JPH01207221A - External preparation for skin and hair - Google Patents

Abstract

PURPOSE:To obtain the title external preparation which contains hydrogenated lanolin acetate, and/or liquid hydrogenated lanolin acetate, thus showing excellent safety and stability to oxidation. CONSTITUTION:Lanolin acetate and liquid lanolin acetate are combined with a copper or nickel catalyst and subjected to hydrogenation at 100-200 deg.C under 1-5kg/cm<2> pressure to effect selective hydrogenation of double bonds in sterols and triterpene alcohols whereby hydrogenated lanolin acetate or liquid lanolin acetate with improved stability to oxidation is obtained without substantial change of intrinsic properties. The product is added to an external preparation for skins and hairs in an amount of 0.1-30wt.%. When the preparation is allowed to stand for a long time, the deterioration due to oxidation with the passage of time can be prevented, whereby adverse effects of peroxides formed by oxidation on the skins such as allergy or stimulation can be avoided.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention comprises hydrogenated acetic acid lanolin and/or hydrogenated acetic acid 1ffl lanolin with improved oxidative stability,
The present invention provides a skin and/or hair external preparation with excellent safety and oxidative stability.

(Prior Art) Since ancient times, lanolin has been incorporated into cosmetics such as creams, milky lotions, and lipsticks because it has excellent affinity, adhesion, and wettability to the skin, and also has water-holding power. In recent years, in order to improve skin permeability and diffusivity, liquid lanolin has been developed by removing the waxy ester portion with a high melting point by solvent fractionation, etc., and is widely used in cosmetics.

However, it has been reported that lanolin causes allergic reactions due to oxidation, and the main cause is said to be the polar components in lanolin (free lanolin alcohol, lanolin fatty acids, and other polar substances). Due to its manufacturing process, liquid lanolin contains more polar components than lanolin and has the same allergy problems as lanolin.

It also has a unique animal odor, so when adding it to cosmetics, you need to be careful about the amount.

Furthermore, lanolin is an ester compound of higher alcohols and higher fatty acids, which consist of sterols whose main component is cholesterol and triterpene alcohols whose main component is lanosterol, so if cosmetics containing lanolin are left for a long period of time, they will There is a problem in that it causes rancidity and significantly reduces the commercial value of cosmetics.

It is also said that the peroxides produced by rancidity have adverse effects on the skin, such as irritation and allergies.

The main cause of lanolin allergies is free alcohol with hydroxyl groups and other polar components, so acetic acid lanolin, which is made hypoallergenic by acetylation using acetic anhydride, is used. Lanolin is dissolved in mineral oil and used in heavy oils, etc., but due to its hydrophilic nature, it has the disadvantage of becoming cloudy or precipitating over time. Lanolin acetate has been improved by acetylating properties thought to be caused by hydroxyl groups.

Also, acetic acid liquid lanolin has recently been used for the same purpose. However, the oxidative stability remains unchanged, and cosmetics containing acetic acid lanolin or acetic acid liquid lanolin become rancid over time.

(Solution Means) In order to improve the above-mentioned drawbacks, the present invention, as a result of intensive studies, added a catalyst such as steel or nickel to acetic acid lanolin and acetic acid liquid lanolin, and a pressure of 1 to 5 kg/cv.
a2. At a temperature of 100 to 200°C, hydrogenation is performed selectively on the double bonds of sterols, triterpene alcohols, etc. to improve the oxidative stability of lanolin acetate and liquid lanolin acetate without significantly changing their original physical properties. It is highly improved.

There is no problem even if acetylation is performed after hydrogenation. The hydrogenated acetic acid lanolin and hydrogenated acetic acid liquid lanolin obtained in the manner described above can be used in cream emulsions, lipsticks, etc., and cosmetics with little color and odor and excellent oxidation stability can be obtained. When used in hair cosmetics such as hair creams, it is possible to obtain hair cosmetics that have excellent luster, are easy to comb, give a moist feel, and have excellent roughness and oxidation stability. The amount added to creams is not particularly limited, but is generally 0.
It can be blended in an amount of 1 to 30% (wt%).

