JPS61267504A - Cosmetic and external drug - Google Patents

Abstract

PURPOSE:To provide a cosmetic or external drug containing an ester derived from 13-docosene or docosanoic acid and an alcohol produced by reducing the above compound as a base, free of skin irritation, having excellent color, odor, stability and feeling to the skin and having stabilized quality. CONSTITUTION:A cosmetic such as lipstick, pomade, various creams, hair conditioner, eye shadow, etc., or an external drug such as cream, ointment, etc., containing the ester compound of formula I (R' is -CH=CH-; R'' is -CH=CH- or -CH2CH2-), i.e. the ester having the structure of formula II and formula III, as a base. All raw materials of the ester can be produced easily from 13- docosenoic acid, which is producible easily from rapeseed oil.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (
I) CH3(CHJt (Rtsu(CH2)11COOCHd
CH2) 11(R' (CHJyCHs (wherein, R
'a-CH=CH- to R' is -CH=CH- or
This product relates to cosmetics and external preparations containing as a base an ester compound represented by -CH, CH, -, which is non-irritating to the skin, has excellent color, odor, stability and feeling of use, and - The aim is to provide cosmetics and external preparations of consistent quality.

By the way, the characteristics of bases for cosmetics and external preparations include (1) less skin irritation, (2) less odor and color, and (2) chemical stability. It has an excellent feel and good elasticity, and (e) there is little variation in the physical and chemical properties of the raw material depending on the loft. The object of the present invention is to provide a base that has all of the ideal properties of Kutani seeds as described above, and thereby to obtain cosmetics and external preparations with better performance. Among the oil-based bases that are solid at room temperature and are conventionally used in tag materials, lanolin,
Naturally produced products such as vaseline, paraffin, carnauba wax, candelilla wax, beeswax, and wood wax are often used, and all of these have unique properties and are therefore important as raw materials for cosmetics. However, these products have major drawbacks such as the supply of natural products, large fluctuations in price, uneven quality due to variations in the proportion between lofts, and the problems of aqueous color and hue. ,
Furthermore, although they are said to be safer than chemically synthesized products, they often deteriorate and deteriorate easily and require special attention to maintain a constant quality, so stricter quality control is necessary. At present, its use as a raw material for cosmetics is not very wide. Due to this unfortunate 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, they can retain their properties and become natural products. Semi-synthetic products with fewer defects 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 found that 18 having 22 carbon atoms.
The esterification product of 7 docosenoic acid or tocosanoic acid (also known as behenin H) and 13-tocosevenyl alcohol or tocosyl alcohol (CMIJ name hehenyl alcohol) obtained by reducing them does not have the above disadvantages. He discovered that it was useful as a base for cosmetics and external preparations, and completed the present invention. In other words, the above ester compounds of the present invention are: - non-irritating to the skin, colorless, odorless, and have excellent stability over time, and have an excellent feel to the skin; therefore, they can be included as a base in cosmetics and external preparations; It is suitable for doing so. 18-Tocoheptanoic 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. , especially the seed oil of cross-grafts.

For example, since it is abundant in rapeseed oil, it is relatively easy to obtain raw materials. If you reduce the double bond of 1g-tocoheptanoic acid, you will get tocosan#! (also known as behenic acid) is obtained, and 1
By selectively reducing only the carboxyl group of B-toco7yl alcohol, 18-toco7yl alcohol can be obtained, and 1 g
-Docosyl alcohol (also known as behenyl alcohol) can be obtained by simultaneously reducing the double bond and the carboxyl group of tocoheptanoic acid. Separated and extracted raw materials may be used.The following (A) and CB having a carbon number of 44 obtained from m* obtained in this way (no change in the content of the specifications) and two types of alcohols The object of the present invention is to provide cosmetics and external preparations that contain an ester having the following structure as a base.

Ester of the present invention (A) CHs(C1b)tCH<H(CHJllCOOCHz
(CHt)ttCH=CHCCHJyCHs Inventive ester CB) CHs(CH2)? CH=CH(CHJxICOO(C
Hs)n CHs The reason why the above-mentioned acid having 22 carbon atoms and alcohol having 22 carbon atoms are used in the present invention is as follows.

0) Esterification was performed to reduce the polarity of the compound and significantly increase the molecular weight) to minimize skin irritation.

