HU193545B - Process for the production of collagen-polyanion complex and of cosmetics therefrom - Google Patents

Abstract

Complexes of collagen with poly-electrolytes of general formula I are prepd. by mixing a 1-30 wt.% aq. soln of the copolymer of formula I - where n is an integer between 25 and 500 - adjusting the pH of the soln. with alkali hydroxide to 3.8-5.5 and mixing this soln. with a freshly prepared aq. soln. of 1-7 wt.% gelatin to obtain a mixed soln. in which the ratio of gelatin and copolymer is between 2:1 and 1:2, pref. 1:1. The resulting soln. is opt. lyophilized. - The collagen-polyanion complex is mixed into the appropriate cosmetic prepns. like face-milk, body-milk, regenerating cream, shampoo, foam-bath etc., in amts. of 0.1-1.0 wt.% at a temp. not exceeding 50 deg.C.

Description

The present invention relates to a process for the preparation of a cosmetic additive from natural and synthetic polymers in the presence of alkali metal ions, comprising: collagen hydrolyzate, gelatin and poly (1-vinyl-2-pyrrolidone-co-maleic acid) a. n is an integer from 50 to 200 - they form a water-soluble complex.

In recent years, more and more cosmetic products containing collagen hydrolyzate have been produced because it has been found that active collagen of natural origin increases the water-binding capacity of the skin, promotes skin regeneration, removes elasticity and wrinkles (Henkel - Dehydag, Kosmetik - Grundstoff Jahrbuch 1978, 1979, 1980, 1981; Catalog CLR Wiskstoffe für die Kosmetik 1981).

Experiments have shown that only a collagen derivative that is acidic and water-soluble has an active, i.e. rehydrating, regenerative effect (A. Huc, M. Journot, D. Hartmann, Parfums, Cosmet., Aromes, 1981 40 (CA) 95,225649w)). However, the solubility of collagen hydrolyzate is limited, insoluble below 40 ° C, but begins to decompose above 60 ° C. In addition, neutral or only slightly acidic gelatin solutions are bacterial media. Gelatin solutions and gelatin-containing cosmetics should be preserved in order to prevent the growth of micro-organisms and to prevent decay. The problem with this, on the one hand, is that in the presence of acidic preservatives (citric acid, boric acid, ascorbic acid), the solubility of gelatin is reduced or even precipitated, and on the other hand, non-acidic preservatives are generally toxic or odorous.

Gelatin is known with macromolecular acids such as poly (methacrylic acid) (K. Bolewski, B. Rychly, L. Spotanska, Ciolakowska: Farm. Pol. 1969, 25 (5), 333340 (CA 71, 92139)), and poly (styrene sulfonates) (FR Eirich, S. Jabarin, J. Katchev, G. Thomas: Polym. Prepr., Amer. Chem. Soc., Div. Polym. Chem. 1970, 11 (2)). , 775-9 (CA 77, 9997 c)), which, however, have the great disadvantage of being insoluble in water and thus virtually unsuitable for use in cosmetic formulations.

It is an object of the present invention to provide a water soluble gelatin synthetic polymer complex that combines the water retention and skin regeneration properties of natural collagen with the skin protective, bacteriostatic properties of the synthetic polyanion: vinylpyrrolidone-maleic acid copolymer.

The invention is based on the discovery that the above copolymer of formula (I) forms a water-soluble, stable complex with the polypeptides in the presence of alkali metal ions. The complex 2 can also be prepared in solid form, since the aqueous solution retains its structure by freezing and, if necessary, the material can be lyophilized (-70 ° C).

In the process of the present invention, the copolymer of formula (I) is prepared in an aqueous solution at a concentration of from 1 to 30% by weight with an alkali metal hydroxide solution, preferably NaOH, to a desired value, e.g. Set to 4.0. This solution is mixed with a freshly prepared gelatin solution at a concentration of 1-7% by weight such that the ratio of constituents in the resulting complex is from 1: 2 to 2: 1, preferably 1: 1. The resulting solution is optionally lyophilized and the resulting solid is used in an amount of 1 to 10% by weight in the preparation of cosmetic compositions such that 1 to 10, preferably 46% by weight, of the complex is aqueous or aqueous alcoholic solution. The mixture is stirred at a temperature below 50 ° C for the other ingredients.

