JPH06116584A - Method for purifying cholesterol ester and skin external preparation containing cholesterol ester obtained by this method - Google Patents

Abstract

PURPOSE:To simply and efficiently obtain a cholesterol ester useful for skin external preparations, etc., and having high cholesterol content by purifying oil and fat such as wool grease having a specific cholesterol content in an unsaponifiable material thereof by a solvent fractional crystallization and a column chromatography. CONSTITUTION:A raw material oil and fat consisting of wool grease, lanolin or a lanolin derivative and having at least 25% cholesterol content in unsaponifiable material thereof is dissolved in a solvent such as methyl ethyl ketone by heating at 50-60 deg.C for 30min and then cooled to 5 deg.C and allowed to stand at this temperature for 24hr and the deposited material is filtered by filter paper and the separated and deposited material is dried by a solvent fractional crystallization to afford a crude cholesterol ester. Then, the ester is dissolved in n-hexane and purified by a column chromatography in which fractionation is carried out by passing through silica gel column and further passing n-hexane through the column to simply and efficiently provide the objective compound having extremely high cholesterol content of >=50% in the unsaponifiable material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying cholesterol ester and an external preparation for skin containing the cholesterol ester obtained by the method, which aims to easily and easily collect cholesterol ester directly from wool grease, lanolin or a lanolin derivative. It is an object of the present invention to provide a purification method capable of efficient purification, and a skin external preparation excellent in emollient effects such as moistness and water retention. still,
In the present invention, the external preparation for skin refers to all external preparations for use on the human body for the purpose of makeup and hair growth, regardless of whether they belong to the cosmetics, quasi-drugs, or pharmaceuticals referred to in the Pharmaceutical Affairs Law.

[0002]

BACKGROUND OF THE INVENTION Oils and fats are used as a raw material for cosmetics for the purpose of softening the cells of the skin and suppressing the evaporation of water in the epidermis to prevent dryness and rough skin. Above all, lanolin has been used as a raw material for cosmetics since ancient times as a component having a composition closest to that of human sebum. Lanolin is an ester of a complex fatty acid and a higher alcohol, and about half of the higher alcohol is said to be cholesterin and isocholesterine. In this way, lanolin, which contains a large amount of cholesterin, is insoluble in water, but has the property of absorbing and conjugating about twice as much water, so it has a very good affinity for the skin and an excellent emollient effect, and is effective in creams, emulsions and lipsticks. Widely used as a raw material for cosmetics such as hair cosmetics. However, this lanolin may be altered or cause an allergic reaction to a person with a specific constitution depending on the conditions at the time of collection, the time elapsed after collection, etc. It is also used in a form such as a derivative that retains its characteristics. On the other hand, esters are also widely used as cosmetic raw materials for creams, emulsions, etc. since they have good permeability to the skin, have a dry feeling of use, and have good compatibility with other cosmetic ingredients. . Among the esters, cholesterol ester has been particularly attracting attention in place of the above-mentioned lanolin as a component for moisturizing the skin and recently as an important component for intercellular lipid. Examples of the cholesterol ester include lanolin fatty acid cholesteryl, cholesteryl stearate, and cholesteryl isostearate. Among them, lanolin fatty acid cholesteryl has a unique fatty acid composition, and has affinity for skin, permeability and diffusion, and a softening effect. Since it is superior to lanolin and has a remarkable function of keeping skin moist and healthy, it is focused on its use alone as a cosmetic raw material.

[0003]

2. Description of the Related Art Generally, since lanolin is a natural product and has a very complicated composition, and its properties are very similar to each other, it is impossible to efficiently purify high-purity cholesterol ester. It was Therefore, conventionally, an organic synthesis method of reacting cholesterol with a fatty acid has been adopted as a method for preparing a cholesterol ester. However, in the preparation of cholesterol ester by this organic synthesis method, an expensive and unstable reaction reagent is required, and the reaction conditions are severe,
It was not an efficient production method because the yield of cholesterol ester obtained was low, as it had a problem in safety and a by-product was easily generated. In view of such circumstances, a method of enzymatically synthesizing cholesterol ester has been disclosed instead of the organic synthesis method. This technology
An enzyme selected from lipase and cholesterol esterase was used to prepare cholesterol ester from fatty acid or fatty acid ester and cholesterol or long chain fatty alcohol.

