Sun protection agents

Drug – bio-affecting and body treating compositions – Topical sun or radiation screening – or tanning preparations

Reexamination Certificate

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Details

C424S060000, C424S400000, C424S401000, C424S404000, C424S405000, C424S195160, C514S054000

Reexamination Certificate

active

06500410

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to the field of sun cosmetics and concerns to novel preparations with a content of specific glucans and UV light protection factors as well as the use of the glucans for improvement of the photosensitivity of the light protection factors.
PRIOR ART
The cosmetic sun protection products protect the human skin not only against the direct results of UV-A and UV-B radiation, i.e. against sunburn, but also against the indirect results in the form of skin aging and skin cancer. Therefore normally organic filtering substances are used, which because of their chemical structure are able to absorb ultraviolet light. Through the uptake of the UV-radiation electrons in the filter molecule are brought into an excited state. The energy which thereby is taken up is thereafter again set free as radiation of heat, whereby photosensitive molecules are going back into their energetic ground state, whereas in the case of photoinsensitive filters, to which the bigger part of the known light protection factors belong, a chemical change occurs, such as e.g. an isomerization or a radical degradation. In addition to the not always satisfactory photostability of the light protection factors, another problem resists in that the filters—also in cosmetic oils—only have a limited solubility, respectively dispersing ability. Thereby it can happen that the substances during storage precipitate or sediment, whereby the light protection preparation looses a substantial part of its efficiency.
In this connection reference is made to the European patent EP-B1 0500718 (Donzis), from which the use of glucans in sun protecting agents is known. The glucans are obtained through extraction from the cell walls of yeasts, they are insoluble in water and contain (1,6) linkages. Further in EP-A1 0681830 (Unilever) sun protection agents are suggested which contain ethylene/vinyl acetate copolymers and polyacrylates, UV light protection filters and possibly also up to 10% by weight of glucans.
Therefore the task of the present invention was to improve both the oil solubility and the oil dispersability of UV light protection factors, and also their photosensitivity. Further preparations should be made available which compared to the products according to known art should be distinguished through immune modulating or immune stimulating properties, improved adhesion, film forming abilities and water resistance.
DESCRIPTION OF THE INVENTION
The object of the invention is sun protection agents, containing
(a) water soluble &bgr;-(1,3) glucans, substantially free from &bgr;-(1,6)-bonds, and
(b) UV light protection factors.
Surprisingly it was found that the addition of &bgr;-(1,3) glucans, which are substantially free from &bgr;-(1,6) linkages not only increase the solubility or dispersability of UV light protection factors in cosmetic oils, but also vitally improve their photosensitivity, whilst glucans, which are insoluble in water, and which have noteworthy contents of &bgr;-(1,6) links, show no effect both in direction of solubilisation and in direction of photosensitivity. The invention comprises the perception that the agents stimulate the immune system and have an improved adhesion, film formation and water resistance.
Water Soluble &bgr;-(1,3) Glucans
The term glucans is intended to mean homopolysaccharides based on glucose. Depending on sterical linking there is a difference between &bgr;-(1,3), &bgr;-(1,4) and &bgr;-(1,6) glucans. &bgr;-(1,3) Glucans normally show a helical structure, whereas glucans with a (1,4) linkage generally have a linear structure. The &bgr;-glucans of the invention have a (1,3) structure, i.e. they are substantially free from undesired (1,6) linkages. Preferably such &bgr;-(1,3) glucans are used where the side chains exclusively show (1,3) linkages. Especially the agents contain glucans which are obtained on the basis of yeast from the family Sacchaomyces, especially
Saccharomyces cerevisiae
. Glucans of this type are available in technical amounts according to known methods. The international patent application WO 95/30022 (Biotec-Mackzymal) describes e.g. a method for producing such substances, wherein glucans with &bgr;-(1,3) and &bgr;-(1,6) linkages are brought in contact with &bgr;-(1,6) glucanases in such a way, that practically all &bgr;-(1,6) linkages are loosened. Preferably used for the manufacture of these glucans are glucanases based on
Trichodermia harzianum
. As to the manufacture and availability of the glucans contained in these agents, reference is made to the above cited publication.
UV Light Protection Factors
UV light protection factors are e.g organic substances (light protection filters) which by room temperature are in liquid or crystalline form, and which are capable of absorbing ultraviolet radiation and to give free the received energy in the form of radiation with long wavelength, e.g. in the form of heat. UVB filters can be soluble in oils or in water. As oil soluble substances the following are mentioned as examples:
3-Benzyliden camphor, respectively 3-benzylidene norcamphor and the derivatives thereof, e.g. 3-(4-methylbenzylidene) camphor as described in EP-B1 0693471;
4-aminobenzoic acid derivatives, preferably 4-(dimethylamino) benzoic acid 2-ethylhexylester, 4-(dimethylamino) benzoic acid 2-octylester and 4-(dimethylamino) benzoic acid amylester;
esters of cinnamonic acid, preferably 4-methoxy cinnamoic acid 2-ethylhexylester, 4-methoxy cinnamoic acid propylester, 4-methoxy cinnamoic acid isoamylester, 2-cyano-3,3-phenyl cinnamoic acid 2-ethythexylester (octocrylene);
esters of salicylic acid, preferably salicylic acid 2-ethylhexylester, salicylic acid 4-isopropyl benzylester, salicylic acid homomenthylester;
derivatives of benzophenone, preferably 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-methoxy-4′-methyl benzophenone, 2,2′-dihydroxy-4-methoxy benzophenone;
esters of benzalmalonic acid, preferably 4-methoxy benzmalonic acid 2-ethylhexyl ester,
triazine derivatives, such as e.g. 2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine and octyltriazone, as described in EP A1 0818450;
propane-1,3-diones, such as e.g. 1-(4-tert.-butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dion;
ketotricyclo(5,2,1,0)-decane derivatives, as described in EP-B1 06945521.
As water soluble substances can be mentioned:
2-Phenylbenzimidazol-5-sulfonic acid and the alkali, aalkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenon-5-suflfonic acid and their salts;
sulfonic acid derivatives of 3-benzylidencamphen, such as e.g. 4-(2-oxo-3-bomylidenmethyl)-benzolsulfonicc acid and 2-methyl-5-(2-oxo-bornyliden)-sulfonic acid and their salts.
As typical UV-A filter especially derivatives of benzoyl methane comes in question, such as e.g. 1-(4′-tert.-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dion, 4-tert.butyl-4′-methoxydibenzoyl-methan (Parsol 1789), or 1-phenyl-3-(4′-isopropylphenyl-propane-1,3-dion. The UV-A and UV-B filters of course also can be used in mixtures. In this case combinations of octocrylene or camphor derivatives with butyl methoxydibenzoylmethane are especially photosensitive.
In addition to the mentioned soluble substances also insoluble light protection pigments can be used for this purpose, i.e. fine disperse metal oxides or salts. Examples of suitable metal oxides are especially zinc oxide and titanium dioxide and in addition other oxides of iron, zirconium, silicon, manganese, aluminium and cerium, as well as their mixtures. As salts silicates (talk), barium sulphate or zinc stearate can be used. The oxides and salts are used in form of the pigments for skin caring 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 especially between 15 and 30 nm. They can have a spherical shape, but particles can also be used which have an ellipsoidal form or e

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