DE102004017982A1 - Composition, useful or cosmetic or medicinal purpose e.g. in the form of mask, comprises collagen (e.g. fish collagen) and carbohydrates (e.g. carboxymethyl cellulose) - Google Patents

Abstract

Composition (I) comprises collagen (A) and carbohydrates (B). Independent claims are also included for a cross-linked composition comprising (I) and additionally a chemical cross-linker; and a method for preparing sponge comprising making of a mixture containing water and (I), freezing the mixture and freeze-drying (lyophilization) the frozen mixture.

Description

The The present invention relates to a composition comprising collagen, especially fish collagen, and a carbohydrate as well as the preparation of sponges from this composition and the use of these sponges.

DE-A 195 41 555, DE-A 27 34 503 and DE-A 40 28 622 disclose sponges for cosmetic and medical purposes based on bovine collagen.

DE-A 199 32 075, DE-A 199 32 076 and DE-A 196 43 066 disclose sponges for cosmetic and medicinal purposes based on chitosan.

The outstanding positive properties of mammalian collagen in the cosmetic and medical field are the ethical, with the origin and the BSE problem linked disadvantages across from. For this reason, collagen of marine origin (marine collagen), especially fish collagen for Applications used in the cosmetic and medical field (eg DE-A 199 29 802, DE-A 199 34 120).

The linked to the origin Odor problem of fish collagen is in the prior art solved different ways. DE-A 199 29 802 discloses suitable methods for purification and Deodorization of marine collagen and fish collagen.

fish gelatin is a raw material for Fish Collagen.

Of the The present invention is based on the object, compositions to make ready, from which sponges for cosmetic and medical Purposes can be produced the one higher tear strength have, as known from the prior art sponges.

These Task is solved by a composition comprising collagen and a carbohydrate. This composition is called the composition of the invention and is an object of the present invention.

In an embodiment In the present invention, collagen is marine collagen.

In an embodiment In the present invention, the collagen is fish collagen.

In an embodiment In the present invention, the collagen was prepared by known methods deodorized.

In an embodiment In the present invention, the carbohydrate is selected from the group consisting of guar gum, carboxymethyl cellulose, xanthan gum, Locust bean gum, carrageenan, starch, cellulose, chitosan and Mixtures of these carbohydrates.

One Another object of the present invention is a crosslinked Composition available from a composition according to the invention, this composition of the invention additionally a chemical crosslinker. This crosslinks the composition according to the invention by chemical reaction, so that the crosslinked composition is obtained.

A embodiment the present invention is this crosslinked composition, wherein the chemical crosslinker is selected from the group consisting from a diisocyanate (eg hexamethylene diisocyanate (HMDI)), a Dialdehyde (eg, glutaraldehyde), a diepoxide (eg, ethylene glycol diglycidyl ether) and a diacid chloride (eg succinic acid dichloride or glutaric acid dichloride).

One Another object of the present invention is the composition of the invention, the composition being a sponge.

• a) das Bereitstellen einer Mischung enthaltend Wasser und die erfindungsgemäße Zusammensetzung
• b) das Einfrieren dieser Mischung
• c) das Gefriertrocknen (Lyophilisierung) der gefrorenen Mischung.

Another object of the present invention is a method for producing the sponge according to the invention comprising

• a) providing a mixture containing water and the composition according to the invention
• b) the freezing of this mixture
• c) freeze drying (lyophilization) of the frozen mixture.

One Another object of the present invention is the use of the sponge according to the invention for cosmetic or medical purposes. All uses come into consideration, those in the prior art, as shown for example in the present Appreciated scripture is described.

Of the Content of collagen in the composition according to the invention (and thus especially in the dried sponge according to the invention) may preferably be between 5 and 95% by weight, more preferably between 20 and 80% by weight, in particular between 30 and 70% by weight lie.