(Smell) JOJOBA is a type of shrub that is a woody plant that grows naturally in desert areas as a natural oil base.
1 is called jojoba and the scientific name is SIMMONDIIA (jH
Jojoba oil extracted from the fruit of INHNsIs) is being used, but its main components are not the glycerides found in general fats and oils, but linear unsaturated fatty acids of O, O-(i) and C1° to C□. Because the main component is ester consisting of linear unsaturated alcohol (Oil Chemistry: Vol. 27, No. 10)
It was thought that esters obtained by purely synthesizing some of the constituent components of jojoba oil (see No. 650, 1978), or esters obtained by reducing them, could have effects different from those of jojoba oil.

(In terms of 81 raw materials, jojoba is cultivated only in desert or dry land buds, whereas 18-dose di) acid, which is the raw material of the present invention, is used in the seed oil of cruciferous transplants, especially rapeseed. From oil (also known as oily oil) to Aichi technology (for example, Japanese translation ortan)
1c 5yntheses 1 Volume 2, Volume 1, 340
-842 pages 1951). In particular, rapeseed oil is the most important oil crop in Asia, with 70% of the world's oil produced in the world, and in Japan it is the most important oil crop along with soybean oil.It is widely cultivated throughout the country, so there is no concern about the supply of raw materials.
・No change to the content of the specification (4) The esters of the present invention are compounds known in the literature, but the compound (6) is disclosed in the same volume 67, 65738z). Therefore, its effectiveness as a base for cosmetics and external preparations was completely unknown and unpredictable.

Since all the raw materials of the present invention can be easily derived from 13-tocosenoic 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 product can be obtained in good yield. Furthermore, since the raw material alcohol is partially alcohol, the esterification reaction progresses easily and by-products are less likely to be produced. Esters have poor hydrolytic stability and are likely to cause skin irritation.

Also, esters of CIO-011 with higher alcohols, which are generally widely used, have a slight odor and have an unpleasant feel when applied to the skin.

Based on the above-mentioned reasons, we synthesized the esters of the present invention containing new compounds, conducted careful 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, 18-tocosenyl alcohol is synthesized by reducing 18-tocosenic acid or its lower alkyl ester by a known reduction method. As a reducing agent at that time, LiAIHa-NaAIH4-NaAIH
*(00HtOHt00Hm)t, NaAIH
(U(3tHs)x.

Na+alcohol etc. are used. Industrially, it is preferable to reduce the material to be handled using metal ha in alcohol. The 18-tococenyl alcohol thus obtained is further catalytically reduced using platinum oxide, palladium, nickel, etc. as a catalyst to obtain tocosyl alcohol. Furthermore, tocosanoic acid can be obtained by catalytic reduction of 18-tocosenoic acid in a similar manner. Of course, without using the above reduction method,
Raw materials isolated and extracted from natural oils may also be used. In this way, the esters of the present invention can be obtained by utilizing the general esterification method using the above-mentioned acid and alcohol. 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
Either heat at ~260°C for about 4 to 15 hours, or combine the above acid and the above alcohol under a dehydrating agent such as a mineral acid such as sulfuric acid or a benzenesulfone group such as para-toluenesulfonic acid. You may react.

The above reaction is carried out under a stream of inert gas such as nitrogen gas or carbon dioxide gas, and the specific gravity also helps prevent coloring, so considering the purity of the product, favorable results can be obtained at7.
If you want to color the material, treat it with activated carbon or activated clay to get good results. 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 bromides or chlorides of the above acids, and the above alcohols are added to the bromides or chlorides of the above acids. It can be obtained in high yield by reacting these compounds in the presence of a basic catalyst such as triethylamine or pyridine. Further treatment by column chromatography etc. yields a highly pure ester of the target product.

Of course, it is also possible to manufacture by known methods other than the method 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.

Example 1 Method for producing 1B-do-heptanoic acid-18-toco-sevenyl ester (cis-cis form) (also known as Eruca silyl ester, hereafter abbreviated as EKE) Xylene aooy was placed in a 2-ton four-touch flask, and metal sodium was added to it. 616g
and heat and stir at 110-120'C4. Then, add 200g of methyl erucate and methylisobutylcarbinol.

Gradually add the mixed solution of 1459. After the dropwise addition is completed, the mixture is refluxed for 1 hour. After the reaction is completed, 500 d of water is carefully added gradually for 1 decomposition. After washing four times with warm water, dry with anhydrous sodium sulfate and pass through the mouth. After removing the solvent under reduced pressure, the residue was subjected to vacuum distillation.

(With 15 meters, you can get 180-190" colorless or pale yellow erucil alcohol 1451 tea 8 points 82~
84.5°C, acid value α5, hydroxyl value 17α1. Iodine number 7
&1, refractive index nll, L 45 ? 4゜neat
-s.

