JPH06306387A - Concentration of vegetable squalane - Google Patents

Abstract

PURPOSE:To obtain a colorless, odorless and highly pure vegetable squalane concentrate at good efficiency by hydrogenating a squalane-bearing vegetable fat or oil (deodorized concentrate) and wintering the hydrogenate in an organic solvent. CONSTITUTION:A vegetable fat or oil such as squalane-bearing olive oil or rice bran oil or a disdeodorized distillate thereof is hydrogenated to obtain a hydrogenate of an iodine value of desirably 10 or below more desirably 1 or below. This hydrogenate is dissolved or dispersed in an organic solvent (e.g. ethyl acetate) and wintered to separate impurities. The wintering treatment consists of cooling the hydrogenate with a freezing medium such as dry ice at a rate of cooling of 0.2 deg.C per min or slower to a final cooling temperature of -15 deg.C or below and keeping the hydrogenate at this temperature for at least 24hr. The precipitated crystals are filtered off, and the solvent is distilled off from the filtrate to obtain a vegetable squalane concentrate. The obtained concentrate can be desirably used in fields of cosmetics, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for concentrating vegetable squalane, which can be used in the fields of cosmetics and pharmaceuticals. More specifically, the present invention relates to a method for concentrating vegetable squalane, which comprises hydrogenating a vegetable oil containing squalene or a deodorized distillate thereof and then performing wintering in an organic solvent.

[0002]

2. Description of the Related Art Paraffins (C
_n H _{2n + 2} ) and naphthenic compounds (C _n H _2n ), most of which have long been used as raw materials for cosmetics or pharmaceuticals are C ₁₅ or more paraffinic hydrocarbons. These are classified as mineral hydrocarbons because they are collected from petroleum resources, but other hydrocarbons are squalane (2,6,10,15,19,23-hexamethyltetracosane) and pristane ( Some of them are collected separately from animal sources, such as (2,6,10,14-tetramethylpentadecane). Although liquid paraffin is the most widely used and abundant in hydrocarbons, squalane is less oily than liquid paraffin and has a good feeling of use, so it is widely used as an oily base for various cosmetics and pharmaceuticals. Has been. The purpose of use is as follows.

A) Cleans the skin surface using the solvent effect. b) To promote the friction effect on the skin surface. c) A hydrophobic film is formed on the skin surface to suppress evaporation of water from the skin surface. d) A waterproof coating is formed on the skin surface to enhance the makeup effect. Conventionally, the commonly used natural squalane is animal squalane, and the sole raw material thereof is shark. This is a squalene (2,6,10,1) sampled from deep-sea shark liver oil.
Hydrogenated 5,19,23-hexamethyl-2,6,10,14,18,22-tetracosahexaene) with a low freezing point of -38 ° C and high stability.

By the way, in recent years, although the demand for squalane has been increasing year by year, the catch of sharks has been declining, and the prices have been forced to soar. In Norway, the main source of sharks, changes in ocean currents due to worsening weather conditions have led to lower shark catches, and Spanish (African) products are limited to European demand.
Therefore, it is expected that the difficulty in obtaining squalane derived from sharks will continue in the future. As mentioned above, the natural squalane that has been put on the market to date is essentially derived from sharks, and due to the recent growing interest in animal protection, it is becoming more difficult to obtain natural squalane.

Therefore, the present inventors focused their attention on the production of plant-derived squalane in the face of a tight supply and demand of natural squalane. It was already known that squalene and its homologue squalene are also contained in plant tissues, especially in fruits and oil seeds. It was practically impossible to extract / separate into. For example, the unsaponifiable matter contained in olive oil usually contains 60 to 75% by weight of squalane and squalene, but the unsaponifiable matter contained in olive oil is about 0.5 to 1.4% by weight.

The above-mentioned unsaponifiable matter is generally obtained as a deodorizing distillate in the production process of edible oil, but its composition is extremely complicated and various physical properties such as chemical structure, boiling point and polarity of squalane are approximated. Components such as saturated and unsaturated hydrocarbons having similar carbon numbers are also contained in large amounts, and it has been difficult to concentrate squalane to a high concentration.

[0007]

Therefore, the present inventors have found that
As a result of intensive studies on a method for producing natural squalane using a plant as a raw material, it was found that components other than squalane can be removed by treating the plant extract under specific conditions, and the present invention has been completed. That is, the present invention is
An object of the present invention is to provide a method for easily and efficiently obtaining a plant-derived squalane at a high concentration.