Particularly suitable carbohydrates according to the invention are: guar gum, carboxymethyl cellulose, xanthan gum, locust bean gum, carrageenan, starch, cellulose Chito san and mixtures of said carbohydrates. These are preferably present in the composition according to the invention at from 5 to 95% by weight, in particular from 30 to 70% by weight.

Of the Dry matter content of the mixture according to the invention can be between 0.1 and 15 wt .-%, preferably zw. 0.5 and 10 wt .-%, in particular between 1.0 and 5.0% by weight and in particular between 1.5 and 2.5% by weight.

Of the pH of the mixture according to the invention may be between 2.0 and 9.0, preferably between 4.0 and 7.5.

to Achieving a high wet tensile strength of the Sponge according to the invention can the composition of the invention additionally be mixed with a chemical crosslinker.

Basically suitable as a crosslinker all compounds that cause a crosslinking reaction in the composition of the invention to lead. This are usually divalent compounds that are capable of having the functional groups of the gelatin or the collagen and the optionally present other additives (amino groups and carboxyl groups, but also thiol groups and hydroxyl groups) a chemical bond enter into.

The Sponges of the invention are preferred water-insoluble. You can for cosmetic and medical purposes (eg as wound dressings).

The Compositions of the invention have many advantages. They are suitable for the production of sponges, which for cosmetic and medical purposes. These sponges have a high tear resistance in dry and wet condition. They can be used as masks in the cosmetic and medical field. These masks appear optically dense, have a uniform structure and possess a soft grip. These properties are linked to the benefits that the use of fish collagen entails, like this The prior art is known in part.

One Difference of the present invention to the prior art in that the stated advantages of the present invention are achieved become the mixture according to the invention by the addition of consistency-giving carbohydrates. Without the addition of these carbohydrates, you get brittle, hard masks that are visually translucent.

The present invention employs favored with the use of purified fish collagen (free of impurities and odors) as is the state of the art Technique (eg DE-A 199 29 802) e.g. for fish gelatine, native fish collagen extracts, marine atelocollagen etc. describes.

To is in a preferred embodiment the purified fish collagen is dissolved completely or partially in water and with various additives added. The mixture is poured into molds, snap frozen and subsequently dehydrated by lyophilization. The resulting product may be according to the prior art directly, or after cutting, in various formats and layer thicknesses for the desired Purpose to be used.

When Additives are the auxiliaries and additives described below, those in preferred embodiments additionally in the composition of the invention may be included.

When Auxiliaries and additives can Substances are used which are compatible with the compositions according to the invention (also called preparations) are compatible and the physical Properties of the preparations positively influence and / or the Preparations additional functionalities to lend. Particularly preferred as auxiliaries and additives Fabrics selected are from the group consisting of polyols, emulsifiers, fibers, dyes, Perfume oils, flavorings, cosmetic active ingredients, pharmaceutical agents and food additives.

The Preparations according to the invention can be described in minor amounts as further auxiliaries and oil bodies, synthetic and natural Hydrocarbons, waxes, cationic polymers, thickeners, Silicone compounds, biogenic agents, film formers, preservatives, solubilizers, Structuring agents and protective solutions (Cryoprotectant agents = CPA), UV sun protection factors and the like.

• • Glycerin;
• • Alkylenglycole wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1000 Dalton;
• • technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• • Niedrigalkylglucoside, insbesondere solche, mit 1 bis 8 Kohlenstoffen im Alkylrest wie beispielsweise Methyl- und Butylglucosid;
• • Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Sorbit oder Mannit,
• • Zucker mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Glucose oder Saccharose;
• • Aminozucker wie beispielsweise Glucamin.

Polyols, which come within the meaning of the invention as additional constituents of the preparations into consideration, preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are:

• • glycerin;
• Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of 100 to 1000 daltons;
• Technical Oligoglyceringemische with an intrinsic degree of condensation of 1.5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;
• Low alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical such as methyl and butyl glucoside;
• Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,
• • sugars with 5 to 12 carbon atoms, such as glucose or sucrose;
• • Aminosugars such as glucamine.

