JPS6126965B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the general formula () CH ₃ (CH ₂ ) ₇ (R′) (CH ₂ ) ₁₁ COOCH ₂ (CH ₂ ) ₁₁ (R″) (CH ₂ ) ₇ CH useful as a base for cosmetics and external preparations. ₃ ………() (However, in the formula, R′ represents −CH ₂ CH ₂ −, and R″ represents −CH=
This product relates to cosmetics and external preparations containing an ester compound represented by CH- or -CH ₂ CH ₂ - as a base, and is non-irritating to the skin and has excellent color, odor, stability and feeling of use. The purpose is to provide cosmetics and external preparations of consistent quality. By the way, the characteristics of bases for cosmetics and external preparations include (a) low irritation to the skin, (b) low odor and coloring, (c) chemical stability, and (d) no irritation to the skin. It has a good feel and spreads well, and (e) there is little variation in physical and chemical properties from raw material lot to lot. The object of the present invention is to provide a base having the above-mentioned various ideal properties, thereby obtaining cosmetics and external preparations with even better performance. Conventionally, the main oil bases that are solid at room temperature used in cosmetics are naturally occurring ones, such as lanolin, petrolatum, paraffin, carnauba wax, candelilla wax, beeswax, and wood wax. All of them have unique properties, making them important ingredients for cosmetics. However, since these products are natural products, there are concerns about supply, large fluctuations in price, and inconsistent quality due to variations in ingredients between lots.Odor and color problems are considered to be major drawbacks. Although they are said to be safer than chemically synthesized products, many of them are susceptible to deterioration and require special care to maintain a constant quality.
Currently, it is said that stricter quality control is required, and its use as a cosmetic raw material is not very wide. Due to this current situation, efforts have been made in recent years to improve the shortcomings of natural products. For example, by extracting some of the constituent components of natural products or reacting them with other substances, natural products have been created while retaining their characteristics. Semi-synthetic products with fewer drawbacks are used as raw materials for cosmetics and external preparations. However, even after these modifications, there are still few ideal products. In view of the current situation, the present inventors conducted intensive research and discovered that 13-docosenoic acid or docosanoic acid (also known as behenic acid) having 22 carbon atoms and 13-docosenyl alcohol or docosyl alcohol obtained by reducing them. The present invention was completed by discovering that a product obtained by esterification with behenyl alcohol (also known as behenyl alcohol) does not have the above-mentioned drawbacks and is useful as a base for cosmetics and external preparations. That is, the above-mentioned ester compounds of the present invention do not cause skin irritation, are colorless, odorless, have excellent stability over time, and have a very good feel on the skin, so they can be included as a base in cosmetics and external preparations. It is particularly suitable for this purpose. 13-docosenoic acid, which is the raw material of the present invention, has two geometric isomers, cis-erucic acid and trans-brassidic acid, but erucic acid is preferable for use in the present invention.
This substance is particularly abundant in seed oils of cruciferous plants, such as rapeseed oil, and is therefore relatively easy to obtain as a raw material. If the double bond of 13-docosenic acid is reduced, docosanoic acid (also known as behenic acid) is obtained, and if only the carboxyl group of 13-docosenic acid is selectively reduced, 13-docosenyl alcohol is obtained, and further 13 - If both the double bond and the carboxy group of docosenoic acid are reduced simultaneously, docosyl alcohol (also known as behenyl alcohol) will be obtained. Of course, raw materials isolated and extracted from natural oils may be used without using the above reduction method.
Cosmetics and external preparations characterized by blending as a base esters having the structures [A] and [B] below and having 44 carbon atoms obtained from the acid obtained in this way and two types of alcohols. This is the object of the present invention. Invention ester [A] CH ₃ (CH ₂ ) ₂₀ COOCH ₂ (CH ₂ ) ₁₁ CH = CH (CH 2 ) ₇ CH ₃ Invention ester [B] CH ₃ (CH ₂ ) ₂₀ COO ( _{CH 2 ) 21} CH ₃ The reason why the above-mentioned acid having 22 carbon atoms and alcohol having 22 carbon atoms were used in the present invention is as follows. (1) Esterification was performed to reduce the polarity of the compound and considerably increase the molecular weight, in order to minimize skin irritation. (2) JOJOBA (pronounced jojoba in Spanish, scientific name SIMMONDSIA
