US 2006O188465A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0188465 A1 Perrier et al. (43) Pub. Date: Aug. 24, 2006 (54) CROSS-LINKED POLYMER OF (30) Foreign Application Priority Data CARBOHYDRATE, NOTABLY BASED ON POLYSACCHARIDES, AND/OR ON Feb. 18, 2005 (FR)............................................ O5 O1674 OLGOSACCHARDES AND/OR ON POLYOLS Publication Classification (75) Inventors: Eric Perrier, Les Cotes D'Arey (FR): (51) Int. Cl. Nabil Abdul-Malak, Caluire (FR): A6IR 8/73 (2006.01) Julie Saget, Lyon (FR) A6II 3/765 (2006.01) C08G 63/9. (2006.01) Correspondence Address: (52) U.S. Cl. ................... 424/70.13; 424/78.37; 525/54.2 MERCHANT & GOULD PC P.O. BOX 2903 (57) ABSTRACT MINNEAPOLIS, MN 55402-0903 (US) (73) Assignee: Engelhard Lyon, Lyon (FR) The invention discloses a cross-linked polymer of at least one carbohydrate component comprising at least one pri (21) Appl. No.: 11/174,414 mary alcohol function in particular for the manufacture of a composition which is intended to be applied onto the skin to (22) Filed: Jul. 1, 2005 obtain a tensing and/or toning effect. US 2006/0188465 A1 Aug. 24, 2006 CROSS-LINKED POLYMER OF CARBOHYDRATE, which be capable of obtaining a tensing and/or toning effect NOTABLY BASED ON POLYSACCHARIDES, on the cutaneous Surface in a way which is perceptible by the AND/OR ON OLGOSACCHARDES AND/OR ON users, without inducing any identifiable allergic reaction. POLYOLS 0010. An aim of the present invention is to solve the 0001. The present invention relates to the preparation of technical problem consisting of providing a toning Solution an active principle having a tensing effect, based on various which is preferably based on a starting material of excellent protein or peptide Substances, so as to avoid problems of biocompatibility, of total biodegradability, of complete allergies encountered with these substances. The present assimilation, of total innocuousness, originating from a invention thus relates to the preparation of cross-linked renewable biological material, and being able to be present polymers of carbohydrates. not only in the animal kingdom, but also in the plant kingdom, and also being able to be produced by microbial STATE OF THE ART fermentation. 0002 Cosmetic formulations very often contain sub 0011. An aim of the present invention is also to solve the stances which enable characteristic tensing effects to be technical problem consisting of providing a novel method of induced. These effects in particular enable improving the manufacture of the compounds which enable solving the perception of effectiveness of a cosmetic formulation by technical problem mentioned above. sensory effects which are perceived significantly by con 0012. The whole of these technical problems is solved for SUCS. the first time in a manner which is satisfactory, inexpensive, 0003. Furthermore, these tensing effects enable on the which can be used on an industrial scale, notably cosmetic one hand an immediate but temporary reduction to be scale. brought about of the wrinkles and small wrinkles of the skin, and, on the other hand, a tension of the skin used for the DESCRIPTION OF THE INVENTION formulations of eye Surround, neck, neckline or hand type. 0013 Starting off from the prior art known to the inven 0004 Bovine serum albumin or collagen have been the tors, i.e. of polymerized proteins, the inventors have discov molecules which have been the most used in the past from ered in a Surprising way that cross-linked polymers of at amongst the Substances which are the best known for this least one type of carbohydrate or carbohydrate derivative property. More recently, the substances developed for this enabled a tensing and/or toning effect to be obtained of a activity are turned towards Substances of plant origin: plant proteins have in particular be widely used for this activity. cutaneous tissue, such as the skin of a human being. 0014 Thus, according to a first aspect, the invention 0005 Thus, for example, the plant albumin fraction of relates to a cross-linked polymer of at least one type of cereal grains or of leguminous plants has been the Subject of carbohydrate comprising at least one primary alcohol func a particularly interesting patent for its analogy with bovine tion, and in particular relates to a cross-linked polymer serum albumin (Coletica, FR 2,701,847, W094/18944). which is obtainable according to the method defined below. Similarly, the polymerization of plant proteins with the aid This polymer excludes polymers of at least one type of of bifunctional agents has been described for various cos carbohydrate comprising at least one primary alcohol func metic applications (Coletica, FR 2,766,090 (corresponding tion in the form of capsules or spheres; particularly in the to U.S. Pat. No. 5,912,016); FR 2,780,901, (corresponding form of microcapsules or of microspheres, or in