KR102444926B1 - Vegetable recombinant mimic mink oil and cosmetic composition comprising same - Google Patents

Abstract

The present invention provides a recombinant vegetable mink oil analogue. More specifically, the present invention relates to oil that makes it possible not only to solve the rancidity and color, which are problems found in animal oils while having the functionality of mink oil, but also to have ecological advantages by substituting for oils derived from endangered animals, and to a cosmetic composition comprising the same.

Description

Vegetable recombinant mimic mink oil and cosmetic composition comprising same

The present invention relates to a plant-like recombinant mink oil and a cosmetic composition comprising the same.

In modern society, skin diseases are rapidly increasing due to fine dust and UV exposure caused by environmental pollution, and cosmetics are expected to function as daily necessities to prevent them. On the other hand, in the case of animal oil, which is a natural material, although it is more friendly and safe to the human skin, the demand for it is insignificant due to its unique smell, heavy feeling of use, and consumer rejection. is increasing rapidly.

As an animal oil used as a cosmetic composition, representative mink oil is obtained from Adipose tissue, a separation membrane that exists as a component of subcutaneous cells in the abdomen of mink, and only about 5 to 10 g per animal is extracted. It is a refined oil.

Mink oil contains 13 to 20% by weight of palmitoleic acid, and serves to maintain the balance of the skin barrier. Palmitoleic acid has excellent spreadability and penetration as a carrier and softener, and has excellent absorbency, leaving a soft, non-sticky feeling when applied to the skin. In addition, it prevents skin aging and activates the flow of blood or lymph to protect the skin from free radicals. Palmitoleic acid can be used as a supplement for palmitoleic acid in the skin, which is reduced due to skin aging, and helps to maintain the lipidmantel of the skin. It is suitable for all skin types, especially dry skin or skin elasticity and moisturizing It is suitable for flaky skin. Since mink oil contains palmitoleic acid, it has an excellent effect in effectively protecting the skin barrier, which is easily destroyed by external or internal factors and seasonal factors.

Mink oil can exhibit the effects of preventing wrinkles due to nourishment and moisturizing, alleviating or preventing spots, freckles, and blemishes caused by promoting skin cell regeneration, blocking UV rays, and neutralizing sensitive or oily skin. In addition, mink oil improves seborrheic dermatitis that is very itchy due to swelling of the face and neck, helps make-up work well, and improves the luster of the skin color. In case of burns, apply immediately to prevent blisters and scars. In addition, it relieves or improves skin troubles such as housewives eczema, atopic dermatitis. It supplements the lack of sebum to prevent dry skin, prevents stretch marks during pregnancy or diet, and has excellent effects on itchy and cracking athlete's foot.

Despite the many effects expected when used as a cosmetic, mink oil is not widely used in cosmetics due to the following problems. It is rare enough that only about 5 to 10 g per animal can be extracted, so the unit price is high, and there is an ethical problem because it is obtained by slaughtering animals. In addition, the peculiar fishy smell and rancid odor of animal oil are also difficult to use as cosmetics, so improvement of these problems is urgently needed.

Korean Patent Publication 10-2019-0075408 A Chinese Patent Publication 106937937 A

An object of the present invention is to provide a plant-recombined similar mink oil to solve the problems of rancidity and color of animal oil while having the nourishing and moisturizing function of mink oil, and to replace the oil derived from an endangered species of animal, thereby providing ecological and environmental protection. It is to provide an oil that can have advantages and a cosmetic composition comprising the same.

The present invention provides a vegetable recombinant-like mink oil, characterized in that vegetable oil: fatty acid is included in a weight ratio of 1: 0.001 to 0.05, and is prepared through an enzymatic esterification reaction.

The vegetable recombinant-like mink oil according to an embodiment of the present invention contains 35.0 to 45.0 wt% of oleic acid, 11.0 to 21.0 wt% of palmitic acid, 11.0 to 21.0 wt% of linoleic acid, 10.0 to 20.0 wt% of palmitoleic acid, in advance It may contain 1.0 to 7.0% by weight of stic acid, 1.0 to 6.0% by weight of stearic acid, 0.5 to 2.0% by weight of eicosenoic acid, and 85 to 99% by weight of the composition of animal mink oil and constituent fatty acids.