Usually the polyols are used in amounts of 0.1 to 20, preferably 1 to 10 wt .-%, based on the dry matter of the collagen, used, the use of glycerol and polyethylene glycols being preferred is.

• • Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;
• • C_12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;
• • Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;
• • Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga;
• • Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• • Polyol- und insbesondere Polyglycednester wie z. B. Polyglycerinpolyricinoleat oder Polyglycerinpoly-12-hydroxystearat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;
• • Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• • Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C_12/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z. B. Sorbit) sowie Polyglucoside (z. B. Cellulose);
• • Trialkylphosphate;
• • Wollwachsalkohole;
• • Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• • Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäßs DE-A 11 65 574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin sowie
• • Polyalkylenglycole.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group;
• C _12/18 fatty acid _mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;
• Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
• • alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;
• Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• • Polyol and especially Polyglycednester such. As polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Also suitable are mixtures of compounds of several of these classes of substances;
• Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Partial esters based on linear, branched, unsaturated or saturated C _12/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol) and polyglucosides (eg cellulose) ;
• • trialkyl phosphates;
• • wool wax alcohols;
• Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• • mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-A 11 65 574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol, and
• • polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are mixtures of homologs whose mean Alkoxylierungsgrad the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C _12/18 fatty acid _mono- and diesters of addition products of ethylene oxide with glycerol are known from DE-A 20 24 051 as refatting agents for cosmetic preparations.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use as surfactants are for example US 3,839,318 . US 3,707,535 . US 3,547,828 . DE-OS 19 43 689 . DE-OS 20 36 472 and DE-A1 30 01 064 and EP-A 0 077 167 known. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With respect to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably about 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Usually are the emulsifiers in amounts of 0.1 to 20, preferably 1 used to 10 wt .-% based on the dry matter of the collagen.

Examples of oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₀ fatty acids with linear C ₆ -C ₂₀ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids with linear C ₆ -C ₂₀ -fatty alcohols, esters of linear C ₆ -C ₁₈ -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ -fatty acids, esters of C ₆ -C ₂₂ -fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers, Silicone oils and / or aliphatic or naphthenic hydrocarbons into consideration.

As synthetic hydrocarbons z. As hydrogenated polyisobutene (synthetic squalane), polyisobutene, polyethylene, polypropylene can be used. Terpenes such as squalene or squalane can be used as natural hydrocarbons. Usually the hydrocarbons in amounts of 0.1 to 20, preferably 1 to 10 wt .-%, based on the dry matter of the collagens used.

suitable Thickeners are, for example, polysaccharides, in particular Xanthan gum, guar guar, agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, and also higher molecular weight polyethylene glycol mono and diesters of fatty acids, Polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone.

Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as. B. Luviquat ^® (BASF AG, Ludwigshafen / FRG), condensation products of polyglycols and amines, quaternized collagen polypeptides such as Lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat ^® L, Grünau GmbH), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such. B. Amidomethicone or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine ^® , Sandoz / CH), polyaminopolyamides such. As described in FR-A 22 52 840 and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products of dihaloalkylene such. B. dibromobutane with bis-dialkylamines such as. B. bis-dimethylamino-1,3-propane, cationic guar gum such. B. Jaguar ^® CBS, Jaguar ^® C-17, Jaguar ^® C-16 of Celanese / US, quaternized ammonium salt polymers such as. B. Mirapol ^® A-15, Mirapol ^® AD-1, Mirapol ^® A2-1 Miranol / US.

suitable Silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty, alcohol, polyether, epoxy-, fluoro- and / or alkyl-modified silicone compounds which both liquid at room temperature as well as resinous may be present.

Under biogenic active substances are, for example, bisabolol, allantoin, phytantriol, Panthenol, AHA acids, Plant extracts, marine extracts, vitamins and vitamin complexes to understand.

film formers are, for example, chitosan, microcrystalline chitosan, quaternized Chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, Polymers of the acrylic acid series, quaternary cellulose derivatives, Collagen, hyaluronic acid or their salts and the like Links.

