CN112334124A

CN112334124A - Kit for caring for skin

Info

Publication number: CN112334124A
Application number: CN201980043523.5A
Authority: CN
Inventors: 张亮; Z·李
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2018-06-28
Filing date: 2019-03-13
Publication date: 2021-02-05
Also published as: WO2020001069A1

Abstract

A kit, comprising: 1) a first composition comprising at least one water insoluble substrate; and 2) a second composition in dry form comprising a water-soluble/dispersible active agent and a disintegrant.

Description

Kit for caring for skin

Technical Field

The present invention relates to a cosmetic system, and in particular a kit, for caring for keratin materials, and in particular the skin. The invention also relates to the use thereof, in particular as a body membrane (mask) for caring for keratin materials, in particular the skin.

Background

The ultimate goal in the cosmetic field has always been to provide products that are beneficial to the skin, such as hydrating, moisturizing, whitening, cleansing, and the like.

In all compositions for caring for keratin materials, in particular the skin, the body membranes are known to have a high penetration efficacy on keratin materials. Thus, for example, a two-digit market for body film cosmetic products is seen in china.

There are generally four types of body films, namely, paste type, peel-off type, gel type, and wet wipe type. Among them, the paste type and the peel type are mainly used for cleansing of keratin materials, while the gel type and the wet towel type films are more commonly used for skin care. It is known to incorporate water-soluble/water-dispersible active agents in gel or tissue masks (tissue masks). These body membranes are said to provide high efficacy to the skin, such as hydration, whitening, etc., due to the osmotic capacity of the body membranes.

However, these products are still unsatisfactory. Some water-soluble/dispersible active agents are generally less stable in the dissolved/dispersed state (e.g., in aqueous solution) than in their dry form, thus affecting their cosmetic benefits. For example, some water-soluble vitamins, such as ascorbic acid (also known as vitamin C), react more readily in aqueous solution. In particular, at lower or higher pH, vitamin C tends to hydrolyze.

It is known, particularly in the food and pharmaceutical field, to formulate these types of ingredients in dry form (e.g. beads, granules, particles, tablets, etc.). For example, it is known to produce tablets containing ascorbic acid to maintain high amounts of active ingredient without degradation. These tablets were then dissolved in water prior to use.

However, the inventors have found that these dry form products are still not suitable for use in the cosmetic field, particularly in body film products. On the one hand, large amounts of water are usually required to completely dissolve the product in dry form, and on the other hand, some products are so difficult to dissolve that long-term massage or external forces are required.

Based on the above, there is a need for new compositions for caring for keratin materials, in particular the skin, such as cosmetic body films, which combine two or more of the advantages exhibited by the known types of body films, but which do not suffer from one or more of the problems associated therewith.

Objects of the invention

Thus, in one aspect, it is preferred to provide a composition for the care of keratin materials to more effectively dispense water-soluble/dispersible active agents, particularly solvent-containing compositions.

In another aspect, it is preferred to provide compositions for the care of keratin materials, in particular the skin, with improved ease of use.

In another aspect, it is preferred to provide a body film that is capable of undergoing a texture transformation, such as changing from a paper towel to a gel, to bring about a pleasant consumer experience.

In another aspect, it is preferred to provide a body film having at least comparable or even better moisture or active (e.g., whitening agent) delivery capabilities than observed with wet wipe-type body films.

In another aspect, it is preferred to provide a body membrane that combines all of the benefits described in the above aspects.

In another aspect, the inventors have discovered that the concepts or principles of the present invention are applicable not only to the cosmetic field, but also to other fields, such as the medical field, and thus can extend the body films of the above aspects to kits that also exhibit the benefits described herein with respect to these body films.

DISCLOSURE OF THE INVENTION

One subject of the present invention is therefore a kit I comprising: 1) a first composition in dry form comprising a substrate comprising at least one water-insoluble polyvalent metal salt and optionally, a water-soluble/dispersible active agent which is unstable in its dissolved/dispersed state, and 2) a second composition comprising at least one aqueous phase, and a) at least one water-soluble chelating agent for polyvalent metal ions, and b) at least one water-soluble gelling agent capable of forming a gel with polyvalent metal ions; wherein the first composition and the second composition are placed apart from each other.

