JP2009079016A - Raw material for cosmetic and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a raw material for a cosmetic which can inhibit the formation of 8-hydroxy-2'-deoxyguanosine (8-OHdG) and can accelerate the synthesis of collagen to particularly improve wrinkles and sagging of the skin and the like and a cosmetic having a very high effect on improving a rough dry skin by using the raw material. <P>SOLUTION: The cosmetic raw material comprises a proteoglycan extracted from a shark cartilage and ethylbisiminomethylguaiacol manganese chloride and can inhibit the formation of 8-hydroxy-2'-deoxyguanosine and can accelerate the synthesis of collagen. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a cosmetic raw material having the ability to suppress the formation of 8-hydroxy-2'-deoxyguanosine and the ability to promote collagen synthesis, and a cosmetic having a very high effect of improving skin roughness by blending this cosmetic raw material.

Conventionally, proteoglycan has been used as an external preparation for skin. For example, a whitening cosmetic is known in which L-ascorbic acid phosphate is blended in a proteoglycan extract (Patent Document 1). Further, as a proteoglycan used in a skin external preparation, a method for obtaining shark cartilage-derived proteoglycan is known (Patent Document 2). Compared to the proteoglycans derived from higher animals such as cattle and pigs that have been used in the past, shark cartilage-derived proteoglycans are highly transparent and effective as a raw material for external preparations for skin, wrinkles, and tarmi. It is known that this shark cartilage-derived proteoglycan is combined with a melanin production inhibitor and a herbal extract having an active oxygen scavenging action (Patent Document 3).
In addition, it is known to use a salen-metal complex as an antioxidant (Patent Document 4).

The effect required for external preparations for skin, particularly cosmetics, is basically fulfilling the demand to make younger than the actual age. There are also stains for the reason that the age seems to be high, but the proportion of cocoons and tarmi is high. As a cause of wrinkles and tarmi, formation of 8-hydroxy-2′-deoxyguanosine (hereinafter referred to as “8-OHdG”) due to oxidative damage of guanine base in DNA by the action of active oxygen, extracellular matrix Examples include reduction of collagen as a component.
However, there is no known cosmetic raw material that can suppress 8-OHdG formation and promote collagen synthesis, and this cosmetic raw material can be used to reduce wrinkles and tarmi, thereby improving skin roughness. No good cosmetics are known.
JP-A-4-210614 JP 2003-246740 A Japanese Patent Laid-Open No. 2003-300858 Japanese National Patent Publication No. 8-504 211

  The present invention was made to cope with such problems, and in particular, for the purpose of improving skin wrinkles and talmi, providing a cosmetic raw material having an ability to suppress 8-OHdG formation and an ability to promote collagen synthesis, And it aims at provision of the cosmetics excellent in the rough skin improvement effect by using this raw material.

The raw material for cosmetics of the present invention contains proteoglycan extracted from shark cartilage and ethylbisiminomethyl guaiacol manganese chloride, and has the ability to suppress 8-OHdG formation and promote collagen synthesis.
Furthermore, it is characterized by further blending one or more amino acids. The amino acid is at least one amino acid selected from glycine, glutamic acid, and arginine.

  The cosmetic of the present invention is characterized by blending a cosmetic raw material having the above-mentioned 8-OHdG formation inhibitory ability and collagen synthesis promoting ability.

The cosmetic raw material of the present invention contains proteoglycan extracted from shark cartilage and ethyl biiminomethyl guaiacol manganese chloride, which is a salen metal complex. By combining these two components, the action of detoxifying the latter active oxygen, which is an antioxidant component, and the action of inhibiting the former matrix metalloprotease activity brought about a synergistic effect, compared to those used alone. Thus, a cosmetic raw material having excellent 8-OHdG formation inhibiting ability and collagen synthesis promoting ability is obtained. Furthermore, since an amino acid is blended, the ability to suppress 8-OHdG formation and the ability to promote collagen synthesis are further improved.
As a result, a cosmetic containing this cosmetic raw material has a very high effect on improving rough skin and is very effective against wrinkles.

As a result of research on the above problems, the problem could be solved by adding proteoglycan extracted from shark cartilage and ethylbisiminomethyl guaiacol manganese chloride.
Proteoglycan is a substance in which 100 to 200 mucopolysaccharides are bound to a protein core, is present in connective tissues such as cartilage and skin, and is a substance necessary for maintaining these tissue structures. Proteoglycans obtained from cattle and pigs are also used as topical skin preparations, but proteoglycans obtained from shark cartilage were more effective in inhibiting matrix metalloprotease activity. The type of shark that can be used in the cosmetic raw material of the present invention is not limited, and any shark belonging to the cartilage fish class may be used. Often used are blue sharks, mouse sharks, and gray sharks. These sharks have many cartilage in their wings and can be easily extracted, but there is no problem using other sharks or other parts. Extraction of proteoglycan from shark cartilage can be performed according to a conventional method. In addition, since the purity of proteoglycan obtained by extraction is not particularly problematic, the degree can be selected according to the use and usage.

