properties were as follows: As shown in ■.

Example 2 (Production example of arginine oleic acid) The same method as in Example 1 above was carried out, replacing lysine with 174 J of arginine, and a gel-like product with a melting point of 169°C was obtained (
It was. The analytical values and properties are as shown in Table 1.1■.

Example 3 (Example of use of lysine oleate - production of emulsion) Lysine oleate 5 parts propylene glycol 10 parts hydroalcohol
5th part stearin
Add water to 10 parts to make 100 parts (plus some preservatives). An emulsion with a softening effect was obtained.

Example 4 (Example of use of lysine stearate - production of emulsion) Lysine stearate 5 parts Propylene glycol 10 parts Polyoxyethylene fatty alcohol 5 parts Soft almond oil
Add water to 5 parts to make 100 parts (plus some preservatives). An emulsion with a softening effect was obtained.

Example, 5 (Example of use of arginine oleate - production of emulsion) Arginine oleate 5 parts Glycerol 10 parts Sunflower oil
10 parts polyoxyethylene cetyl alcohol 10 parts stearin 8 parts ribamino acid 3 parts, add water to 100 parts
(with a small amount of other preservatives). An emulsion with excellent softening action was obtained.

Example 6 (Example of use of lysine oleate in soap) Cocopalmitin 6 brass 95 parts Lysine oleate 5 parts Example 7 (Example of use of lysine stearate in soap) Coco tallow soap 95 parts Lysine stearic acid Salt 5 parts Example 8 (Example of use of lysine oleate in shampoo) Sodium lauryl sulfate 30 parts Lysine oleate 5 parts Water
65 copies Example 9
(Example of use of lysine oleate in shampoo) Lauryl 5A acid ether 20 parts Lauryl collagen sodium 10 parts Lysine oleate 5 parts Water
65 parts Example 10 (Example of use of lysine oleate in permanent solution) Ammonium thiolactic acid 15 parts Lysine olein M salt 2 parts Ammonia
10 parts water
The same result was obtained when 73 parts ammonium thiolactic acid was replaced with thioglycolammonium. Note that lysine oleic acid was used after being made into a 20% aqueous solution.

The oral stability of the obtained permanent emulsion is good, and the waving properties during its use show that there is almost no decrease in application, the finish is not rough or stiff, and
It was quiet.

Claims (1)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼...[I] However, R: A saturated/unsaturated or branched aliphatic group having 4 to 30 carbon atoms R': -CH_2- group or -C -NH- group R″: Complex of basic amino acid and fatty acid represented by a hydrocarbon chain of amino acid (2) General formula R-COOH・H_2N-R′-(R″)-CH-CO
OH... [I] However, R: A saturated, unsaturated or branched aliphatic group having 4 to 30 carbon atoms R': -CH_2- group or -C-NH- group R'': Represented by a hydrocarbon chain of an amino acid Cosmetic additive consisting of a complex of basic amino acids and fatty acids