JPH02115112A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic, containing solubilized collagen having a prescribed steric molecular structure and specified weight of combined saccharide content with moderate moisture absorbing and releasing properties and excellent in obstruction properties. CONSTITUTION:A cosmetic obtained by containing solubilized collagen having a helical structure (subunits; alpha1, alpha2 and alpha3) consisting of three different kinds of alpha-chains with at least >=3wt.%, preferably >=5wt.% combined saccharide content. The solubilized collagen is derived from jellyfishes (e.g., ECHIZEN- jellyfish or esculent jellyfish) belonging to the order Rhizostomeae of the class Scyphozoa and readily available by hydrolyzing the living bodies of the jellyfishes with an enzyme. The amount of the solubilized collagen blended in the cosmetic is 0.0005-1wt.%, especially preferably 0.005-0.1wt.%. Examples of the cosmetic used are toilet water, milky lotion, cream, shampoo, rinse and hair tonic.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a novel cosmetic containing solubilized collagen having a certain three-dimensional molecular structure, and more particularly, to a solubilized collagen containing collagen having a certain three-dimensional molecular structure. By using collagen, the present invention aims to provide a cosmetic that has appropriate hygroscopicity and moisture-releasing properties, and has excellent occlusive properties.

(Prior art) Collagen is one of the well-known raw materials that can be used in cosmetics, and has been incorporated into various cosmetics for the purpose of beautifying the skin, moisturizing, and adding moisture. ing.

Furthermore, the types of collagen currently in use are diverse, including natural soluble collagen, insoluble collagen, and solubilized collagen obtained by decomposing cow or pig bones, skin, etc. with darkness, alkali, enzymes, etc.

By the way, these conventionally used natural soluble collagens or solubilized collagens have a collagen subunit structure (α1...
α1. α2) and have a bound sugar content of approximately 1% by weight, but when used as cosmetics on the skin, they can provide some degree of moisturizing and water-retaining effects to the skin due to their hygroscopic ability. However, on the other hand, since the skin occlusion property itself is low, it has the disadvantage that it cannot provide a sufficient skin water retention effect as a result.

On the other hand, hyaluronic acid is also well known as a raw material with high skin occlusive ability and excellent water retention effect, but when hyaluronic acid is used in cosmetics, it has a unique slimy feeling when applied to the skin, and When used in large quantities, it may feel sticky, so care must be taken when formulating the formulation from a tactile perspective.

(Problems to be Solved by the Invention) The present invention solves the drawbacks of the conventional natural soluble collagen and solubilized collagen, maintains appropriate moisture absorption and moisture release properties, and has skin occlusion ability, thereby improving skin care. An object of the present invention is to provide a cosmetic that has a water-retaining effect (7) and also has a good texture.

[Means to solve the problem]

Therefore, the present inventors conducted intensive research to solve the above problems and found that, unlike conventional collagen, solubilized collagen has a three-dimensional structure consisting of a certain polypeptide chain and bonded sugars, and has moderate hygroscopicity and release properties. It has been found that it has moisture properties, excellent skin occlusive properties, and does not cause any discomfort to the touch. The present invention is based on this knowledge.

That is, the present invention includes solubilized collagen that has a helical structure (subunit: α1.α2.α3) consisting of three different α chains and has a bound sugar content of at least 3% by weight. The present invention relates to a cosmetic composition characterized in that the solubilized collagen is preferably derived from a jellyfish belonging to the class Scyphozoa, and particularly preferably derived from a medusa belonging to the class Scyphozoa. be.

The present invention will be explained in detail below.

The solubilized collagen applied to the present invention has a helical structure (subunits: α1, α, α3) consisting of three different polypeptide chains in its molecular three-dimensional structure. Sugars are bound in an amount of 3% by weight or more, preferably in a maximum of 5% or more.

The general property of these solubilized collagens is that they are white fibrous powders and are soluble in acidic solutions.

Such solubilized collagen can be easily obtained by enzymatically hydrolyzing a specific species, that is, a species belonging to the class Scyphozoa, preferably the order Rhizomata. Here, specific examples of suitable lags include Echizen jellyfish, Bizen jellyfish, Moon jellyfish, and Sunairo lags.

For example, the middle layer of the Echizen jellyfish contains approximately 60% by weight of collagen on a dry weight basis, and this is α1.
α2. It is known to form an α3 heterotrimer.

(Kiku et al., The Journal of Biological Chemistry, Vol. 260, 15352 (1985), Shigeru Kiku, Chemistry and Biology, Sub(5), 311 (1987)
,Such).

However, other than some of these flags being used for food, there has been little consideration given to their effective use.
Rather, the reality is that it is treated as a problem when it occurs in large quantities, and attempts to use biologically derived collagen in cosmetic stones from an external standpoint are hotly debated, and when used, it is difficult to use conventional collagen. The exceptional properties of collagen are still largely unknown.