When Dyes can the for used for cosmetic purposes suitable and approved substances as described, for example, in the publication "Cosmetic Colorants" of the Dye Commission the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, Pp. 81 - 106 are. These dyes are commonly in concentrations of 0.001 to 1 wt .-%, based on the dry matter used the collagen.

When Fibers can both natural Fibers and synthetic fibers and mixtures thereof used become. As natural Fibers are, for example, lignin, polyose, pectin and in particular Cellulose, suitable as synthetic fibers are, for example, polyesters, Polyamides or their mixtures. Preferably, the fibers are in an amount of 1 to 50, preferably 5 to 10 wt .-% used.

Under Growing is natural or synthetic materials which kneadable at 20 ° C, solid until brittle hard, coarse to fine crystalline, translucent to opaque, but not are glassy, above 40 ° C melt without decomposing, just above the melting point low viscosity and non-stringy. The in the sense of the invention usable waxes differ, for example, from resins in that They usually between about 50 and 90 ° C, in exceptional cases, too up to 200 ° C, in the molten, low-viscosity Pass state and are virtually free of ash forming compounds. After her Origin divide the waxes into the following three groups: natural Waxes, such as Candelilla wax, carnauba wax, Japan wax, Esparto grass wax, Cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, montan wax, Beeswax, shellac wax, spermaceti, lanolin (wool wax), cuddly fat, Ceresin, ozokerite (groundwax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), such as. B. montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as z. B. polyalkylene waxes and polyethylene glycol waxes. In this context is the use of natural Grow, especially preferred by vegetable waxes.

flavorings are concentrated preparations of odorous substances or flavors that are destined to give food a special smell or taste to rent. Examples are vanillin, peppermint oil, Maillard products, banana flavor and many others.

Important flavoring agents are the essential oils, also mixtures of individual, generally synthetically produced, one speaks here of "nature identical", components of these oils. At the moment there are about 600 natural u. about 4200 nature-identical flavorings for food, cosmetics and pharmaceutical products. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum.

typical synthetic fragrance compounds are products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons. fragrance compounds the type of ester are z. Benzyl acetate, p-tert-butylcyclohexyl acetate, Linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count to the Ethem for example, benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. As the Jonone and Methylcedrylketon, to the alcohols anethole, Citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances, which together create an appealing scent. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as Perfume oils, e.g. B. Sage oil, Chamomile oil, Clove oil, Balm oil, Mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil. Preferably be bergamot oil, Dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, 945-hexyl cinnamic aldehyde, Geraniol, benzylacetone, cyclamenaldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allylamyl glycolate, Cyclovertal, lavandin oil, Muscat sage oil, &946; Damascone, geranium Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, Evernyl, Iraldeine gamma, Phenylacetic acid, Geranyl acetate, Benzyl acetate, Rose oxide, romilate, irotyl and floramate alone or in mixtures, used.

When Food additives become substances with or without nutritional value, usually consumed neither as food nor as characteristic food ingredient can be used and a food for technological reasons in the manufacture, processing, preparation, treatment, packaging, promotion or storage are added, understood; whereby she or herself By-products become or become ingredients of the food can. Some food additives are of natural origin such. B. the carotene from carrots, Chlorophyll from green Plants, lecithin from eggs or soybeans. Others are against it purely synthetic chemicals such. As the azo dyes tartrazine u. Amaranth, the antioxidants BHA u. BHT u. the sweeteners Saccharin u. Cyclamate.

Under Pharmaceutical active substances are active substances and medicinal substances as well as their carrier in the various dosage forms. As examples may be mentioned azelaic acid as anti-acne agent or PVP-iodine complex for disinfection.

When cosmetic active ingredients can all substances are used which are suitable in cosmetic To be used.

When Preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, Pentanediol or sorbic acid and the other listed in Appendix 6, Part A and B of the Cosmetics Regulation Classes.