Production Example-1 0.3 part of acetic anhydride was added to 1 part of lanolin, and the mixture was heated and stirred at 110°C for 1 hour to effect acetylation. After acetylation, wash with warm water until neutral, 105
Dehydrate and dry at ℃ for 1 hour. A nickel catalyst was added to the obtained lanolin acetate and the pressure was 5 kg/cm 2.20
Hydrogenation is carried out at 0°C. 2 parts of n-hexane is added to the obtained hydrogenated acetic acid lanolin and dissolved by heating, then 0.1 part of activated alumina and 0.03 part of activated carbon are added and stirred for 10 minutes. After filtering this, n-hexane is collected,
0.9 part of pale yellow paste was obtained. The physical properties and oxidation stability at 60°C of the obtained lanolin acetate are shown in Tables 1 and 2.

Table-1 Physical properties table-Oxidation stability at 260°C (peroxide value) Production example-2 Add a nickel catalyst to 1 part of liquid lanolin and apply at a pressure of 5 k
g/am 2. Hydrogenation is carried out at 200°C. 1 part of n-hexane is added to the obtained hydrogenated liquid lanolin and dissolved, followed by filtration to remove the catalyst. 1α is n-
After collecting hexane, add 0.3 parts of acetic anhydride,
Acetylation was carried out by heating and stirring at 10°C for 1 hour.

After washing with water until it becomes neutral after acetyl death, 105
Dehydrate and dry at ℃ for 1 hour. Add 3 parts of n-hexane to 1 part of the obtained hydrogenated acetic acid liquid lanolin and dissolve. This n
- After passing the hexane solution overnight through a column packed with 3 parts of activated alumina, 3 parts of n-hexane was further passed through the column, and the obtained eluate 1α was taken into a flask and the n-hexane was distilled off. A liquid, hydrogenated acetic acid lanolin was obtained. The yield was 59.2%.

The physical properties and oxidation stability at 60°C of the obtained hydrogenated acetic acid iα lanolin are shown in Tables 3 and 4.

Table 3 Physical property values Example 1 Cream was mixed with hydrogenated acetic acid lanolin obtained in Production Examples 1 and 2 and water thermometer liquid lanolin according to the formulation shown in Table 5, and the cream was colorless and transparent. The product was packed in a glass bottle and left next to a window for one year to test its stability over time. Result is,
It is as shown in Table-6. For comparison, unhydrogenated lanolin acetate and lanolin acetate in the i-alpha form were also mixed into creams with the same formulation and evaluated.

Table-6 ◎: Odorless O: Slightly 1. ! Abnormal odor Δ: Specific odor A prescription example is shown next.

Prescription example-1 Emollient cream beeswax
6.0 Weight 27 Tanon

5.0 Hydrogenated Acetate Rahashi
8.0 IPM
13.5 Squalane
10.0
Fluid 1 birafish
10.0 Ollie Lake
4.0 lipophilic type E Noste? Phosphate - Lycerin
4.04") 4+n1fLn)n and 19'JE
)λ7? ')) m Il? R(20EO>4.0 preservative il! Purified water
35.5 Prescription Example-2 Emulsion Prescription Example-3 Hair Cream Hydrogenated Acetic Acid Liquid Lanolysi
Samples of 5.0 Formulation Examples 1 to 3 packed in colorless transparent glass bottles were left in Shigiwa for one year to test their stability over time. The results are shown in Table-7.

Table 7 ◎: Odorless O: Slightly specific As shown in the results of 7, even after 12 months, there was only a slight specific odor, and the oxidation stability was excellent.

Procedural amendment 1, Indication of the case 1988 Patent application No. 30286 2, Title of the invention Skin and hair external preparation 3o Person making the amendment Relationship to the case Patent applicant Address 1-37 Tokuimachi, Higashi-ku, Osaka Name Clodagh Japan Co., Ltd. May 31, 1988 (shipping date) September 27, 1988 (shipping date) 5. Target of amendment f late application J and specification 6, contents of amendment A, r application” (1) In accordance with the partial amendments to the Patent Act, etc. that came into effect on January 1, 1988, "r (patent application pursuant to the proviso to Article 38 of the Patent Act)" will be deleted.