Jojoba oil extracted from the fruits of the Chinese chinensis tree is increasingly being used, but its main components are _C20 - _C22 linear unsaturated fatty acids and _C20 - _C22 linear chains, rather than the glycerides found in general fats and oils. Since the main component is an ester consisting of unsaturated alcohol (see Oil Chemistry: Vol. 27, No. 10, p. 650, 1978), the esters of [A] and [B], which are similar to the constituent components of this product, are similar to jojoba oil. thought that other effects could be expected. (3) In terms of raw materials, unlike jojoba, which is cultivated only in deserts and arid regions, 13-docosenic acid, which is the starting material of the present invention, is derived from cruciferous plant seed oils, especially rapeseed oil (also known as oilseed oil). oil) to known techniques (e.g. Japanese translation organc syntheses, Volume 2, Volume 1, 340-
342 pages, 1951). In particular, 70% of the world's rapeseed oil is produced in Asia, and in Japan, along with soybeans, it is the most important oil crop, and as it is widely cultivated throughout the country, there is no concern about the supply of raw materials. (4) In the esters of the present invention, the above compound [A] is a compound unknown in the literature, and (compound [B] is a chemical abstract, Vol. 16).
36318) There is no known literature on its use as a base for cosmetics and external preparations, and its effects as a base for cosmetics and external preparations are completely unknown and unpredictable. (5) Since all the raw materials of the present invention can be easily derived from 13-docosenoic acid, they are industrially very economical and advantageous. (6) Both acid and alcohol as raw materials of the present invention have large molecular weights and are chemically stable, so even if the reaction temperature is raised during synthesis, the starting materials do not volatilize and the ester can be obtained in good yield. Furthermore, since the raw material alcohol is a primary alcohol, the esterification reaction progresses easily and by-products are less likely to be produced.Therefore, it is less likely to be colored and there is little variation between lots. (7) Lower alcohol esters of 13-docosanoic acid have poor hydrolytic stability and are likely to cause skin irritation. Also, esters with commonly used higher alcohols of _C10 to _C18 have a slight odor.
It has the disadvantage that it does not feel good when applied to the skin. Based on the above reasons, we synthesized the esters of the present invention containing novel compounds, conducted studies to discover their usefulness as bases for cosmetics and external preparations, and completed the present invention. Next, the method for producing an ester according to the present invention can be synthesized as follows. First, 13-docosenyl alcohol is synthesized by reducing 13-docosenic acid or its lower alkyl ester using a known reduction method. At that time, the reducing agent was LiAlH ₄ ,
NaAlH ₄ , NaAlH ₂ (OCH ₂ CH ₂ OCH ₃ ) ₂ , NaAlH
(OC ₂ H ₅ ) ₃ , Na + alcohol, etc. are used. Industrially, reduction with metal Na in alcohol, etc., which is easy to handle, is preferred. The 13-dococenyl alcohol thus obtained can be further catalytically reduced using platinum oxide, palladium, nickel, or the like as a catalyst to obtain docosyl alcohol. Furthermore, docosanoic acid can be obtained by subjecting 13-docosenoic acid to a catalytic ring element in a similar manner. Of course, raw materials isolated and extracted from natural oils may also be used without using the above-mentioned cyclic method. The esters of the present invention can be obtained by using the above-mentioned acid and alcohol obtained in this way and using a general esterification method. For example, a method using an acid halide under a basic catalyst, a method of esterification without a catalyst or in the presence of a suitable catalyst, etc. can be employed. For example, industrially, the above acid and the above alcohol obtained by reducing it are heated at 200 to 250°C for about 4 to 15 hours, or a mineral acid such as sulfuric acid or para-toluenesulfonic acid is heated. The above acid and the above alcohol may be reacted under a dehydrating agent such as benzenesulfonic acids. It is better to carry out the above reaction under a flow of an inert gas such as nitrogen gas or carbon dioxide gas to prevent coloring, and thus to obtain a preferable result from the viewpoint of product purity. If it is colored, good results can be obtained by treating it with activated carbon or activated clay. If even higher purity is required, the above acids and their reactive derivatives, such as thionyl bromide, thionyl chloride, and other halogenating agents, are used to form the bromides or chlorides of the above acids, and the above alcohols are added to the bromide or chloride of the above acids. can be obtained in high yield by reacting them under a basic catalyst such as triethylamine or pyridine. Further treatment with column chromatography etc. yields a highly pure ester form of the target product. Of course, production is also possible using known methods other than those described above. The esters of the present invention are useful as bases for cosmetics such as lipsticks, pomades, various creams, hair conditioners, and eye shadows, and they can be used singly or in combinations of two or more. Furthermore, the esters of the present invention can be used as part of the base of external preparations such as pharmaceutical creams and ointments. Next, specific examples of esters in the present invention will be shown. Reference Example 1 Method for producing 13-docosenic acid-13-docosenyl ester (cis-cis form) (also known as erucic acid erucyl ester) Put 800 g of xylene into the four-piece flask from Step 2, add 62.6 g of metallic sodium thereto,