The complex produced by the process of the invention has a natural acidity of the skin. also soluble in water in the corresponding pH range (4.2-6.0). The complex solution is clear, can be diluted with alcohol to a 1: 1 weight ratio, and a 5% w / w aqueous solution is well stored, does not gel, and does not rot.

The solid product is white in color. Thanks to its well-structured filamentous structure, it dissolves quickly in warm water. It can be stored indefinitely without loss of quality, and is also more advantageous from the transport point of view than any known material. When used, it can be reconstituted to any concentration.

The complex solution is easily absorbed, giving the skin a soft, velvety feel, making it ideal for face and body creams, milks, shampoos, shower baths, hair conditioners.

The main advantages of the collagen-polyanion complex of the invention are summarized below:

- its use in cosmetics makes it possible to replace collagen preparations from hitherto imported products with domestic products;

- outperforms the Collagen CLR formulation in the form of an aqueous or an aqueous alcoholic emulsion used for comparison in some essential properties. The amount of alcohol used in the mixed solvent product for preservation should not be greater than 15% by volume, otherwise the collagen will be denatured and precipitated. The disadvantage of the preparation is that it is immiscible with oils and fats and can only be stored protected from frost at 15-25 ° C. In contrast, the gelatin polyanion complex of the present invention forms a clear solution over the entire pH range of the skin (4.2-6.0), without denaturing

-2193545 even at 50% vol .; mixes well with oils, fats. It is not damaged by frost and can be lyophilized after freezing at -70 ° C.

simplifies the cosmetic formulation technology due to the listed beneficial properties of the complex.

The invention is illustrated in detail by the following non-limiting Examples.

Example 1 g of a copolymer of formula (I), wherein π is dissolved in 100-100 ml of distilled or deionized water. The pH of the solution was adjusted to 4.0 with 360 mL of 0.1 M sodium hydroxide. 10 g of edible gelatin were dissolved in 200 ml of water at 50 ° C and the two solutions were mixed. The resulting 3 wt% solution can be used directly for cosmetic formulations.

Example 2 g Copolymer of formula (I), wherein n is 75-50 ml in distilled or deionized water. The pH of the solution was adjusted to 4.0 with 0.5 M sodium hydroxide solution and the solution was made up to 200 ml with distilled water. 10 g of edible gelatin were dissolved in 200 ml of water at 50 ° C and the two solutions were mixed. 400 ml of a 5 wt% complex solution are obtained which can be used directly for cosmetic preparations.

Example 3

All were carried out in the same manner as in Example 2, but using potassium hydroxide instead of NaOH. The resultant 400 ml of a 5% w / w solution can be incorporated directly into cosmetic compositions.

Example 4 g of copolymer (1), wherein n is from 150 to 20 ml of water. The pH of the solution was adjusted to 4.0 with 0.5 M NaOH. Then, 5 g of gelatin was dissolved in 80 ml of water at 50-60 ° C.

To the still warm gelatin solution was added the copolymer solution. The resulting solution was quick frozen and lyophilized in acetone / dry ice (-70 ° C). 10.4 g of solid gelatin-polymer complex were obtained (100% yield).

Example 5

7.5 g of the copolymer of the formula I are dissolved in 170-60 ml of distilled water. The solution was adjusted to pH 4.0 with 270 mL of 0.1 M sodium hydroxide. Subsequently, 13 g of edible gelatin were dissolved in 330 ml of water at 50 ° C, and the two solutions were combined. 650 ml of a 3% solution can be used directly for cosmetic preparations.