[0004]

However, in the method for synthesizing cholesterol ester by the reaction with the above-mentioned enzyme, cholesterol used as a synthetic raw material is expensive and cannot be easily obtained. There was a problem of not having it. Moreover, since the cholesterol ester obtained by this method is a synthetic product, there is a problem that the effects such as affinity with skin and permeability are significantly inferior to those of natural ones. Therefore, in the industry, cholesterol ester such as lanolin fatty acid cholesteryl that exerts an excellent effect on the skin can be directly and simply separated from the naturally occurring wool grease or lanolin or lanolin derivative, and a method capable of being purified. Further, it has been desired to create an excellent external preparation for skin containing a cholesterol ester directly separated from naturally occurring lanolin.

[0005]

In the present invention, selected from wool grease, lanolin or lanolin derivatives,
Cholesterol ester in which the cholesterol content in the unsaponifiable matter is 50% or more is purified from the raw fat or oil whose cholesterol content in the unsaponifiable matter is at least 25% or more by the combination of the solvent fractionation crystallization method and the column chromatography method. A method for purifying a cholesterol ester characterized by comprising: and a skin external preparation characterized by comprising a cholesterol ester having a cholesterol content in an unsaponifiable matter of at least 50% or more. Solve the problem of.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the method for purifying cholesterol ester according to the present invention and the composition for a skin external preparation containing cholesterol ester obtained by this method will be described in detail. First, the method for purifying cholesterol ester will be described in detail. In the purifying method of the present invention, wool grease, lanolin or a lanolin derivative is selected, and the cholesterol content in the unsaponifiable matter is at least 2.
Raw fats and oils of 5% or more are used as starting materials.
Wool grease is sheep (Ovis aries Linne (Bovidae))
It is present in the secretions that adhere to the hair of the cattle and is recovered from the wool washing waste liquor. Lanolin is obtained by purifying this. The composition of this lanolin is very complicated and mainly consists of esters of complex fatty acids having 10 to 33 carbon atoms and sterols having 13 to 30 carbon atoms, triterpene alcohols, aliphatic alcohols and the like. Specifically, it is said to include esters of cholesterin, lanosterine, agnosterine and the like with lanoseric acid, lanopalmitic acid, lignoceric acid and the like and free cholesterin, cetyl, ceryl and carnauba alcohol. Examples of the lanolin derivative include hard lanolin, lanolin acetate, hard lanolin acetate, hydroxy lanolin, lanolin acetate alcohol, and polyoxyethylene lanolin.

These wool greases, lanolin and lanolin derivatives usually contain about 10 to 90% of unsaponifiable unsaponifiable alkali, and the unsaponifiable matter generally contains about 1% of hydrocarbons. , 20% higher alcohols, 30-40% sterols, 40% triterpene alcohols. In the present invention, one or more raw material oils and fats selected from wool grease lanolin or lanolin derivatives in which at least 25% or more of cholesterol is contained in such an unsaponifiable material are used as a starting material.

Cholesterol ester is separated and purified by using the above starting materials in combination with the solvent fractional crystallization method and the column chromatography method. In the solvent fractional crystallization method, the raw oils and fats are mixed in the organic solvent at about 50-60 ° C
While being heated to room temperature, it is cooled to a temperature range from room temperature to about 5 to -10 ° C, and left to stand for at least 24 hours or more in this state to precipitate a component containing a large amount of cholesterol ester.