Heat and stir to ~120°C. Add 200g of methyl erucate and 145g of methyl isobutyl carpinol.
Gradually add the mixed solution. After the dropwise addition is completed, the mixture is refluxed for 1 hour. After the reaction is complete, slowly add 500 ml of water and decompose. After washing four times with warm water, dry over anhydrous sodium sulfate and filter. After distilling off the solvent under reduced pressure, it was subjected to vacuum distillation to give a 0.5mm
145g of colorless or pale yellow erucil alcohol was obtained at 180-190°C with Hg. Melting point 32-34.5℃,
Acid value 0.5, hydroxyl value 170.1, iodine value 78.1, refractive index ^n35D _1.4574 . Infrared absorption spectrum ν ^neat _nax cm ^-1 : 3250 (
hydroxyl group), 2850-3000 (methylene). (b) Next, about 20 g of thionyl chloride was added to 6.76 g (0.02 mol) of erucic acid, and after heating at 70-80°C for 1 hour,
Excess thionyl chloride is distilled off under reduced pressure. Furthermore, in order to completely distill off thionyl chloride, 50 ml of chloroform is added, and the mixture is further distilled off under reduced pressure. Add to this 6.48g (0.02mol) of the erucil alcohol obtained above.
was added, and then 1.9 g of pyridine was added dropwise while stirring. Dripping is accompanied by heat generation. After dropping, heat at 70-80°C for an additional 30 minutes to complete the reaction. After cooling, add 50 ml of 10% hydrochloric acid and extract with ether. The ether solution is washed twice with water and then dried over anhydrous sodium sulfate. and distill off the ether. The residue was dissolved in a chloroform-ether mixture and passed through an alumina column chromatography layer. The solvent was distilled off, and 12.51 g of erucic acid erucyl ester was obtained as a colorless waxy residue. yield
97.1%, melting point 23-26℃, infrared absorption spectrum ν ^neat _nax cm ^-1 : 1742 (ester), 2850-3000
(methylene), oxidation 0.4, hydroxyl value 0.8, saponification value 86.5,
Iodine value 77.9. (b) Mix 50 g of erucic acid and 56.2 g of erucil alcohol, and heat to 240-250 g while blowing _N2 gas.
The reaction was allowed to proceed at a temperature of 4 hours with stirring. After the reaction is complete, some unreacted materials are heated under reduced pressure (1 mmHg).
To leave. The residue was decolorized twice with activated carbon in a conventional manner to obtain 90.5 g of colorless waxy erucyl ester. Melting point 20.5~25℃,
Acid value 0.5, hydroxyl value 0.8, saponification value 85.8, iodine value
76.3, ester value 86.2, refractive index n ³⁰ _D 1.4632. The infrared absorption spectrum of the product obtained by this method completely matched that of the product obtained in Reference Example 1. Reference example 2 13-docosenic acid-docosyl ester (cis form)
Production method (also known as erucic acid behenyl ester) Esterification was carried out in the same manner as in Reference Example 1 using 6.76 g (0.02 mol) of erucic acid and 6.52 g (0.02 mol) of behenyl alcohol to produce 12.48 g of colorless waxy erucic acid behenyl ester. Obtained. Yield 96.6%,
Melting point 44.5-50.8°C, acid value 0.8, hydroxyl value 0.6, saponification value 88.7, iodine value 40.0, refractive index n ⁵⁰ _D 1.4514, infrared absorption spectrum ν ^neat _nax cm ^-1 : 1740, (ester),
2850-2980 (methylene). Example 1 Method for producing docosanoic acid-13-docosenyl ester (cis form) (also known as behenic acid erucyl ester, hereinafter abbreviated as BEE) Using 6.80 g (0.02 mol) of behenic acid and 6.48 g (0.02 mol) of erucyl alcohol Then, esterification was performed in the same manner as in Reference Example 1 to obtain a colorless wax-like BEE.
12.37g of was obtained. Yield 95.7%, melting point 47-48.5℃, acid value 0.8, hydroxyl value 0.6, ester value 87.5, saponification value
88.3, iodine value 39.8, refractive index n ³⁰ _D 1.4514, specific gravity d ⁵⁰
₂₀
0.8423, infrared absorption spectrum ν ^neat _nax cm ^-1 :
1738
(ester), 2840-2950 (methylene). Example 2 Method for producing docosanoic acid docosyl ester (also known as behenic acid behenyl ester, hereinafter abbreviated as BBE) Esterification in the same manner as in Reference Example 1 using 6.80 g (0.02 mol) of behenic acid and 6.52 g (0.02 mol) of behenyl alcohol. colorless wax-like BEE
It weighed 12.61g. Yield 97.3%, melting point 70.0-70.7℃,
Acid value 0.7, hydroxyl value 0.4, saponification value 88.8, iodine value 0.1,
Ester value 88.1, infrared absorption spectrum ν ^neat _na
x cm
^-1 : 1735 (ester) 2850-2960 (methylene). Example 3