The vegetable oil contained in the vegetable recombinant-like mink oil according to an embodiment of the present invention is from soybean oil, macadamia oil, sea buckthorn fruit oil, avocado oil, corn oil, walnut oil, coconut oil, palm oil, grapeseed oil and hazelnut oil. One or two or more may be selected, and the fatty acid may be one or two or more selected from myristic acid, palmitic acid, and stearic acid.

In the vegetable recombinant-like mink oil according to an embodiment of the present invention, the content of monoglyceride and diglyceride may be 0.1 to 1.0% by weight, and the content of free fatty acid may be 0.01 to 0.1% by weight.

Also, in one embodiment, the enzyme may be a fixed enzyme, and the enzymatic esterification reaction may be performed at 40 to 90 °C for 5 to 20 hours.

The present invention provides a cosmetic composition comprising 0.1 to 10.0% by weight of the vegetable recombinant-like mink oil.

The vegetable recombinant-like mink oil of the present invention has the natural nourishment and moisturizing function of mink oil, solves the problems of rancidity and color of animal oil, and replaces oil derived from endangered animals, thereby having ecological and environmental advantages. can

In addition, the process using the enzymatic esterification reaction, which is a method of producing the plant-recombined similar mink oil, has a low generation of impurities that may occur in the chemical process, and does not use a solvent, so it can have advantages for use as a raw material for cosmetics, It is an economical process and has high industrial use value.

The cosmetic composition containing the plant-derived recombinant-like mink oil can solve the ethical problems of price, rancidity, color, and animal origin due to the scarcity of mink oil, and has commercial value by having excellent cosmetic properties. can

1 is a diagram showing the results of measuring the phase stability of Example 1, Comparative Example, and mink oil after 7 days.
2 is a diagram showing the GC analysis results of Example 1. FIG.
3 is a diagram showing the GC analysis results of Example 2. FIG.
4 is a view showing a panel test for feeling of use of Example 1 and mink oil.
5 is a diagram showing the GC analysis results of Example 1 and mink oil.

The present invention provides a vegetable recombinant-like mink oil and a cosmetic composition comprising the same.

The singular form used in the present invention may also be intended to include the plural form unless the context dictates otherwise.

In addition, the numerical range used in the present invention includes a lower limit and an upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, "comprises" is an open-ended description that has a meaning equivalent to expressions such as "comprises", "contains", "has" or "characterizes", and is an element not listed further; Materials or processes are not excluded.

Hereinafter, the present invention will be specifically described. At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by a person of ordinary skill in the art to which this invention belongs, and may unnecessarily obscure the subject matter of the present invention in the following description. Descriptions of possible known functions and configurations will be omitted.

The present invention provides a vegetable recombinant-like mink oil, characterized in that vegetable oil: fatty acid is included in a weight ratio of 1: 0.001 to 0.05, and is prepared through an enzymatic esterification reaction. Preferably, for the efficiency and lifespan of the enzyme used in the esterification reaction, the vegetable oil: fatty acid may be included in a weight ratio of 1: 0.003 to 0.05, more preferably 1: 0.005 to 0.03 by weight.

Enzymatic reactions have high substrate specificity compared to reactions with normal chemical catalysts. In addition, it has advantages such as being able to react under mild conditions of room temperature and normal pressure. Enzymes are originally water-soluble proteins, and when performing an enzymatic reaction, the enzyme is generally dissolved in a reaction solution. However, in this general method, it is not easy to recover the used enzyme from the reaction solution after completion of the reaction, and the enzyme is disposable. This is particularly a big problem when the enzyme cannot be obtained at low cost or when the operation for producing the enzyme is complicated.

For effective use of the enzyme, the enzyme must be easily recovered from the reaction solution by any method. An enzyme processed for this purpose is an immobilized enzyme. By filling the column with the immobilized enzyme and flowing the reaction solution, it is also possible to continuously carry out the enzymatic reaction.