• • 3-Benzylidencampher bzw. 3-Benzylidennorcamphen und dessen Derivate, z. B. 3-(4-Methylbenzyliden)campher wie in der EP 0693471 B1 beschrieben;
• • 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino) benzoesäure-2-ethylhexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoesäureamylester;
• • Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester, 4-Methoxyzimtsäurepropylester, 4-Methoxyzimtsäureisoamylester 2-Cyano-3,3-phenylzimtsäure-2-ethylhexylester (Octocrylene);
• • Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-isopropylbenzylester, Salicylsäurehomomenthylester;
• • Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methyibenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;
• • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethylhexylester;
• • Triazinderivate, wie z. B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin und Octyl Triazon, wie in der EP 0818450 A1 beschrieben oder Dioctyl Butamido Triazone (Uvasorb^® HEB);
• • Propan-1,3-dione, wie z. B.1-(4-tert.Butyiphenyl)-3-(4'methoxyphenyl)propan-1,3-dion;
• • Ketotricyclo(5.2.1.0)decan-Derivate, wie in der EP 0694521 B1 beschrieben.

Under UV sun protection factors are, for example, at room temperature, liquid or crystalline organic substances present (sunscreen) to understand that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg. B. to give off heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances z. To name, for example:

• • 3-Benzylidencampher or 3-Benzylidennorcamphen and its derivatives, eg. B. 3- (4-methylbenzylidene) camphor as in EP 0693471 B1 described;
• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);
• Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
• Triazine derivatives, such as. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone, as described in U.S.P. EP 0818450 A1 Dioctyl Butamido Triazone or described (Uvasorb HEB ^®);
• • Propane-1,3-dione, such as B.1- (4-tert.Butyiphe nyl) -3- (4'methoxyphenyl) propane-1,3-dione;
• • Ketotricyclo (5.2.1.0) decane derivatives as described in U.S. Pat EP 0694521 B1 described.

• • 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze;
• • Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze;
• • Sulfonsäurederivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bomylidenmethyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bomyliden)sulfonsäure und deren Salze.

Suitable water-soluble substances are:

• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds as described in U.S.P. DE 197 12 033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed metatoxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as. Example, titanium dioxide T 805 (Degussa) or Eusolex ^® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. In sunscreens, so-called micro- or nanopigments are preferably used. Preferably, micronized zinc oxide is used. Further suitable UV light protection filters can be found in the review by P. Finkel in SÖFW Journal 122, 543 (1996).

In addition to the two groups of primary light stabilizers mentioned above, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples are amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosine, D-camosine, L-camosine and their derivatives (eg anserine), carotenoids, carotenes (eg alpha-carotene, beta-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose , Propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, Oleyl, gamma-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinsulfoximine , Butioninsulfone, Penta-, Hexa-, Heptathioninsulfoxi min) in very low tolerated dosages (eg. Pmol to mol / kg), furthermore (metal) chelators (eg alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), alpha hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid , Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg gamma-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives ( for example, ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, alpha Glycosylrutin, ferulic acid, furfurylidene glucitol, camosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, hi-acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and the like Derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg. B. selenium-methionine), stilbenes and their derivatives (eg, stilbene oxide, trans-stilbene oxide) and the invention suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.

cryoprotectant agents are, for example, sugar solutions such as sucrose, maltose o. Ä., Glycerol, PVP or buffer solutions.

Of the Total content of the auxiliaries and additives may be 0.1 to 50 preferably 0.5 to 10% by weight, based on the dry matter of the collagen, be.

Examples

example 1

2.4 kg of a solution of native fish collagen (about 1%, for example Collagen Native M from from CTPP, France) were mixed with 36 g of cellulose (fiber length 300 microns). The mixture thus obtained was then homogenized by means of a colloid mill. Care was taken that the temperature of the mixture did not exceed 15 ° C. 2 kg of this mixture was then poured into a shallow dish (Dimensions approx. 360 × 250 × 22 mm) and for 12 h at 5 ° C ditched. The resulting gel became within 1 hour frozen in a brine basin at -30 ° C. The frozen block was demolded and lyophilized at 80 ° C and 1 mbar, so that a sponge was obtained. The dried block (sponge) was subsequently to a layer thickness of 1.2 mm and a format of 200 × 300 mm cut so that sponge column were obtained.