To illustrate how to obtain proteoglycan from shark cartilage, use a solution obtained by chopping shark wrinkles and adding one or a mixture of water, water and low-molecular alcohol, sodium chloride, magnesium chloride, guanidine hydrochloride and other salts. To extract.
Furthermore, concentration, desalting, decolorization, solvent removal, drying (spraying, freezing), molecular weight fractionation, proteolytic enzyme treatment, etc. are performed as necessary.
As shark cartilage proteoglycans, those commercially available as cosmetic raw materials can be used.
The amount of proteoglycan extracted from shark cartilage varies depending on the application and the like, but is 0.0001 to 10% by weight, preferably 0.001 to 5% by weight as the solid content with respect to the total amount of the cosmetic raw material of the present invention.

In addition to proteoglycan extracted from shark cartilage, ethylbisiminomethyl guaiacol manganese chloride is added.
Ethyl bisiminomethyl guaiacol manganese chloride is commercially available under the chemical name Chloro [[2,2 '-[1,2-ethanediylbis [(nitrilo-κN) methylidyne]] bis [6-methoxyphenolato-κN]]]-manganese. For example, trade name EUK-134 manufactured by ATRIUM can be used.
The compounding amount of ethylbisiminomethyl guaiacol manganese chloride is 0.00001 to 1.0% by weight, preferably 0.0001 to 0.1% by weight, based on the total amount of the cosmetic raw material of the present invention.
Ethylbisiminomethyl guaiacol manganese chloride works like superoxide dismutase and catalase, and can convert highly toxic active oxygen and hydrogen peroxide, which is an intermediate product, into water and oxygen that are harmless to the living body. A very strong active oxygen scavenging effect can be obtained. Moreover, it has a self-regenerative characteristic function and can continuously obtain the above effects. Furthermore, it has an erasing action such as nitric oxide which is active oxygen in a broad sense.
Addition of proteoglycan extracted from shark cartilage to ethyl bisiminomethyl guaiacol manganese chloride synergistically enhanced the effect of ethyl bisiminomethyl guaiacol manganese chloride on inhibition of gene damage (suppression of 8-OHdG formation) and the promotion of collagen synthesis. .

  Furthermore, when an amino acid is blended, it is more effective. As amino acids, neutral amino acids such as glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, proline, phenylalanine, tryptophan, tyrosine, acidic amino acids such as glutamic acid, aspartic acid, lysine, arginine, Examples include basic amino acids such as histidine. Of these, glycine, glutamic acid, and arginine are preferred. In the cosmetic raw material of the present invention, one or more of these are blended. As a result of studies by the present inventors, it has been found that the effect is enhanced when a plurality of types of amino acids are used in combination. In particular, it has been found that it is very effective to add one or more of neutral amino acids, acidic amino acids, and basic amino acids. In addition, a raw material in which amino acids are mixed, such as a hydrolyzate such as soybean or collagen, can also be used.

Proteoglycan extracted from shark cartilage inhibits the activities of MMP-2 and MMP-9 among matrix metalloproteases (MMP). These enzymes are involved in the degradation of type VII collagen and elastin, and are enzymes that atrophy the extracellular matrix of the skin. This is called animal collagenase, but there are other bacterial collagenases, and amino acids are known to be effective against these. In addition, combining proteoglycan extracted from shark cartilage and amino acids suppresses the action of many types of matrix metalloproteases, promotes the synthesis of collagen, the skin matrix, maintains and strengthens collagen, It is possible to effectively prevent, reduce and prevent tarmi.
According to the present inventor, by adding an amino acid to proteoglycan extracted from ethylbisiminomethyl guaiacol manganese chloride and shark cartilage, the ability to suppress 8-OHdG formation, and particularly the action of promoting collagen synthesis, synergistically increases the effect. It was found.

  The amount of amino acid varies greatly depending on the application and usage, and cannot be generally shown, but it is preferably about 0.1 to 5% by weight based on the total amount of the cosmetic raw material of the present invention.

In addition to the cosmetic raw materials described above, the necessary raw materials are added to produce cosmetics. Among them, the combined use of other effective substances such as ascorbic acid and its derivatives, vitamin A and its derivatives, analogs, hyaluronic acid and its salts, various plant extracts, etc. increases the added value of the present invention. Therefore, it is more preferable to mix them.
Moreover, there is no problem in selecting the cosmetics of the present invention from arbitrary dosage forms such as creams, emulsions, lotions, packs, sprays, gels, etc. depending on applications. Moreover, any of pharmaceuticals, quasi-drugs, and cosmetics may be used. As long as they are applied to the skin, forms such as bathing agents and foundations may be used.

  Although an Example is described below, naturally it is not limited to this. In addition, the compounding quantity in the following table | surface was represented by the weight part.

Examples 1 to 4 and Comparative Examples 1 to 4
The raw materials shown in Tables 1 and 2 were stirred and mixed at the blending ratios shown in Tables 1 and 2 to obtain cosmetic raw materials. The shark cartilage extract used was trade name MDICOMPLEX (active ingredient content: 0.4% by weight) manufactured by AETERA. As ethylbisiminomethyl guaiacol manganese chloride, trade name EUK-134 (active ingredient content: 95% by weight or more) manufactured by ATRIUM was used.
Using the obtained cosmetic raw material, the following 8-OHdG formation inhibition test and collagen synthesis promotion test were conducted.