Next, a production example in which solubilized collagen according to the present invention is produced from the above-mentioned flags will be shown below.

Production Example 1 500 g of commercially salted Bizen jellyfish was desalted with cold ion-exchanged water and then shredded into small pieces (approximately 5 mm square). Next, this strip was added to 3 g of a 0.5 M acetic acid aqueous solution at 5°C, 3 q of protein hydrolyzed M-pepsin (1:10,000 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 days to perform hydrolysis. I did it.

The lysate thus obtained was subjected to an ultracentrifuge, and the supernatant was collected.

While stirring, 2N sodium hydroxide was added dropwise to the supernatant to adjust the pH to 8.0, and a white 5iIi fibrous solid was precipitated. This was applied to an ultracentrifuge, the supernatant liquid was removed, the precipitate was transferred to a slippery paper, and then ethanol 50%
It was purified by d.

After drying, a white fibrous subunit structure (α1, α2...
α3) and a bound sugar content of 9.6% by weight, 4.6 g of solubilized collagen was obtained.

Production example 2 Cut out the medium glue tissue from 100g of raw Echizen jellyfish,
It was thoroughly desalted with cold ion-exchanged water and shredded into small pieces (approximately 5 m square). This strip was added to 2g of 0.5M acetic acid aqueous solution, and 0% of the protein hydrolase pepsin (same product as in Production Example 1) was added.
．． Hydrolysis was carried out by adding 2Cl and stirring/v for 2 days.

The lysate thus obtained was subjected to an ultracentrifuge, and the supernatant was collected. This supernatant liquid is filtered through a dialysis membrane (cellulose tube:
(manufactured by Union Carbide), and the external solution was dialyzed for 2 days using a 0.02M aqueous 0.02M hydrogen phosphate aqueous solution (25Ω).The external solution was replaced and dialysis was performed for 2 days, and a white fibrous solid was precipitated. This was applied to an ultracentrifuge, the superintestinal fluid was removed, and the precipitate was collected. A small amount of this precipitate (
It was washed and purified with ethanol (approximately 10 precepts). After drying, 0.9 g of solubilized collagen having a white fibrous subunit structure (α1.α, α3) and a bound sugar content of 10.8% by weight was obtained.

Next, the amount of the solubilized collagen of the present invention to be incorporated into cosmetics is preferably 0.0005 to 1% by weight, particularly preferably 0.005 to 0.1% by weight.

If it exceeds 1.5%, the dispersibility will deteriorate, and if it is less than 0.0005%, no effect can be expected.

Next, the cosmetics used in the present invention include basic cosmetics such as lotions, emulsions, creams, bags, shampoos, conditioners, etc.
Hair cosmetics such as hair tonics and hair liquids.

(Examples) The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Note that all amounts are in parts by weight.

Example 1 Emulsion (A>Squalane 20.0 Lipophilic monostearic acid glycerin 1.5 ml) Comparative Example 1 Emulsion (A> Squalane 20.0 Lipophilic monostearic acid glyceryl 1.5 ml (C) Solubilized collagen (Production Example 1) 0.08(
Production method) Stir C overnight to dissolve the solubilized collagen.

A and B are each dissolved by heating at 70° C., and added little by little to BAA while stirring to emulsify. Thereafter, the mixture was cooled to 30° C. while stirring, and C was added to obtain a milky lotion.

(Manufacturing method) A was heated and dissolved at 70°C, and B was similarly heated to 70'C.
Add it little by little while stirring to emulsify. Thereafter, the mixture was cooled to 30°C while stirring to obtain a milky lotion.

Example 2 Cream (A>Squalane 16.0 Cethanol 4, O lipophilic glyceryl monostearate 1.0 ton (B) Vinegar base-sodium acetate buffer solution, 3.5 (pi
-14,0 Glycerin 3.0 (C) Acceptable) Hexalated collagen (Production example 2> 0.04 Hyaluronic acid (Seikagaku Corporation) 0.04 Acetic acid-sodium acetate buffer solution 39.90 (pH 4,
0> Fragrance (manufacturing method) According to Example 1, a cream was obtained.

Example 3 Shampoo N-7 Silu L-Glutamic acid triethanolamine solution (30%) Lauryl ether FA acid Sodium lauryl sulfate Triethanolamine d1-Pyrrolidone carphone salt I Noum solution 50%) 2.5 1, O Solubilized collagen (Production example 1) Preservative 0.1 0.1 Flavor
0.1 Purified water 67
．． 9 (Production method) The entire amount was stirred and dissolved uniformly to obtain a shampoo.

Example 4 Hair tonic (A>Ethyl alcohol 35.0 Menthol 0.3 Salicylic acid
0.1 polyoxyethylene (50) hardening
0.5 and mustard oil incense (B) Citrate Sodium Citrate Solubilized Collagen <Production Example 2> Purified Water (Production Method) A and B were each dissolved by stirring and added to obtain Atonic.