In one embodiment of the present invention, the immobilized enzyme is used by filling the column, but is not limited thereto, and the method using the immobilized enzyme known in the art is not limited.

The enzyme used in the esterification reaction according to an embodiment of the present invention is Candida Antarctica B, Thermomyces lanuginosus, Rhizomcor miehei, Rhizomcor miehei (Rhizopus delemar), Mucormiehei, Alcaligenes sp., Aspergillus niger, Candida cylindraces, Burkholderia cepacia and Zeo It may be one or two or more selected from Tricume candidum (Geotricum candidum), and preferably Thermomyces lanuginosus (Thermomyces lanuginosus), rhizomcor miehei (Rhizomucour miehei) or a mixture thereof.

Mink oil is similar to the sebum component of the skin, so it is not greasy and has a high absorption feeling without feeling stuffy. In contrast to the ethical problem of slaughtering animals, and the problem of being reluctant as a component of cosmetics due to the rancid odor and color as an animal-derived raw material, the plant-derived recombinant-like mink oil according to an embodiment of the present invention is It can solve the above problems while maintaining the original advantages of mink oil, so it has a very high use value as a material that can replace the demand for mink oil.

The vegetable recombinant-like mink oil according to an embodiment of the present invention contains 35.0 to 45.0 wt% of oleic acid, 11.0 to 21.0 wt% of palmitic acid, 11.0 to 21.0 wt% of linoleic acid, 10.0 to 20.0 wt% of palmitoleic acid, in advance It may contain 1.0 to 7.0% by weight of stic acid, 1.0 to 6.0% by weight of stearic acid, and 0.5 to 2.0% by weight of eicosenoic acid, and the composition of animal mink oil and constituent fatty acids may match 85 to 99% by weight, preferably 86 to 99% by weight, more preferably 90 to 99% by weight.

The vegetable oil contained in the vegetable recombinant-like mink oil according to an embodiment of the present invention is from soybean oil, macadamia oil, sea buckthorn fruit oil, avocado oil, corn oil, walnut oil, coconut oil, palm oil, grapeseed oil and hazelnut oil. It may be one or two or more selected from, specifically soybean oil, macadamia oil, walnut oil, coconut oil, palm oil, and grapeseed oil may be one or two or more selected from, and more specifically, soybean oil, macadamia oil, palm oil and grapeseed oil It may be one or two or more, but is not limited thereto.

Macadamia nut oil (Macadamia ternifolia seed oil) is a vegetable oil extracted from macadamia fruits harvested in Australia, Hawaii, Brazil, South Africa, and Israel. have The macadamia oil is composed of oleic acid, which is a monounsaturated fatty acid, in an amount of about 80% by weight or more of the total weight, and the oleic acid exhibits skin anti-aging activity. In addition, macadamia oil contains about 20% by weight of palmitoleic acid based on the total weight, and the palmitoleic acid is an essential component constituting the sebum of animal skin. Palmitoleic acid, which accounts for about 22% by weight of the lipid component of human skin, together with palmitic acid, occupies about half of the skin lipid, and has a lubrication, softening, and protein structure of the skin. It has functions such as protection.

Palm oil consists of unsaturated fatty acids and saturated fatty acids in a ratio of almost 1:1, so it is solid at room temperature, and the content of saturated fatty acids is similar to animal fats, but it contains tocopherol, which is a characteristic of vegetable oils, and contains no cholesterol. is distinguished from The fatty acid composition of palm oil is about 45% by weight of palmitic acid, about 35% by weight of oleic acid, and about 10% by weight of linoleic acid. In addition, palm oil contains carotene, which is 15 times that of carrots and 300 times that of tomatoes. The carotene content of palm oil is high, so it has the same UV protection effect as the SPF 15 sunscreen, so it can damage the skin from UV rays and prevent pigmentation. has the effect of reducing In addition, palm oil reduces moisture loss in the skin to prevent dryness, can be used for sensitive skin, and effectively nourishes areas with eczema, psoriasis and stretch marks.