Test 1 8-OHdG formation inhibition test Using human-derived keratinocyte cultured cells, the 8-OHdG formation inhibition effect was examined using the cosmetic raw materials of Examples 1 to 4 and Comparative Examples 1 to 4 described above.
Each of the examples and comparative examples was cultured for 4 days in a medium in which the final concentration of the cosmetic raw material was 0.01% or 0.1%. Thereafter, ultraviolet rays of 0 mJ / cm ² (unirradiated), 50 mJ / cm ² and 100 mJ / cm ² were irradiated to extract DNA from keratinocytes, and 8-OHdG formation rate using immunodot blotting Was measured.

Similarly, cultured cells grown in the same manner were fixed in formalin, added to a 1% crystal violet solution and stained. The cell growth rate for each concentration of each cosmetic raw material was measured with a monocerator (manufactured by Olympus).
These results are shown in Tables 3 to 10. In the table, the numerical value indicates the 8-OHdG formation rate, and the numerical value in parentheses indicates the cell growth rate. When the amount of ultraviolet rays does not include any example (or comparative example) is 0 mJ / cm ² (unirradiated) Was displayed as 1.

  In cells cultured in a medium using the cosmetic raw materials of Examples 1 to 4, 8-OHdG formation is less likely to occur even when the amount of ultraviolet rays is increased, compared to cells using Comparative Examples, and excellent 8-OHdG A formation inhibitory effect was observed. Moreover, compared with the thing using the comparative example, even if it increased the amount of ultraviolet rays, the fall rate of the cell growth rate was low and what was cultured with the culture medium using Examples 1-4 also suppressed deterioration of cell growth ability. The effect was seen.

Test 2 Collagen synthesis promotion test Human skin fibroblasts (ATCC CCL 110) were used to seed 5000 cells / well of human skin fibroblasts in a 96-well plate, and in Eagle's MEM medium containing 10% fetal bovine serum. The cells were cultured for 4 days at 37 ° C. under 5% CO ₂ until they became confluent. To this, Examples 1 to 4 and Comparative Examples 1 to 4 were serum-free Eagle's MEM (50 μg / ml L-ascorbic acid, 50 μg / ml β-amino) adjusted to a culture concentration of 1.0%. The mixture was replaced with propionitrile (containing 18.5 KBq 3H-proline) and cultured for 24 hours. Then, immediately after adding a pepsin solution to each well and incubating, 3H-proline labeled collagen was extracted. After purification by salting out, the radioactivity in the collagen protein was measured with a liquid scintillation counter. Each sample was measured in 5 wells, and the sample-free sample was used as a control. The results are shown in Table 11.

  In Examples 1 to 4, good results were obtained in the collagen synthesis promotion magnification as compared with Comparative Examples. In particular, Example 4 using all three amino acids glycine, glutamic acid, and arginine had excellent ability to promote collagen synthesis.

Examples 5 to 8 and Comparative Examples 5 to 6
In the formulations shown in Table 12 and Table 13, the A component and the B component were weighed, each was heated to 70 ° C., and the A component was gradually added to the B component while stirring, and then slowly stirred. A cosmetic was obtained by cooling to 30 ° C.
Using the resulting cosmetic, the following rough skin improvement test was conducted.

Test 3 Rough skin improvement test Hydrophilic Exaflex hydrophilic vinyl silicone impression material was used to take a replica of the skin surface morphology of a healthy female face and observed with a microscope. According to the criteria shown in Table 14, 60 persons judged to have rough skin evaluations 4 and 5 were divided into 3 groups, and Examples and Comparative Examples were applied to the left and right halves of the face twice a day for 1 month.
One month later, the skin surface morphology of the face was again observed by the above replica method, and evaluated according to the criteria shown in Table 14. The results of the first team are shown in Table 15, the results of the second team are shown in Table 16, and the results of the third team are shown in Table 17.

  Since the raw material for cosmetics of the present invention has an ability to suppress 8-OHdG formation and promotes collagen synthesis, it can obtain a cosmetic with a very high effect of improving rough skin, such as cream, emulsion, lotion, pack, spray, gel. , Bathing agents, foundations and other cosmetics, pharmaceuticals, or quasi-drugs.

Claims (4)

  A raw material for cosmetics comprising proteoglycan extracted from shark cartilage and ethylbisiminomethyl guaiacol manganese chloride, and having an ability to suppress 8-hydroxy-2'-deoxyguanosine formation and an ability to promote collagen synthesis.   Furthermore, 1 or more types of amino acids are mix | blended, The raw material for cosmetics of Claim 1 characterized by the above-mentioned.   The cosmetic raw material according to claim 2, wherein the amino acid is at least one amino acid selected from glycine, glutamic acid, and arginine.   A cosmetic comprising the cosmetic raw material according to claim 1, 2 or 3.