[0008]

The present invention provides a method for concentrating vegetable squalane, which comprises hydrogenating a vegetable oil containing squalene or a deodorized distillate thereof and then wintering it in an organic solvent. Regarding In the present invention, the vegetable oil or fat as a raw material is a plant tissue such as fruits and oil seeds containing squalene, for example, olive, rice bran, soybean, palm and the like are squeezed and / or an organic solvent such as hexane. The crude oil obtained by processing by a conventional method such as extraction used, its degummed oil, deoxidized oil, or decolorized oil, which can be collected from a usual edible oil production process.

Further, in the present invention, a deodorizing distillate obtained by deodorizing such vegetable oils and fats by a conventional method can be used as a raw material. In the present invention, the thus obtained olive oil, rice bran oil, soybean oil, palm oil and the like or deodorized distillate thereof can be used as a raw material, but olive oil and rice bran oil are particularly preferable, and olive oil and rice bran are particularly preferable. Each deodorant distillate of oil is advantageous. These raw materials do not necessarily have to be a single type, and two or more types may be mixed.

In the method of the present invention, it is important that the raw material is first hydrogenated by a conventional method to reduce the iodine value to preferably 10 or less, and more preferably 1 or less. The hydrogenation can be carried out by a known method using a nickel catalyst or the like under normal pressure or under pressure. If the next step of the present invention is applied while the unhydrogenated or iodine value exceeds 10, not only cannot squalene be converted into squalane, but also unsaturated impurities (hydrocarbons having similar carbon number) Is difficult to remove, and even if hydrogenation treatment is performed in a later step, it is necessary to remove the saturated impurities newly generated after the hydrogenation treatment again, and the removal efficiency of impurities that should originally be removed Is significantly reduced, and squalene, which is a source of squalane, is also lost, resulting in a reduction in the yield of squalene, which is the object of the present invention. In the present invention, the raw material may be pretreated, if necessary, prior to the hydrogenation.

The hydrogenated raw material is then dissolved or dispersed in an organic solvent to give a solution. The organic solvent that can be used may be any of halogen-based, hydrocarbon-based, alcohol-based, ketone-based and ester-based solutions, or a mixed solution thereof is suitable, but ketone-based and ester-based solvents are preferable, and methyl-based ketone is used for the ketone-based solvent. In the ester system, ethyl acetate is preferable. If the amount of such a solvent used is small, the yield of the desired product will decrease, and if it is large, it will lead to an increase in equipment and manufacturing costs. A volume of 5 to 10 times is suitable.

Subsequently, the solution is subjected to wintering treatment. As a cooling method, a cryogen such as dry ice or dry ice-acetone, an antifreeze solution, liquid nitrogen, or the like may be used, and the mixture may be stirred or left standing. Although the cooling condition depends on the kind and composition of the raw material, the cooling rate is commonly 0.2 ° C./min or less, preferably 0.02 ° C./min to 0.2.
C./min. If the temperature exceeds 0.2.degree. C./min, rapid cooling cannot increase the purity of the target product, and conversely, even if the temperature is slowly cooled to more than 0.02.degree. C./min, further purification is possible. I can't hope. The ultimate cooling temperature is -15 ° C or lower, preferably -20 to 20 ° C.
-30 ° C is good. If the temperature does not reach -15 ° C, the degree of crystal precipitation of impurities in the treatment solution is small, and as a result, it becomes difficult to obtain a high-purity target product. It is also necessary to maintain the treatment solution at the cooling ultimate temperature for at least 24 hours or longer, preferably 72 to 96 hours, in order to increase the purity of the target product.

The crystals thus precipitated in the treatment solution are filtered using a filter paper, an ultrafiltration membrane or the like, and the solvent is distilled off from the filtrate to give the plant squalane concentrate of the present invention. Obtainable. The concentrate has a squalane concentration of about 80 to 95% by weight, has no offensive odor due to coloring or raw materials, does not form crystals in the range of room temperature to about -35 ° C, and does not have a cloudiness. It does not lose its liquidity.