Grape seed oil is generally non-scented and very light oil without stickiness, so it penetrates into the skin well. , it is characterized by slow rancidity despite the high content of unsaturated fatty acids, which are rapidly oxidized. Grape seed oil contains abundant unsaturated fatty acids such as linoleic acid and oleic acid, which play an important role in the skin cell membrane, and thus has an excellent skin regeneration effect.

In one embodiment of the present invention, the fatty acid used in the preparation of the vegetable recombinant-like mink oil may be one or two or more selected from myristic acid, palmitic acid and stearic acid, preferably myristic acid, palmitic acid, or these may be a mixture of The weight ratio of the myristic acid: palmitic acid may be 1: 0.1 to 1, preferably 1: 0.1 to 0.5, more preferably 1: 0.2 to 0.3.

A method for producing a plant-derived recombinant-like mink oil according to an embodiment of the present invention,

a) mixing a fatty acid or fatty acid ester with a vegetable oil;

b) performing an esterification reaction by adding an enzyme to the mixture;

c) filtering and purifying the reactant; and

d) performing a deoxidation process; may include.

The enzyme in step b) may be a stationary enzyme, and the enzymatic esterification reaction is performed at 40 to 90° C. for 5 to 20 hours, preferably at 50 to 80° C. for 7 to 18 hours, more preferably from 60 to It may be carried out at 70° C. for 9 to 15 hours.

In one embodiment of the present invention, as a by-product of the reaction of step b), a monoglyceride in which one OH group of the OH groups of glycerol forms an ester with a fatty acid and a diglyceride in which two OH groups form an ester with a fatty acid are can be created This not only adversely affects the physical properties of the final oil, such as odor and color, but also has a possibility of causing deterioration and should be removed. Therefore, the process of removing monoglycerides and diglycerides may be performed by performing step c), which may be filtration and purification, specifically filtration and distillation, and more specifically, filtration and distillation using a thin film distillation device. have.

The distillation process is performed at a pressure of 1x10 ^-4 to 5x10 ^-3 mbar and a temperature of 140 to 200°C, preferably at a pressure of 5x10 ^-4 to 3x10 ^-3 mbar and a temperature of 150 to 190°C, more preferably 8x10 It may be carried out at a pressure of ^-4 to 2x10 ^-3 mbar and a temperature of 160 to 180°C.

By performing step c), the vegetable recombinant-like mink oil according to an embodiment of the present invention may have a monoglyceride and diglyceride content of 0.1 to 1.0% by weight, and the raw material by performing step c). The inherent odor of vegetable oils can also be removed.

In one embodiment of the present invention, free fatty acids may be added in step a) for an appropriate fatty acid composition, and additional free fatty acids may be produced in step b) to include free fatty acids in the final oil. These free fatty acids may affect the odor and color of the oil, and may cause deterioration and should be removed. The free fatty acid may be removed by performing the deoxidation process of step d), and the free fatty acid content of the vegetable recombinant-like mink oil according to an embodiment of the present invention in which step d) is performed may be 0.01 to 0.1% by weight. have. In addition, the deoxidation process of step d) may be a titration method using sodium hydroxide or potassium hydroxide.

The present invention provides a cosmetic composition comprising the above-mentioned recombinant plant-like mink oil, and the recombinant plant-like mink oil may be included in an amount of 0.1 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 1.0 to 3.0% by weight.

Hereinafter, a method for producing a plant-derived recombinant-like mink oil according to the present invention will be described in more detail through specific examples.

[Example 1]

Step 1: Enzymatic esterification reaction

Macadamia Oil (Jan dekker, Macadamia Nut Oil CP RBD, 1300.0 g), Palm Oil (Elburg global, RBD Palm Oil, 260.0 g) and NHR Organic oils, Organic Refined grapeseed Oil (320.0 g), Sea buckthorn oil ( Nature in bottle, Sea buckthorn oil, 60 g) was placed in a reactor, and myristic acid (IOI Oleochemical, Palmac 98-14, 50.0 g) and palmitic acid (IOI Oleochemical, Palmac 98-16, 10.0 g) were added. Lipozyme TLIM (Novozymes, 70.0 g), an enzyme immobilized on granules, in which Termomyces Lanuginosus-derived lipase is immobilized on porous silica, was reacted at 65° C. for 12 hours to obtain a reaction product (water). Yield 1934.3g).