The organic solvent used is not particularly limited and can dissolve the raw material oil and fat, has no reactivity with the raw material oil and fat, and has a freezing point of at least 5 ° C.
Any organic solvent can be suitably used as long as it has the following levels. Specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl-n-propyl ketone, 2-methylbutane, n-pentane, n
Hydrocarbons such as hexane and n-octane, various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, esters such as ethyl acetate and isopropyl acetate, ethyl ether and isopropyl ether,
One or a mixture of two or more kinds of ethers such as n-butyl ether and the like is exemplified as a suitable example, but is not particularly limited.

After mixing 100 to 500 parts by weight of raw material fats and oils with 100 parts by weight of the organic solvent in the above organic solvent, the solvent is heated to about 50 to 60 ° C. Thus, by heating the solvent mixed with the raw material oil and fat at about 50 to 60 ° C. for 10 to 30 minutes, only the high melting point component contained in the raw material oil and fat can be dissolved. After heating, add organic solvent from room temperature to 5
The mixture is cooled to a temperature range of up to about −10 ° C. and left in this state for at least 24 hours to precipitate cholesterol ester in the raw material fat and oil, and the precipitate is filtered off using a filter paper. Such solvent fractionation crystallization operation is repeated about 2 to 3 times to separate crude cholesterol ester precipitates from the raw material fats and oils. The obtained crude cholesterol ester precipitate is washed with an organic solvent such as methyl ethyl ketone cooled to about 5 ° C., concentrated under reduced pressure to remove the solvent, and then further purified by column chromatography.

In the column chromatography method, the crude cholesterol ester obtained by the solvent fractional crystallization method is dissolved in a non-polar solvent and is passed through a column filled with an adsorbent to adsorb and separate polar components. As the non-polar solvent used,
Aliphatic hydrocarbons such as petroleum ether, n-hexane, n-pentane, n-butane, n-octane, and cyclohexane, and carbon tetrachloride, trichloroethylene, benzene, toluene and the like can be preferably used without particular limitation.
The adsorbent is also not particularly limited, and silica gel, alumina, activated alumina, ammonium silicate, magnesium silicate, magnesium aluminometasilicate, activated clay, acid clay, zeolite, and mixtures thereof are preferably used. Separation and purification by such a column chromatography method is performed at least once, more preferably 2-3.
Repeat times. The eluate obtained by such a column chromatography method is distilled under reduced pressure to remove the solvent,
At least 50 cholesterol content in unsaponifiable matter
Get a cholesterol ester that is greater than or equal to%. In the present invention, either of the methods of separation by solvent fractional crystallization, purification and separation by column chromatography, purification may be used first, and after purification by column chromatography, purification by solvent fractional crystallization is performed. You may go.

Next, the external preparation for skin containing the cholesterol ester obtained by the above purification method will be described. In this external preparation for skin, cholesterol ester which is refined from a raw material oil selected from wool grease, lanolin or a lanolin derivative and whose cholesterol content in the unsaponifiable matter is at least 50% or more is blended as an essential component. As this cholesterol ester, lanolin such as lanolin fatty acid cholesteryl or its derivative is preferably used. The amount of the cholesterol ester compounded is not particularly limited and may be appropriately determined depending on the purpose and type of the external preparation to be prepared. Also, the form of the external preparation for skin is not particularly limited, and creams such as vanishing cream, aftershave cream, makeup base cream, moisture cream, nutrition cream, baby cream, hair cream, emulsion, cracks, ointment for preventing red crepe. Any form that expects a moisturizing effect and an emollient effect may be used.