Example 2

A solution from 45 g fish gelatin in 2820 ml deionized water with a Temperature of 50 ° C was with 45 g of cellulose (fiber length 300 μm). The mixture thus obtained was then homogenized by means of a colloid mill and at 25 ° C cooled. 2 kg of this cooled Mixture was mixed with 3.0 g of an emulsifier mixture containing 10% PEG-40 sorbitan peroleate, 33% PPG-15 stearyl ether and 57% polyisobutene mixed and stirred well. Subsequently To this mixture was added 60 g of a 0.5% aqueous glutaraldehyde solution and for Intensively stirred for 2 minutes. The mixture was then poured into a shallow dish (mass approx. 360 × 250 × 22 mm) and for 12 h at 5 ° C ditched. The gel thus obtained was within 1 h in a Brine pool frozen at -30 ° C. The frozen block was demolded and lyophilized at 80 ° C and 1 mbar, so that a sponge was obtained. The dried block (sponge) was subsequently to a layer thickness of 1.2 mm and a format of 200 × 300 mm cut so that sponge slices were obtained.

Example 3

A solution from 45 g fish gelatin in 2820 ml deionized water with a Temperature of 50 ° C was with 27 g of cellulose (fiber length 300 μm), 4.5 g of xanthan gum and 4.5 g of locust bean gum added. The thus obtained Mixture was subsequently by means of a colloid mill homogenized and cooled to 25 ° C. 2 kg this cooled Mixture was with 3.0 g of an emulsifier mixture containing 10% PEG-40 Sorbitan peroleate, 33% PPG-15 stearyl ether and 57% polyisobutene mixed and stirred well. Subsequently was this mixture is admixed with 60 g of a 0.5% aqueous glutaraldehyde solution and for 2 minutes intensely stirred. The mixture is then poured into a shallow dish (mass approx. 360 × 250 × 22 mm) and for 12 h at 5 ° C ditched. The gel thus obtained was within 1 h in a Brine pool frozen at -30 ° C. The frozen block was demolded and lyophilized at 80 ° C and 1 mbar, so that a sponge was obtained. The dried block was subsequently to a layer thickness of 1.2 mm and a format of 200 × 300 mm cut so that sponge slices were obtained.

Claims (10)

A composition comprising collagen and a Carbohydrate. The composition of claim 1, wherein the collagen Marine collagen is. The composition of claim 1, wherein the collagen Fish collagen is. The composition according to any one of claims 1 to 3, wherein the collagen was deodorized by known methods. The composition according to any one of claims 1 to 4, wherein the carbohydrate is selected from the group consisting of guar gum, carboxymethylcellulose, Xanthan gum, locust bean gum, carrageenan, starch, cellulose, chitosan and Mixtures of these carbohydrates. A crosslinked composition available from A composition according to any one of claims 1 to 5, additionally comprising chemical crosslinker. The crosslinked composition of claim 6, wherein the chemical crosslinker selected is selected from the group consisting of a diisocyanate (eg hexamethylene diisocyanate (HMDI)), a dialdehyde (e.g., glutaraldehyde), a diepoxide (e.g. Ethylene glycol diglycidyl ether) and a diacid chloride (eg, succinic acid dichloride or glutaric acid dichloride). The composition according to any one of claims 1 to 7, wherein the composition is a sponge. A method for producing the sponge according to claim 8 comprising a) providing a mixture containing water and the composition according to the invention b) freezing this mixture c) freeze drying (lyophilization) of the frozen mixture. The use of the sponge according to claim 8 for cosmetic or medical purposes, e.g. B. in the form of a mask.