[0014]

【Example】

Example 1 Steam was blown into olive oil pressed by a conventional method to obtain 5
The distillate (iodine value: IV = 295) deodorized at 250 to 265 ° C. under reduced pressure of 10 mmHg was hydrogenated by a conventional method using a nickel catalyst. This hydrogenated product (IV =
1) 500 g was dissolved in 5 times volume of ethyl acetate, and the mixture was allowed to stand at 4 ° C. for one day and night, and then the precipitated crystal product was filtered off with a filter paper. The obtained filtrate was further cooled at a cooling rate of 0.2 ° C./minute, and finally allowed to stand at −20 ° C. for 72 hours, and then the crystalline substance was similarly filtered off. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain 395 g of an olive-derived plant squalane concentrate. Squalane purity in this concentrate (by GLC)
Was 87%, was colorless and had no offensive odor, did not become cloudy even at -30 ° C, and did not lose its fluidity.

Example 2 A deodorized distillate (IV = 270) obtained by treating rice bran oil in the same manner as in Example 1 was hydrogenated by a conventional method using a nickel catalyst. 1 kg of this hydrogenated product (IV = 3)
It was dissolved in a double volume of methyl ethyl ketone, cooled to −30 ° C. at a cooling rate of 0.05 ° C./min, allowed to stand at the same temperature for 48 hours, and then separated by filtration to separate a filtrate and crystals. The crystalline substance was dissolved again in methyl ethyl ketone in a volume 5 times the weight of the starting material with heating, cooled to −20 ° C. at the same cooling rate, and allowed to stand still for one day at the same temperature, and then the precipitated crystalline substance was filtered off. Both filtrates were combined and the solvent was distilled off under reduced pressure to obtain 225 g of a rice-derived plant squalane concentrate. Squalane in this concentrate is GL
It had a C purity of 90%, was colorless and odorless, and did not lose its fluidity even at -30 ° C.

Example 3 Soybean crude oil obtained by pressing soybean and extracting with hexane was subjected to saponification and solvent extraction according to a conventional method to obtain an unsaponifiable matter. 100 g of this unsaponifiable matter was hydrogenated by a conventional method using a nickel catalyst, and the catalyst was removed.
98 g of hydrogenated product of = 1 was obtained. The hydrogenated product was dissolved in a 3-fold volume of ethyl acetate / methyl ethyl ketone = 1/1 mixed solvent and treated in the same manner as in Example 1. In addition, -30 ℃
It was left still for 96 hours. The crystallized product was filtered off, and 23 g of a plant-based squalane concentrate derived from soybean was recovered from the filtrate. GL
Squalane purity by C: 94%, colorless, odorless, -35
It did not become cloudy at 0 ° C and maintained fluidity.

Comparative Example 1 The hydrogenated product of the rice bran oil deodorizing distillate used in Example 2 exhibits a cloudy gel at room temperature and almost solidifies in a refrigerator at 4 ° C. 15 g of the filtrate obtained by subjecting this 100 g to the wintering treatment as it was was returned to a refrigerator at the same temperature and became cloudy (squalane purity by GLC: 25%). Thereafter, the crystal precipitation temperature was finally lowered to -20 ° C in five stages (the cooling rate and the crystal precipitation temperature holding time were the same as in Example 2). A squalane purity of 83% was obtained, but the yield was 1 g or less.

Comparative Example 2 500 g of the olive oil deodorizing distillate obtained in Example 1 was dissolved in 5 volumes of acetone and cooled at a rate of 1 ° C./min to -20 ° C.
After standing still for 72 hours, the precipitated crystal was filtered off.
When the composition of the obtained crystal was analyzed by GLC, linear saturated hydrocarbon and squalene were detected as the main components.
When the filtrate was hydrogenated after distilling off the solvent, the whole became cloudy and lost its fluidity at room temperature. This was again subjected to wintering treatment under the same conditions as above, and the squalane purity was 78%.
There was obtained 135 g of This produced some cloudiness at -20 ° C.

[0019]

According to the method of the present invention, a plant is used as a raw material,
Impurities similar to squalane in the chemical structure and physical properties present in the extract could be easily separated, and it was possible to efficiently concentrate highly pure vegetable squalane without odor and odor.

Claims (4)

[Claims] 1. A method for concentrating vegetable squalane, which comprises hydrogenating a vegetable oil containing squalene or a deodorized distillate thereof and then wintering it in an organic solvent. 2. The method according to claim 1, wherein the vegetable oil is at least one selected from the group consisting of olive oil, rice bran oil, soybean oil and palm oil. 3. The method according to claim 1, wherein the organic solvent is a ketone type, an ester type or a mixed liquid thereof. 4. The wintering has a cooling rate of 0.
Cool at 2 ° C or lower, and set the ultimate cooling temperature to -15 ° C or lower,
The method according to claim 1, wherein the temperature is maintained for at least 24 hours.