[0013] (Formulation Example 1) Milk solution% cholesterol ester 10.0 sorbitan monoisostearate 3.0 Liquid paraffin 25.0 Stearic acid 2.0 Cetyl alcohol 0.3 Polyethylene glycol monostearate 1.2 Triethanolamine 1. 0 Glycerin 1.0 Purified water 56.5 100.0 (Formulation example 2) Moisture cream % Cholesterol ester 5.0 Stearic acid 7.0 Cetanol 5.0 Squalane 8.0 Polyoxyethylene cetyl ether 1.0 Propylene glycol mono stearate 3.0 (self-emulsifying) triethanolamine 3.0 glycerin 4.0 propylene glycol 8.0 purified water 56.0 100.0 (formulation example 3) Hair cream% cholesterol ester 8.0 liquid paraffin 30 0 Vaseline 5.0 Beeswax 12.0 sorbitan sesquioleate 3.0 polyoxyethylene sorbitan monolaurate 4.5 borax 0.5 Purified water 37.0 100.0

[0014]

[Examples] The effects of the method for purifying cholesterol ester according to the present invention and the external preparation for skin containing cholesterol ester obtained by this method will be further clarified with reference to Examples. It is not limited in any way by the embodiment. Incidentally, the determination of cholesterol in this example, all the general test method of cosmetic raw material standard, by the unsaponifiables measurement method, the unsaponifiable matter is first separated and quantified, and this is used as a sample by the quantitative method of lanolin alcohol for cosmetic raw material standard. The cholesterol was quantified.

[0015]

[Purification example]

(Purification Example 1) Cholesterol content in unsaponifiable matter is 2
To 100 g of 8.5% lanolin, 200 ml of methyl ethyl ketone was added, dissolved by heating at 50 to 60 ° C. for 30 minutes, cooled to 5 ° C., and allowed to stand for 24 hours while maintaining this temperature. 24 hours later,
Filtration was performed using filter paper to separate the precipitate. The separated precipitate was washed with a small amount of methyl ethyl ketone cooled to 5 ° C., the methyl ethyl ketone was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated twice to obtain 54 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of the obtained crude cholesterol ester was 44%. Next, 10 g of this crude cholesterol ester was dissolved in 100 ml of n-hexane, passed through a column previously packed with 50 g of silica gel, and further passed through 200 ml of n-hexane to obtain n-hexane. The eluate was distilled off under reduced pressure with a rotary evaporator and again passed through the column to obtain 3.9 g of cholesterol ester. The cholesterol content in the unsaponifiable matter of this cholesterol ester was 63.7%.

(Purification Example 2) 200 ml of ethyl acetate was added to 100 g of lanolin having a cholesterol content of 28.5% in the unsaponifiable matter, dissolved by heating at 50-60 ° C for 30 minutes, and then cooled to 5 ° C. It was left for 24 hours while maintaining the temperature. 24 hours later,
Filtration was performed using filter paper to separate the precipitate. The separated precipitate was washed with a small amount of ethyl acetate cooled to 5 ° C., ethyl acetate was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated twice to obtain 42 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of the obtained crude cholesterol ester is 45%
Met. Then, the obtained crude cholesterol ester
Dissolve 10 g in 100 ml petroleum ether and prepare 50 g in advance.
After passing through the column filled with silica gel of No. 1, 200 ml of petroleum ether, and distilling off the obtained petroleum ether eluate under reduced pressure with a rotary evaporator, again pass through the column in the same manner. Then, 3.9 g of cholesterol ester was obtained. The cholesterol content in the unsaponifiable matter of this cholesterol ester was 61.6%.

(Purification Example 3) To 100 g of lanolin having a cholesterol content of 30.1% in the unsaponifiable matter, 200 ml of ethyl acetate was added and dissolved by heating at 50 to 60 ° C for 30 minutes and then cooled to 5 ° C. I kept it for 24 hours. 24 hours later,
Filtration was performed using filter paper to separate the precipitate. The separated precipitate was washed with a small amount of ethyl acetate cooled to 5 ° C., ethyl acetate was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated twice to obtain 47 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of this crude cholesterol ester was 41%.
Then, 10 g of the obtained crude cholesterol ester was added to 100 m
It was dissolved in 1 n-hexane, passed through a column filled with 50 g of silica gel in advance, and 200 ml of n-hexane was passed through to obtain an n-hexane eluate, which was decompressed with a rotary evaporator. After distilling off, the column was again passed through the column to obtain 3.9 g of cholesterol ester. The cholesterol content in the unsaponifiable matter of the obtained cholesterol ester was 63.2%.