Step 2: Distillation

Using a thin film distillation apparatus (VTA, VDL 70-7), it was distilled at a pressure of 1x10 ^-3 mbar and a temperature of 170° C. (yield 95.3%).

Step 3: Deoxidation process

221 mL of a 5 wt% aqueous sodium hydroxide solution was slowly added and mixed, heated at 60 to 90° C. and cooled, followed by centrifugation to separate the water layer to obtain an oil.

[Example 2]

The procedure of Example 1 was performed in the same manner as in Example 1, except that the granular immobilized enzyme Lipozyme RM (Novozymes) in which lipase derived from Rhizomcor Miehei was immobilized on acrylic resin was used instead of Lipozyme TLIM.

Examples 1 and 2 were analyzed by GC, and the amount of myristic acid remaining in the oil and fat due to transesterification was compared and shown in Table 1, Figure 2 (Example 1) and Figure 3 (Example 2), Lipozyme TLIM It was confirmed that a more efficient exchange reaction occurred in Example 1 using

Example 1 Example 2 C-18:1 oleic acid 44.2 47.0 C-16:0 Palmitic acid 14.2 13.8 C-18:2 linoleic acid 14.4 14.0 C-16:1 Palmitoleic Acid 13.5 13.1 C-14:0 myristic acid 3.3 2.3 C-18:0 Stearic Acid 3.1 3.4 C-20:1 Eicosenoic Acid 1.7 1.9 C-18:3 Linolenic Acid 0.9 0.9

[Comparative example]

Macadamia Oil (Jan dekker, Macadamia Nut Oil CP RBD, 1300.0 g), Palm Oil (Elburg global, RBD Palm Oil, 260.0 g) and NHR Organic oils, Organic Refined grapeseed Oil (320.0 g), Sea buckthorn oil ( Nature in bottle, Sea buckthorn oil, 60 g) is placed in a reactor, myristic acid (IOI Oleochemical, Palmac 98-14, 50.0 g) and palmitic acid (IOI Oleochemical, Palmac 98-16, 10.0 g) are added and mixed. .

[Experimental Example 1] Melting point analysis

The melting point was analyzed according to the Pharmacopoeia General Test Method 47. Melting Point Measurement Method 2nd method. In Example 1, Comparative Example, and mink oil in a completely dissolved state, 1 cm was filled in one side of the capillary with both sides open, and then left in the freezer for 10 minutes. The capillary sample and the thermometer were set in ethanol at -10°C, and the temperature was raised by 0.5°C per minute. The point at which the oil in the capillary rose was taken as the melting point, and the results are shown in Table 2 below.

mink oil Example 1 comparative example melting point 7.5℃ 8℃ -0.5℃

As shown in Table 1, it can be seen that Example 1 has a melting point similar to that of mink oil.

[Experimental Example 2] Phase stability evaluation

The phase stability of mink oil, Example 1 and Comparative Example after 7 days was evaluated and shown in FIG. 1 . Mink oil and Example 1 were transparent without change even after 7 days as shown in FIG. Therefore, it can be seen that the physical properties of mink oil cannot be represented simply by adjusting the composition of fatty acids, and the phase stability is very deteriorated.

[Experimental Example 3] Evaluation of usability

A panel test was carried out to evaluate the feeling of use of Example 1 and mink oil, and the feeling of use of each oil for 10 panelists was evaluated out of 10 points for 5 items, and the values were averaged and calculated. The results are shown in Table 3 and FIG. 4 below.

spreadability absorption drunk moisturizing residual feeling mink oil 8.2 8.1 5.1 8.8 9.0 Experimental Example 1 8.1 8.4 8.4 8.7 8.5

Example 1 of the present invention showed values similar to those of mink oil in spreadability, absorption feeling, and moisturizing feeling, and showed very improved values in smell. As a result, it can be seen that Example 1 of the present invention exhibits an excellent feeling of use with very low rancidity while maintaining the natural moisturizing feeling of mink oil.