(2) In accordance with the partial amendments to the Patent Act, etc. that came into effect on January 1, 1988, the "number of inventions stated in the scope of claims" will be amended to "the number of claims."

(3) The title of the invention is amended to "External preparation for skin and hair."

B, r statement” (1) Delete the date on the second line of the first page.

(2) The title of the invention is amended to "External preparation for skin and hair."

(3) Add the item "3. Detailed Description of the Invention" between lines 8 and 9 on page 1 of the specification.

Description 18 Name of the invention External preparation for skin and hair 2. Claims External preparation for skin and/or hair characterized by containing hydrogenated acetic acid lanolin and/or hydrogenated acetic acid liquid lanolin 3. Invention DETAILED DESCRIPTION (INDUSTRIAL APPLICATION FIELD) The present invention provides a skin and skin product with excellent safety and oxidative stability, which contains hydrogenated acetic acid lanolin with improved oxidative stability and/or hydrogenated acetic acid liquid lanolin. (or) provides a hair external preparation.

(Prior Art) Since ancient times, lanolin has been incorporated into cosmetics such as creams, milky lotions, and lipsticks because it has excellent affinity, adhesion, and wettability to the skin, and also has water-holding power. In recent years, in order to improve skin permeability and diffusivity, liquid lanolin has been developed by removing the waxy ester portion with a high melting point by solvent fractionation, etc., and is widely used in cosmetics.

However, it has been reported that lanolin causes allergic reactions due to oxidation, and the main cause is said to be the polar components in lanolin (free lanolin alcohol, lanolin fatty acids, and other polar substances). Due to the manufacturing process, liquid lanolin contains more polar ingredients than lanolin, and may have the same allergy issues as lanolin.

It also has a unique animal odor, so when adding it to cosmetics, you need to be careful about the amount.

Furthermore, lanolin is an ester compound of higher alcohols and higher fatty acids, which consist of sterols whose main component is cholesterol and triterpene alcohols whose main component is lanosterol, so if cosmetics containing lanolin are left for a long period of time, they will There is a problem in that it causes rancidity and significantly reduces the commercial value of cosmetics.

It is also said that the peroxides produced by rancidity have adverse effects on the skin, such as irritation and allergies.

The main cause of lanolin allergies is free alcohol with hydroxyl groups and other polar components, so acetic acid lanolin, which is made hypoallergenic by acetylation using acetic anhydride, is used. Furthermore, lanolin is dissolved in mineral oil and used in baby oil and the like, but due to its hydrophilic nature, it has the disadvantage of becoming cloudy or precipitating over time. Lanolin acetate has been improved by acetylating properties thought to be caused by hydroxyl groups.

Also, acetic acid liquid lanolin has recently been used for the same purpose. However, the oxidative stability remains unchanged, and cosmetics containing acetic acid lanolin or acetic acid liquid lanolin become rancid over time.

(Solution Means) In order to improve the above-mentioned drawbacks, the present invention, as a result of intensive studies, added a catalyst such as copper or nickel to acetic acid lanolin and acetic acid (alpha) lanolin, and a pressure of 1 to 5 kg/a.
ya 2. At a temperature of 100 to 200°C, hydrogenation is selectively performed on the double bonds of sterols, triterpene alcohols, etc., and the oxidation stability is improved without significantly changing the original physical properties of lanolin acetate and liquid lanolin acetate. It is highly improved.

There is no problem even if acetylation is performed after hydrogenation. The hydrogenated acetic acid lanolin and hydrogenated acetic acid liquid lanolin obtained in the manner described above can be used in creams, lipsticks, etc., and cosmetics with little color and odor and excellent oxidation stability can be obtained. Furthermore, when used in hair cosmetics such as hair creams, it is possible to obtain a hair-forming extract that gives the hair excellent gloss, easy combing, a moist feel, and is extremely oxidatively stable. . There are no particular restrictions on the amount of cream to be added, but - for boat fishing, 0
．． It can be blended in an amount of 1 to 30% (wt%).