(Purification Example 4) 100 g of lanolin containing 30.1% of cholesterol in the unsaponifiable matter was added to methyl ethyl ketone.
Add 200 ml and heat to dissolve at 55-65 ℃ for 30 minutes.
It was cooled to ℃ and left for 24 hours while maintaining this temperature. twenty four
After a lapse of time, filtration was performed using a filter paper to separate a precipitate. The separated precipitate was washed with a small amount of methyl ethyl ketone cooled to 10 ° C., the methyl ethyl ketone was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated 3 times to obtain 27 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of the obtained crude cholesterol ester was 47.5%. Then, 10 g of the obtained crude cholesterol ester was dissolved in 100 ml of n-hexane, passed through a column previously packed with 50 g of activated alumina, and further passed through 200 ml of n-hexane to obtain the product. After evaporating the n-hexane eluate under reduced pressure with a rotary evaporator, it was again passed through the column in the same manner to obtain 4.1 g of cholesterol ester. The cholesterol content in the obtained unsaponifiable matter of cholesterol ester was 79.5%.

(Purification Example 5) 200 ml of methyl ethyl ketone was added to 100 g of wool grease having a cholesterol content of 25.4% in the unsaponifiable matter, dissolved by heating at 55 to 65 ° C for 30 minutes and then cooled to 5 ° C. It was left for 24 hours while maintaining the temperature. After 24 hours, filtration was performed using filter paper to separate the precipitate. The separated precipitate was washed with a small amount of methyl ethyl ketone cooled to 10 ° C., the methyl ethyl ketone was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated 3 times to obtain 39 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of the obtained crude cholesterol ester was 43.4%. Then, 10 g of this crude cholesterol ester was dissolved in 100 ml of n-hexane and passed through a column previously packed with 50 g of magnesium silicate.
The n-hexane eluate obtained by passing through ml was distilled off under reduced pressure with a rotary evaporator and then passed through the column again in the same manner to obtain 3.9 g of cholesterol ester. The cholesterol content in the obtained unsaponifiable matter of cholesterol ester was 62.7%.

(Purification Example 6) 200 ml of methyl ethyl ketone was added to 100 g of lanolin acetate having a cholesterol content of 28.8% in the unsaponifiable matter, dissolved by heating at 50-60 ° C for 30 minutes, and then cooled to -10 ° C. It was left for 24 hours while maintaining this temperature. After 24 hours, filtration was performed using filter paper to separate the precipitate. The separated precipitate was washed with a small amount of methyl ethyl ketone cooled to -10 ° C, the methyl ethyl ketone was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated twice to obtain 31 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of the obtained crude cholesterol ester was 45.5%. Then, 10 g of the obtained crude cholesterol ester was dissolved in 100 ml of n-hexane and passed through a column previously packed with 50 g of magnesium silicate.
The n-hexane eluate obtained by passing 200 ml was distilled off under reduced pressure by a rotary evaporator, and then again passed through the column in the same manner to obtain 4.1 g of cholesterol ester.
The cholesterol content in the obtained unsaponifiable matter of cholesterol ester was 63.6%.

(Purification Example 7) Lanolin having a cholesterol content of 28.4% in the unsaponifiable matter was purified by the solvent fractional crystallization method using methyl ethyl ketone as a solvent as in the above Purification Example 6 to obtain the cholesterol content in the unsaponifiable matter. Obtained 41.1% of hard lanolin. N-hexane eluate obtained by dissolving 10 g of this hard lanolin in 100 ml of n-hexane, passing it through a column previously filled with 50 g of magnesium silicate, and then passing 200 ml of n-hexane. Was distilled off under reduced pressure with a rotary evaporator, and then again passed through the column to give 4.7 g of cholesterol ester.
Got The cholesterol content in the unsaponifiable matter of this cholesterol ester was 65.2%.