Example 6 g of a copolymer of the formula I, wherein n is 90 to 180 ml of distilled water. The pH of the solution was adjusted to 4.0 with 0.5 M sodium hydroxide solution and the volume was made up to 400 ml with distilled water. 12 g of edible gelatin were dissolved in 220 ml of water at 50 ° C and the two solutions were mixed. 800 ml of a 4% solution can be added directly to the cosmetics.

Comparative experiments were performed with but using polyvinylpyrrolidone, polyvinyl alcohol or polystyrene sulfonic acid-co-acrylamide instead of the copolymer of formula (I) and cosmetics. citric acid, ascorbic acid, boric acid or the sodium salt of the latter are mixed in an aqueous solution with a solution of gelatin.

The use of copolymers resulted in sticky solutions which were not absorbed into the skin, thus having no skin regenerating or moisturizing effect.

The other types of compounds caused irreversible precipitation of gelatin, so that they could no longer be used.

The cosmetic application of the collagen polyanion complex of the present invention is illustrated in the following examples.

Example 7

Body milk was prepared according to the following recipe

Isopropyl myristate 8.0 Cetyl-a Alcohol 2.0 Sorbitan Monostearate (Arlacel 60) 2.0 Poly-oxyethylene monostearate (TWEEN 60) 3.0 Methyi-Propyl-pHBEster 0.2 Water 75.1 Substituted imidazole-imidylurea complex (Germall 115) 0.2 Collagen complex 4.0 Fragrance (lavender oil) 0.5 Lanolin (UMORDANT) 5.0 Example 8 Regenerating cream Diethanolamine cetyl phosphate complex (Amphisol) 3.0 Stearin 5.0 C ₈ -C ₁₂ fatty acid triglyceride based (Miglyol 812) 15.3 Isopropyl palmitate 10.0 Lanolin, liquid 5.0 Methyl propyl pHB ester space 0.5 Distilled water 61.7 70% by weight sorbitol syrup (Karion F) is liquid 5.0 Collagen complex 5.0 3

-3193545

Example 9

Hand regenerating cream

Long Fatty Alcohols Cetyl Stearyl Alk. colloidal dispersion of 1-Na-cetyl and stearyl sulfate (Lanette N) 8.0

Stearin 3.0

Isopropyl palmitate 5.0

Silicone oil AK 500 5.0

Methyl propyl pHB ester 0.5

Carion, liquid 5.0

Collagen complex 5.0

Distilled water gives 100

Example 10

Shampoo for dry, worn hair

Lauryl ether sulfate Na (100%) 14.0

Coconut fatty acid diethanolamide 5.0

Sodium benzoate 0.4% by weight alkyl ester sulfate mixture (Perglanz Conc.) 5.0

Collagen complex 5.0

Water (deionized) gives 100

Example 11 Foam bath

Alkylamidobetaine (100%) 5.0

Na-lauryl ether sulfate (100%) 20.0

Conical fatty acid diethanolamide 3.0

Chamomile Extracts 2.0

Collagen Complex 2.0

Imidazol-imidylurea 0.4

Pine scent 1.0

Water (deionized) ad 100 5 Example 12 Shower Alkylaminobetaine (100%) 10.0 Na-laurine sorbozime (100%) 2.0 10 Triethanolamine lauryl ether sulfate 18.0 Coconut fatty acid diethanolamide 2.0 Collagen complex 5.0 Synthetic organ 1.0 Sodium benzoate 0.4 15 Water (deionized) ad 100

Patent Claim Point

Claims (1)

Patent Claim Point A process for the preparation of a collagen polyanion complex which can be used as a cosmetic additive, comprising the preparation of an aqueous solution of 1-30 wt. -hydroxide, preferably with sodium hydroxide solution, is adjusted to 3.8-5.5, preferably to 4.0, and this solution is mixed with 1-7% by weight of freshly prepared gelatin solution, For 30 hours, ^the weight ratio of gelatin copolymer in ^the resulting complex is 1: 2 to 2: 1, preferably 1: 1, and optionally, the solution is lyophilized in a manner known per se.