[Table] As shown in the table, all of the esters of the present invention are almost colorless, transparent, and odorless, which is superior to the natural bases, which generally exhibit a pale yellow color and emit a characteristic odor. Furthermore, compounds in which erucic acid or behenic acid and commonly used higher straight chain fatty acids are ester bonded have a slight peculiar odor.

[Table] The values are shown after each sample was placed in a test tube and heated in an oil bath at 180°C for 3 hours in the atmosphere. The results in the table show that the ester of the present invention has better thermal oxidative stability than the comparative substance.

[Table] The test method is to place approximately 2g of the test substance and 25ml of 1/3 standard ethanol potash into a saponification value measurement flask.
Attach a cooling tube and heat at 85℃, measure the saponification value of the test substance at regular intervals, and divide the value by the saponification value obtained when reacting with 1N ethanol potassium for 3 hours at 85℃. The decomposition rate was determined. As a result, the ester of the present invention has better alkali hydrolysis resistance than the lower alcohol esters of erucic acid and behenic acid as control substances.

[Table] The above table was conducted on 4 male and 5 female subjects, and compared the feel when a cream consisting of 50 parts by weight of Vaseline and 50 parts by weight of olive oil was applied to the hands.
From the results shown in the table, the esters of the present invention are superior in feel compared to petrolatum, but the control test samples cannot be said to be superior to petrolatum.

[Table] The test method is based on the closed patch test method. Liquid paraffin oil containing 10% by weight of each test substance is prepared on the inner side of the upper or anterior side, and a flannel cloth (1.5 cm square) coated with this is pasted. cover with a cloth and a bandage over it. After 24 hours, the flannel cloth was removed, and the test substance was thoroughly wiped off, and the degree of reaction was judged according to the criteria below, and again after 48 hours. Judgments include no change at all (-), faint erythema (±), clear erythema (+), and edema, blisters, etc. other than erythema (++). I did this. Based on the results shown in the table, the test was carried out on 4 boys and 5 girls, and all of the test subjects tested negative for the esters of the present invention in the above skin irritation test method. However, the known lower alcohol esters of erucic acid and behenic acid were found to cause skin irritation. Example 4 Next, an example of a cosmetic using the ester of the present invention will be shown. (indicates weight unit)

[Table] (Manufacturing method) Component A is heated to a temperature of 70 to 80°C, stirred and mixed to dissolve it, component B is added to this, and appropriate amounts of fragrance and anti-inflammatory agent C are added and mixed. This nourishing cream is extremely smooth and feels great when used.

【table】

[Table] (Manufacturing method) Component A is heated and dissolved, and component B is added thereto and mixed uniformly using a roller. Dissolve this again,
Add fragrance, defoamer, strain, mold, fill into containers, and make a glossy product. This lipstick feels good on the lips, is non-sticky and spreads well.

Claims (1)

[Claims] 1 General formula () CH ₃ (CH ₂ ) ₇ (R′) (CH ₂ ) ₁₁ COOCH ₂ (CH ₂ ) ₁₁ (R″) (CH ₂ ) ₇ CH ₃ ………() (However, in the formula, R′ represents −CH ₂ CH ₂ −, and R″ represents −CH=
Cosmetics and external preparations containing an ester compound represented by CH- or -CH ₂ CH ₂ - as a base.