Production Example-1 0.3 part of acetic anhydride was added to 1 part of lanolin, and the mixture was heated and stirred at 110°C for 1 hour to effect acetylation. After acetylation,
After washing with warm water until neutral, 105℃
Dehydrate and dry for 1 hour. A nickel catalyst was added to the obtained lanolin acetate, and the pressure was 5 kg/e+s 2.200
Hydrogenation is carried out at °C. After adding 2 parts of n-hexane to the obtained hydrogenated acetic acid lanolin and dissolving it by heating, 0.1 part of activated alumina and 0.03 part of activated carbon are added and stirred for 10 minutes. After filtering this, n-hexane was recovered to obtain 0.9 parts of pale yellow paste. The physical properties and oxidation stability at 60°C of the obtained lanolin acetate are shown in Tables 1 and 2.
It is as follows.

Table-1 Physical properties table-Oxidation stability at 260°C (peroxide value) Production example-2 Add a nickel catalyst to 1 part of liquid lanolin and apply at a pressure of 5 k
g/cm 2. Hydrogenation is carried out at 200°C. 1 part of n-hexane is added to the obtained hydrogenated liquid lanolin and dissolved, followed by filtration to remove the catalyst. The filtrate is n-
After collecting hexane, add 0.3 parts of acetic anhydride,
Acetylation is carried out by heating and stirring at 10° C. for 1 hour.

After washing with water until it becomes neutral after acetyl death, 10
Dehydrate and dry at 5°C for 1 hour. Add 3 parts of n-hexane to 1 part of the obtained hydrogenated acetic acid liquid lanolin and dissolve. This n-hexane solution was passed through a column filled with 3 parts of activated alumina, and then 3 parts of 11-hexane was passed therethrough, and the resulting eluate was taken into a flask and the n-hexane was distilled off.
A pale yellow, oily, hydrogenated acetic acid liquid lanolin was obtained. The yield was 59.2%.

The physical properties and oxidation stability at 60°C of the obtained hydrogenated acetic acid liquid lanolin are shown in Tables 3 and 4.

Table-3 Physical property table-Oxidation stability at 460°C (peroxide value) Example-1 Using the hydrogenated acetic acid lanolin and hydrogenated acetic acid liquid lanolin obtained in Production Examples-1 and 2, Table-5 After formulating the cream according to the prescription, the cream was packed in a colorless and transparent glass bottle and left next to a window for one year to test its stability over time. Result is,
It is as shown in Table-6. For comparison, unhydrogenated acetic acid lanolin and acetic acid (alpha) lanolin were also blended into creams with the same formulation and evaluated.

Table-5 Table-6 ◎: Odorless O: Slightly specific odor Δ: Specific odor
X: Strong rancidity As shown in the results of Makura-6, the hydrogenated product clearly has better oxidation stability than the unhydrogenated product. A prescription example is shown next.

Prescription example-1 Emollient cream beeswax
6.0 heavy jl! Setanol

5.0 Hydrogenated acetic acid lanolin
8.0 IPM

13.5 Purified water 35.
5 Prescription Examples - 2 Emulsion Micro Grease 9 Rishiwax
+, oitx mifu 0tsu water

2.0-added acetic acid liquid lanoric acid
2.0 fluidity; pilafine
30.0 Soljitances to Oshiny F
4.0 bottles 6 ri 1 J If & Solhi 9 t no 14th phosphoric acid esthetics A (20 EO) 1.0 note? fulminium phosphate
0.2 preservative
Appropriate amount of coulis B Reno
8.0M ice making
51.8 Prescription example-3 hair cream beeswax
1. ON amount χ flow vJ + birafin 3
5. ON'M
10.0 Hydrogenated acetic acid liquid lanolytic acid 5.0 Solhietance 4LL1-)
2.2 Reference 994~Noethylene Sorhitan (20EO) 2
．． 0 Preservatives Appropriate amount of purified water 44.8 For Prescription Examples 1 to 3, samples packed in colorless and transparent glass bottles were left next to a window for one year to test their stability over time. The results are shown in Table-7.

Table 7 ◎: Odorless O: Slightly specific As shown in the results of 7, even after 12 months, there was only a slight specific odor, and the oxidation stability was excellent.

Claims (1)

[Claims] A skin and/or hair external preparation characterized by containing hydrogenated acetic acid lanolin and/or hydrogenated acetic acid liquid lanolin