(Purification Example 8) 100 g of lanolin having a cholesterol content of 29.7% in the unsaponifiable matter was dissolved in 1000 ml of n-hexane, and the solution was passed through a column previously filled with 500 g of activated alumina, The n-hexane eluate obtained by further passing 2000 ml of n-hexane was distilled off under reduced pressure by a rotary evaporator and then passed through the column again in the same manner to obtain 43.3 g of crude cholesterol ester. The cholesterol content in the unsaponifiable matter of this crude cholesterol ester was 44.3%. Then, 20 ml of methyl ethyl ketone was added to 10 g of this crude cholesterol ester,
It was dissolved by heating at 55 to 65 ° C for 30 minutes, cooled to 5 ° C, and then left at 5 ° C for 24 hours. After 24 hours, filtration was performed using filter paper to separate the precipitate. The separated precipitate was washed with a small amount of methyl ethyl ketone cooled to 5 ° C., the methyl ethyl ketone was distilled off under reduced pressure with a rotary evaporator, and the same operation was repeated 3 times to obtain 2.8 g of cholesterol ester. The cholesterol content in the unsaponifiable matter of this cholesterol ester was 67.7%.

[0023]

[Formulation Example]

(Formulation Examples 1 to 8 and Comparative Examples 1 to 3) Using the cholesterol esters obtained in the above Purification Examples 1 to 8, hand creams of Formulation Examples 1 to 8 were prepared according to the formulations shown in Table 1. In addition, as comparative examples, lanolin (trade name; Super-lanolin (manufactured by Croda Japan Co., Ltd.)), lanolin acetate (trade name: Aceran J (Croda Japan Co., Ltd.)
), Lanolin fatty acid cholesteryl (trade name; YOFCO
Using CLE-S (manufactured by Yoshikawa Oil Co., Ltd.), the hand creams of Comparative Examples 1 to 3 were prepared according to the formulations shown in Table 2.

[Table 1]

[Table 2]

[0024]

[Test example]

(Test Example 1) The hand cream prepared in Formulation Examples 1 to 8 and Comparative Examples 1 to 3 was applied to a total of 20 panelists including 10 girls aged 20 to 30 and 10 girls aged 31 to 45. Let me use
A sensory test was conducted on the feeling of use. The test method was to wash the hands of each panelist with soap in advance and to wipe off water sufficiently, and then apply about 0.2 g each of the hand creams of Prescription Examples 1 to 8 and Comparative Examples 1 to 3 on the back of the left hand. Then, after extending thinly with the right hand, the evaluation of "moistness" and "extension" after 10 minutes was conducted by an interview. Regarding "moisturization", 5 points are very moist, 5 points, moist, 4 points, slightly moist, 3 points, normal, 2 points, and non-moist, 1 point. Also, regarding "extension", 5 points for very good extension, 4 points for good extension, 3 points for extension, 2 points for extension, 2 points for normal extension, and 1 point for not extension are evaluated respectively. The average value was used as an index of "moistness" and "prolongation". The results are shown in Tables 3 to 4.
Shown in.

[0025]

[Table 3]

[Table 4]

(Test Example 2) (Moisture Retention Test) About 0.1 g of the hand cream prepared in Formulation Examples 1 to 2, 6 to 7 and Comparative Example 1 was put on the back of the same panelist's left hand, and the right hand. After rubbing with an index finger for 15 seconds, the electric conductivity after 120 minutes was measured using a skin surface moisture meter (Skikov 301 manufactured by Amic Group). There were 12 measurement points, and the average value was taken as the electrical conductivity. From the obtained electric conductivity, the water retention capacity (%) was calculated according to the following formula (Equation 1). The results are shown in Table 5.