the form of to U.S. Pat. No. 6,197.757). The substances prepared by nanocapsules or of nanospheres. polymerization of hydrolyzed fractions of plant proteins have also been described and used for tensing effects in 00.15 According to a second aspect, the invention relates cosmetics (FR 2,832,157, WO 03/040216 A1). to a cosmetic, and/or dermo-pharmaceutical, and/or phar maceutical composition, comprising a cross-linked polymer 0006. However, the use of proteins in cosmetics becomes problematic since they can induce more or less strong as defined above. immune reactions, even allergies which can lead to total 0016. Also, according to a third aspect, the invention intolerances. The proteins originating from wheat, nuts, relates to the use of a cross-linked polymeras defined above, hazelnuts, peanuts, milk, are a few examples of them which for the manufacture of a composition which is intended to be are well known to the person skilled in the art. applied onto a cutaneous tissue of a Subject to obtain a 0007. It is necessary to consider that in the future, com tensing and/or toning effect on this tissue. pounds of a character which is irritant for the skin, such as 0017. By the term <<carbohydrates>, the inventors mean proteins, will no longer be able to be used, or little usable, carbohydrates as well as carbohydrate derivatives which in cosmetics, notably due to legislation. comprise at least one, or more, primary alcohol functions. 0008. A particular solution is not described in the prior art 0018 Within the context of the present invention, the which would have enabled the inventors to find an obvious tensing and/or toning effect is mainly measured by virtue of solution to alleviate the problems of irritation of the com the opinion of Volunteers, and/or from measurements of skin pounds which can be used in cosmetics or in pharmaceuti roughness, and/or from Viscosity of the aqueous solution of cals for their tensing effect. the cross-linked carbohydrates, by comparison with the aqueous solution of the non-cross-linked carbohydrates. AIMS OF THE INVENTION 0019. According to a variant, the invention relates to the 0009. A main aim of the invention is to solve the novel use of the cross-linked polymer, for the manufacture of a technical problem consisting of providing a compound composition which is intended to be applied onto a cutane US 2006/0188465 A1 Aug. 24, 2006 ous tissue of a subject to obtain a reduction of wrinkles the oligosaccharide, with respect to the cross-linking agent, and/or small wrinkles of this tissue. is greater than 0.1, and preferably greater than or equal to 1. 0020. According to another variant, the invention relates 0032. In a second embodiment, the carbohydrate, par to the use of the cross-linked polymer, for the manufacture ticularly the polysaccharide, has a molecular weight of of a composition which is intended to be applied onto a greater than or equal to 50,000 Da, preferably greater than cutaneous tissue of a Subject to improve the biomechanical or equal to 100,000 Da, more preferably greater than or properties of this tissue. equal to 300,000 Da. In this case, a hydrolysis can be carried out before the cross-linking reaction, so that the polymer 0021 Advantageously, the composition is a cosmetic, ization reaction can lead to polymers mainly soluble. Meth dermo-pharmaceutical or pharmaceutical composition, ods of hydrolyzing carbohydrates are known to the person which is intended to be applied onto at least one part of the skilled in the art. face, particularly onto the contour of the eye, and/or of the neck, and/or of the hands, and/or of the neckline, and/or the 0033 Advantageously, in this second embodiment the bust. molar ratio of the carbohydrate, particularly of the polysac charide, with respect to the cross-linking agent, is less than 0022. The products originating from this invention pos sess a toning effect upon applying a composition containing 0.1, and preferably less than 0.01. them onto the skin. The products originating from this 0034 Advantageously, the polysaccharide comprises 0.5 invention do not have any identifiable allergy forming effect to 4 primary alcohol functions per diosidic moiety. upon applying Such a composition on the skin. 0035 Advantageously, the carbohydrate before reaction 0023 The products of the invention adsorbent onto the is in a mixture with an excipient which is acceptable via the surface of the skin and form an elastic film which is smooth topical route, particularly a cosmetically or dermatologically and continuous. The filmogenic, tensing and plastifying acceptable excipient. properties of the carbohydrates, notably of the polysaccha 0036). According to another particular embodiment vari rides, and/or of the oligosaccharides, and/or of the polyols, ant, the concentration of carbohydrate having a primary thus polymerized, are thus particularly interesting.