Infrared absorption spectrum v/rnaxCm, α260 (hydroxyl group), 2850-8000 (methylene) (a) Then erucic acid a761α02 solute) to about 20 II thionyl chloride
After heating at -80°C for 1 hour, excess thionyl chloride was distilled off under reduced pressure. Furthermore, a method for completely distilling off thionyl chloride, chloroform, etc.5. ．． 0. ml, and further evaporated under reduced pressure. To this was added Erucyl Alcohol 4B,9 (α02 mol) obtained above, and then pyridine L9Ii was added dropwise with stirring. Dripping is accompanied by heat generation. After dropping, the mixture is further heated at 70 to 80°C for 80 minutes to complete the reaction. After cooling, add 50 grams of 10% hydrochloric acid,
Extract with ether. The ether solution is washed twice with water and then dried over anhydrous sodium sulfate. - evaporate and distill off the ether. Remaining amount, wo, ri, shell mouth, form-x-f, I
Dissolve in I/mixture and pass through a layer of alkaline column chromatography. The solvent was distilled off, and the remaining amount was 1 mL of colorless wax-like EEE.
161#ft, yield 971cm, melting point 28~26℃,
Infrared absorption spectrum? ':m;”x'□-1:174
2 (ester), 2850-8000 (methylene), acid value α4, hydroxyl value α8, saponification value 8a5゜Iodine value? ? 9゜(ro)elka*50g,! -erucyl alcohol 5a2
Mix 11 and N! While blowing gas, 240~2
The mixture was reacted at 50°C for 4 hours with stirring. After the reaction is completed, some unreacted substances are distilled off by heating under reduced pressure (1 mmHg). The residue was decolorized twice using Eri activated carbon in a conventional manner to obtain a colorless wax-like EE sample 9α511. Melting point 2α5~
25°C, acid value α5, water base value.

Saponification value 858. The infrared absorption spectra of the nine products obtained by this method, which had an iodine value of 7a8, an ester value of 862, and a refractive index of n''L of 4682°, completely matched those obtained in Examples.

Actual M example! Method for producing 11-tocosenoic acid tocosyl ester (cis form) (also known as erucic acid behenyl ester)
(abbreviated as EEE) Elka [fl? 6. lα02) Esterification was carried out in the same manner as in Example 1 using tobehenyl alcohol a52# (α02) to obtain a colorless waxy KBEfl'';1
48g was obtained. Yield 986%, melting point 44.5-508°C,
Acid value α8. Hydroxyl value α6. # value 8a7. Iodine value 4α0
, refractive index n”L4514, infrared absorption spectrum vJm
axCm, 1740, (ester), 2850-298
0 (methylene)! J Auhi Tocosan #Jt-18-Toco7yl ester (cis form) production method (also known as behenic acid erucyl ester, hereinafter abbreviated as EEE) Using behenin eIla80II (αD 2 mol) and erucyl alcohol &48.9 (α021-l) Example 1
Esterification is carried out in the same manner as to form a colorless wax-like product #) B
g E with IL87.9. , Yield 957chi, A point 47
~4&5℃, acid value α8, hydroxyl value α6, ester value 8?
6. Saponification number 8a8, iodine number 8a8, refractive index n" L46
14. Specific gravity d38α842B, infrared absorption spectrum y'xtcm-': 1788
(ester), zaao~295G (methylene) g Method for producing tocosanoic acid docosyl ester (also known as behenic acid behenyl ester, hereinafter abbreviated as BB, E) Example 1 using behenic acid a801α02 mol) tophenyl alcohol a521α02 mol) Esterification was carried out in the same manner as above to obtain 1161p of colorless wax-like HBE. Yield: 978 cm, melting point: 7α0-7α7°C, acid value α7, hydroxyl value α4. Condensation number 838, iodine number α11, ester number 8&1, infrared absorption spectrum V/maxCm-':
1785 (ester) 2850-2960 (methylene) Engraving of specification (no change in content) Example 3 (a) Surface finish The color and odor of the esters obtained in the present invention were combined with a known base material. A comparison is shown. (Comparison when melted) Like the surface finish, the esters of the present invention are almost colorless and transparent, odorless, and are superior to 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 characteristic odor.

(b) Table! Table 1 shows the thermal oxidative stability (
Gardner) and compare the hue, and the smaller the hue value, the better the thermal oxidation stability.

Place each sample in a test tube and place it in a 1801:3 oil bath under air.
The value after heating for a certain time is shown.

From the results in Table 1, the ester of the present invention has better thermal oxidative stability than the comparative substance.

(c) Table ■ The surface layer shows the test results of the alkali hydrolysis resistance of the ester of the present invention and the control substance.