[Equation 1]

[Table 5]

(Test Example 3) Using the cholesterol esters obtained in the above Purification Examples 1 to 8, vanishing creams of Formulation Examples 9 to 16 were prepared according to the formulations shown in Table 6. Further, as comparative examples, lanolin (trade name; super lanolin (manufactured by Croda Japan Co., Ltd.)) and lanolin acetate (trade name;
Comparative Example 4 according to the formulation shown in Table 7 using Aceran J (manufactured by Croda Japan Co., Ltd.) and lanolin fatty acid cholesteryl (trade name; YOFCO CLE-S (manufactured by Yoshikawa Essential Oil Co., Ltd.)).
~ 6 vanishing creams were prepared respectively. The obtained vanishing cream was tested by a panelist for "moistiness" and "spreadiness" in the same manner as in Test Example 1 above. The results are shown in Tables 8 to 9.

[Table 6]

[Table 7]

[Table 8]

[Table 9]

(Test Example 4) Using the cholesterol esters obtained in the above Purification Examples 1 to 8, emulsions of Formulation Examples 17 to 24 were prepared according to the formulations shown in Table 10. Further, as comparative examples, lanolin (trade name; Super-lanolin (manufactured by Croda Japan Co., Ltd.)), lanolin acetate (trade name; Aceran J (manufactured by Croda Japan Co., Ltd.)), lanolin fatty acid cholesteryl (trade name; YOFCO CLE-S) (Manufactured by Yoshikawa Essential Oil Co., Ltd.) was used to prepare the emulsions of Comparative Examples 7 to 9 according to the formulations shown in Table 11. The emulsion thus obtained was tested by a panelist for "moistiness" and "spreading" in the same manner as in Test Example 1 above. The results are shown in Tables 12 to 13.

[Table 10]

[Table 11]

[Table 12]

[Table 13]

As is clear from the results of Tables 3 to 4, Tables 8 to 9 and Tables 12 to 13, the hand creams, vanishing creams and emulsions formulated with the cholesterol ester obtained in the purified examples were more than those in the comparative examples. It can be seen that the feeling of use such as moistness and elongation is extremely excellent. Also,
As is clear from the results in Table 5, the hand cream formulated with the cholesterol obtained in the purified example has an extremely excellent water retention capacity as compared with the hand cream in the comparative example.

[0030]

As described in detail above, the present invention is a solvent fractional crystallization method in which a raw fat or oil selected from wool grease, lanolin or a lanolin derivative and having a cholesterol content in the unsaponifiable matter of at least 25% or more is used. And a column chromatography method are combined to purify a cholesterol ester having a cholesterol content in the unsaponifiable matter of 50% or more, and a cholesterol content in the unsaponifiable matter is at least Since the external preparation for skin is characterized by containing 50% or more of cholesterol ester, as apparent from the results of the above-mentioned Examples and Test Examples,
It is an excellent method that can directly and easily separate and purify cholesterol ester, which has an extremely high cholesterol content in unsaponifiable matter, from natural wool grease, lanolin, etc. and moisturizes the skin. ,
It has the effect of being a skin external preparation containing a cholesterol ester that exerts an important action as an intercellular lipid and having an extremely excellent moist feeling and water retention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C11B 3/00 2115-4H 3/10 2115-4H 7/00 2115-4H

Claims (3)

[Claims] 1. A raw oil / fat selected from wool grease, lanolin or a lanolin derivative and having a cholesterol content of at least 25% or more in the unsaponifiable matter is obtained by a combination of a solvent fractionation crystallization method and a column chromatography method. A method for purifying cholesterol ester, which comprises purifying cholesterol ester having a cholesterol content of 50% or more in a saponified product. 2. An external preparation for skin, which comprises a cholesterol ester having a cholesterol content of at least 50% in the unsaponifiable matter. 3. The external preparation for skin according to claim 2, wherein the cholesterol ester is lanolin or a derivative thereof.