〔Effect of the invention〕

0.05 0.2 0.1 0.005 63.745 Next to B8A, the solubilized collagen according to the present invention has appropriate hygroscopicity and hygroscopicity, and the cosmetic containing solubilized collagen does not cause occlusion. Learn more about being good at sex.

(1) Experimental method and results for comparison of hygroscopicity and desorption properties> (Test) Sample 1: Solubilized collagen according to the present invention (Production Example 1) Test 142: Hyaluronic Shun (Seikagaku Corporation) Sample 3: L3
-Butylene glycol (manufactured by Daicel Chemical Industries, Ltd.) Sample 4: Collagen derived from beef Achilles Ken (manufactured by Gyudon Kagaku) (Measurement method) Weigh 10 of each sample into a weighing bottle with an inner diameter of 3 crn, and place in a desiccator adjusted to 20% humidity. Transfer to a thermostatic chamber at 20'C for 3 days to dry, then weigh accurately. This dried sample was transferred to a desiccator adjusted to a humidity of 81%, and the hygroscopicity was examined in terms of the relationship between standing time and weight increase. The results are shown in Figure 1.

Next, this moisture-absorbed sample was transferred to a desiccator adjusted to a humidity of 20%, and the moisture release performance was examined in terms of the relationship between standing time and weight loss. The results are shown in Figure 2.

(Results) (i) Hygroscopicity As is clear from Figure 1, the solubilized collagen (1) according to the present invention has a moisture absorption curve similar to that of hyaluronic acid (2), which is famous as a moisturizing agent in the cosmetics industry. However, the polyhydric alcohol 1,3-butylene glycol (3) is too strong, and the collagen derived from bovine Achilles Ken (4) is too weak.

(ii) Moisture release properties As is clear from Figure 2, the d-type collagen (1) according to the present invention has a moisture release curve similar to that of hyaluronic acid (2), which is famous as a moisturizer in the cosmetics industry. However, the polyhydric alcohol 1,3-butylene glycol (3) is too strong, and the collagen derived from bovine Achilles key (4) is too weak.

(2) Occlusion test <Experimental method and results> (Condition of lid) 1: No lid 2: Millibore (pore diameter 0.45μ, manufactured by Millibore) 3: Millibore was impregnated with the emulsion of Comparative Example 1 and then dried in a desiccator. Sample 4: Millibore was impregnated with the emulsion of Example 1 and then dried in a desiccator (Measurement method) 20 CI of purified water was placed in a cylindrical container with an inner diameter of 3.2 Crn, the lid was covered as described above, and the flan container was heated at 37°C. Put it in.

The relationship between the time the occlusion was allowed to stand and the weight loss due to water evaporation was examined. The results are shown in Figure 3.

(Result) The transpiration degree and occlusion rate were calculated using the following formulas.

Table 1 As is clear from Table 1, Example 1 containing the solubilized collagen of the present invention has the best occlusive properties.

In other words, solubilized collagen has moisture absorption and moisture release curves similar to those of hyaluronic acid, which is famous as a moisturizing agent in the cosmetics industry, and has moderate moisture absorption and moisture release properties. It has excellent occlusive properties and can maintain the moisture content of the stratum corneum for a long time.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between standing time and increase in weight in a hygroscopicity test. In the diagram, 1 indicates solubilized collagen (Production Example 1);
2 is hyaluronic acid, 3 is 1゜3-butylene glycol,
4 is collagen derived from bovine Achilles size. FIG. 2 is a diagram showing the relationship between standing time and weight loss in a moisture release test. In the diagram, 1 indicates solubilized collagen (manufacturing example 1);
2 is hyaluronic acid, 3 is 13-butylene glycol, and collagen derived from Peke cow Achilles. FIG. 3 is a diagram showing the relationship between leaving time and weight loss in the occlusion test i~. In the figure, 1 indicates when the cylindrical container item is removed;
2 is when attracting with millibore (pore diameter o645 μm),
3 is when Millibore was impregnated with the tL solution of Comparative Example 1 and dried in a desiccator and attracted, and 4 was when Millibore was impregnated with the emulsion of Example 1 and dried in a desiccator and capped. It is. Figure, 1 Figure, 2

Claims (1)

[Scope of Claims] 1) Contains solubilized collagen that has a helical structure (subunits: α_1, α_2, α_3) consisting of three different α chains and has a bound sugar content of at least 3% by weight. Cosmetics characterized by: 2) The cosmetic according to claim 1, wherein the solubilized collagen is derived from jellyfish belonging to the class Scyphozoa. 3) The cosmetic according to claim 2), wherein the jellyfish belonging to the class Scyphozoa is a jellyfish belonging to the order Rhizomata. 4) The cosmetic composition according to claims 1), 2) and 3), wherein the content of solubilized collagen is 0.0005 to 1% by weight.