Cleaned version of the specification (no changes to the content) The test method is to take approximately 2 tons of the test substance and 25 ml of 173-N ethanol potash into a saponification value measurement flask, attach a cooling tube, and heat it at 85°C, at regular intervals. The saponification value of the test substance was measured, and the decomposition rate was determined by dividing the value by the saponification value obtained when the substance was reacted at 85° C. for 3 hours with ethanol potash having a different Kl specification. As a result, the ester of the present invention has superior alkali hydrolysis resistance compared to lower alcohol esters of erucic acid and behenic acid, which are the control substances.

Table W shows that 50 parts by weight of olive oil is added to 50 parts by weight of the ester of the present invention and the control substance, and then
(No change in content) This is the result of a trial production of the quality and the feel of this cream when applied to the hands.

The table above was conducted with 4 boys and 5 girls, and 50% of Vaseline was used.
The comparison was made by comparing the feel when a cream consisting of 50 parts by weight of olive oil was applied to the hands. According to the results in Table 2, the esters of the present invention are superior in feel compared to petrolatum, but the control test sample cannot be said to be superior to petrolatum.

(E) Table V Table V shows the results of a human skin irritation test of the ester of the present invention and a control substance.

The test method is a closed patch test method, in which liquid paraffin oil containing 103i of the test substance is placed on the inner side of one tie or front tie. I L, flannel cloth coated with this (1.5c
mff1 side) and cover it with a bandage.

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 the judgment was repeated after 4 hours. The evaluation is: no change at all -), faint erythema (±), obvious erythema (-1), and edema, blisters, etc. other than erythema (+). , perform the evaluation.

The results shown in Table V were carried out on 4 male and 6 female subjects, and all of the 9 subjects who applied the esters of the present invention tested negative in the skin irritation test described above. However, esters of low 9-fluoric acid such as erucic acid and behenic acid, which are all known substances, were found to cause skin irritation.

Examples Customers Next, examples of cosmetics using the first aspect of the present invention will be shown. (Indicates weight unit) Prescription L O/W Cold Cream L Glycerin Heptanostearate L5 Total 10α0
(Manufacturing method) Component A is heated to 70 to BO''C, stirred and mixed to dissolve, and the KB acid component is gradually added to emulsify.

Further, component 0 is added and mixed, and then cooled to 80°C to form a product.

This cold cream had a smooth and good texture.

Prescription 2. W/U type nutritional cream Clear #ll [Engraving of F (no changes in content).

Total: 10α0ts (Manufacturing method) Component A is heated to a temperature of 70 to 80'C, stirred and mixed to dissolve it, the KB acid component is added thereto, and an appropriate amount of the fragrance and preservative of C are added and mixed.

This nourishing cream is extremely smooth and feels great when used.

Prescription 1 Lipstick 0 [Fragrance 04 Total 10αOX (Manufacturing method) Component A is heated and dissolved, and component B is added to this and mixed uniformly using a p- and -r. Dissolve this again.

Add fragrance, defoamer, filter, mold, fill into containers, and make a glossy product.

This lipstick has a nice feel on the lips, is non-sticky, and spreads easily.Formulation: Pomade (Production method) Component A is mixed and dissolved by heating. Add the KB acid component to this and cool.

This pomade has excellent transparency and is easy to use.

Prescription a: Pharmaceutical ointment (anti-inflammatory and analgesic topical preparation) total of 1OαOX (manufacturing method) Heat component B a little and mix well. Add KA acid component and knead further until uniform.

The feeling of using this @chemical ointment is that it is made only with hydrophilic ointment without adding the ester of the present invention, and it is less sticky (, ff
It feels good when used.

Procedural amendment (method) % formula % 1, Indication of case Patent application No. 15971 of 1985 2
, Title of the invention Cosmetics and external preparations 3. Relationship with the case of the person making the amendment Patent applicant postal code 541 Postal code 532 4. Date of amendment order (shipment date)) May 27, 1985 5. Amendment Subject a) Request Form 6, Contents of Amendment (1) Submit a separate copy with the correct seal of the patent applicant.

C) Specification letters 1, 5, 7, 15, 16, 17, 18,
I will submit the engravings of pages 19 and 22 for 3JIJJt.

Claims (1)

[Claims] General formula (I) CH_3(CH_2)_7(R')(CH_2)_1_
1COOCH_2(CH_2)_1_1(R″)(CH
＿２）＿７CH＿３・・・・・・・・・・・・・・・(
I) (In the formula, R' is -CH=CH- and R'' is -CH=C
Cosmetics and external preparations containing an ester compound represented by H- or -CH_2CH_2- as a base.