[Experimental Example 3] GC analysis of fatty acid composition

1.5 mL of sodium hydroxide solution (0.5N in methanol) was added to each 0.025 g of Example 1 and mink oil, heated for 5 minutes, and then cooled in a thermostat at 25°C. 2.0 mL of BF ₃ (14 % in methanol) was added, and after heating, it was cooled in a thermostat at 25°C. 2.0 mL of isooctane and 2 mL of brine were added, mixed and left to stand. The supernatant was separated and water was removed, followed by GC analysis.

The analysis results are shown in Tables 4 and 5 below, and it can be seen that Example 1 shows a composition consistent with mink oil by 88% by weight or more in the top 8 autogenous acids.

mink oil Example 1 C-18:1 oleic acid 39.5 44.4 C-16:0 Palmitic acid 16.0 14.2 C-18:2 linoleic acid 16.0 14.4 C-16:1 palmitoleic acid 15.0 13.5 C-14:0 myristic acid 3.5 3.3 C-18:0 Stearic Acid 3.0 3.1 C-20:1 Eicosenoic Acid 1.5 1.7 C-18:3 Linolenic Acid 1.0 0.9

It can be seen that the vegetable recombinant-like mink oil of Example 1 of the present invention is very similar to the actual mink oil in the GC analysis of the melting point and fatty acid component, and is similar in feel or has very improved rancidity.

Therefore, the vegetable recombinant-like mink oil according to an embodiment of the present invention can exhibit the natural feeling of use, nourishment effect and moisturizing effect of mink oil, while solving the problems caused by rejection of animal-derived oils, rancidity and color. . In addition, the plant-recombined-like mink oil can solve the economic problem due to the scarcity of mink oil, and it can also solve the ethical problem of slaughtering animals.

The production method of the plant-based recombinant-like mink oil of the present invention has low production of impurities that may occur in chemical processes due to enzymatic esterification, and is suitable as a cosmetic because there is no use of solvents. Since no filtration process is required, very economical process design is possible. Therefore, it is thought that the vegetable recombinant-like mink oil of the present invention can replace the demand for mink oil, which has not been widely utilized due to the above problems, and its commercial use is highly expected.

As described above, the present invention has been described with specific matters and limited examples and comparative examples, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention is not limited to the above examples. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (10)

Vegetable oil: fatty acid is included in a weight ratio of 1: 0.001 to 0.05;
The vegetable oil is one or two or more selected from macadamia oil, sea buckthorn oil, palm oil and grapeseed oil;
the fatty acid is myristic acid, palmitic acid or a mixture thereof;
A vegetable recombinant-like mink oil, characterized in that it is prepared through an enzymatic esterification reaction using Lipozyme TLIM, Lipozyme RM, or a mixture thereof, which is an immobilized enzyme on granules to which lipase is immobilized. According to claim 1,
The vegetable recombinant-like mink oil contains 35.0 to 45.0 wt% of oleic acid, 11.0 to 21.0 wt% of palmitic acid, 11.0 to 21.0 wt% of linoleic acid, 10.0 to 20.0 wt% of palmitoleic acid, 1.0 to 7.0 wt% of myristic acid, A vegetable recombinant-like mink oil containing 1.0 to 6.0% by weight of stearic acid and 0.5 to 2.0% by weight of eicosenoic acid. According to claim 1,
The vegetable-recombined-like mink oil is an animal-derived mink oil and a component fatty acid composition that matches 85 to 99% by weight, a plant-like recombinant mink oil. delete delete According to claim 1,
The vegetable recombinant-like mink oil has a monoglyceride and diglyceride content of 0.1 to 1.0% by weight, plant-like recombinant mink oil. According to claim 1,
The vegetable recombinant-like mink oil has a free fatty acid content of 0.01 to 0.1% by weight, plant-like recombinant mink oil. delete According to claim 1,
The enzymatic esterification reaction is carried out for 5 to 20 hours at 40 to 90 ℃, plant-like recombinant mink oil. A cosmetic composition comprising 0.1 to 10.0% by weight of the vegetable recombinant-like mink oil according to any one of claims 1 to 3, 6, 7 and 9.

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