Another subject of the present invention is to provide a further kit II comprising: 1) a third composition comprising at least one water insoluble substrate; and 2) a fourth composition in dry form comprising a water-soluble/dispersible active agent that is unstable in its dissolved/dispersed state, and a disintegrant.

Another subject of the present invention is the use of the kits 1 and/or 2 according to the invention for the care of keratin materials, in particular the skin. This use may manifest itself as a method of treating keratin materials, in particular the skin, comprising the steps of admixing the first and second compositions of the kit in a predetermined weight ratio, and then applying the mixture thus obtained to the keratin materials.

Another subject of the present invention is the use of the kits 1 and/or 2 according to the invention for managing skin wounds, for preventing post-operative adhesion formation or for filling or repairing osteochondral defects and the like. This use may manifest itself as a method of managing skin wounds, preventing post-operative adhesion formation, or filling or repairing osteochondral defects, comprising the steps of admixing a first composition and a second composition of the kit in a predetermined weight ratio, and then applying the mixture thus obtained to a desired location.

Other features and advantages of the present invention will become more apparent upon reading the following specification and examples.

Detailed Description

Throughout the specification, including the claims, unless otherwise noted, the terms "comprising a" and "an" should be understood as being synonymous with "comprising at least one". Further, the expression "at least one" used in the present specification is equivalent to the expression "one or more".

Preferably, the "keratin material" is skin according to the invention. By "skin" we mean the whole body of the skin. Still preferably, the keratin material is the face or neck, especially the face.

By "topical application" is meant that the composition is applied or smeared onto at least one area of the surface of the keratin material, such as the skin.

By "rinse-off" is meant a composition that is removed from the skin by a rinsing composition, such as water, after a predetermined time of application to the skin.

"alkali metal" means an element in group IA of the periodic Table, such as sodium, potassium, lithium or combinations thereof, preferably sodium, potassium or combinations thereof.

The term "water-soluble or water-dispersible" refers to the following compounds: said compounds, when introduced into water at 25 ℃ in a concentration by mass equal to 1%, make it possible to obtain a macroscopically homogeneous and transparent solution, i.e. a solution having a maximum light transmission value of at least 60%, and preferably at least 70%, through a 1 cm thick sample at a wavelength equal to 500 nm.

In this application, unless explicitly stated otherwise, amounts, parts and percentages are expressed on a weight basis.

According to the present invention, the kit comprises a first composition and a second composition.

Set box I

The kit I according to the present invention comprises a first composition comprising a water-insoluble substrate comprising at least one water-insoluble multivalent metal salt and optionally, a water-soluble/dispersible active agent which is unstable in its dissolved/dispersed state; and a second composition, wherein the water-soluble/water-dispersible active agent is homogeneously distributed in the substrate.

First composition

First, the first composition according to the invention comprises at least one water-insoluble substrate.

Water insoluble substrate

For the purposes of the present invention, the term "water-insoluble" means that the substrate is insoluble in water and does not disintegrate even when immersed in water, for example having a solubility of less than 0.01g/100g water; or only slightly soluble in water, e.g. having a solubility of less than 0.5g/100g of water, which does not disintegrate into a loose state when immersed in water.

Typically, the substrate may be a woven or nonwoven fabric, which may comprise or be made of: the fibers of at least one water-insoluble polyvalent metal salt (hereinafter also referred to as water-insoluble polyvalent metal salt fibers), especially alginate, alone or together with at least one other fiber selected from natural fibers, such as cotton, pulp, bamboo and cellulose fibers, semi-natural fibers, such as viscose rayon fibers, and synthetic fibers, such as polyester fibers, polyethylene terephthalate fibers, polyethylene fibers and polypropylene fibers, or mixtures thereof. Two or more selected from other fibers may be used in combination.

The substrate may be formed into a wide variety of shapes and forms, such as flat pads, thick pads, thin sheets of irregular thickness, depending on the desired use and characteristics of the kit. By way of example only, in the case of a body membrane, the substrate is typically designed to conform to an area of skin that requires topical application. To this end, the substrate is designed to correspond to the shape of the face, avoiding the eyes, nostrils and mouth area as needed, when applying the body membranes to the face. Non-limiting examples of substrates for use in the present invention are described in, for example, patent application WO 02/062132 or EP 2489286 a.

In particular, the water-insoluble substrate or cloth may comprise water-insoluble alginate fibers, in particular calcium alginate fibers, in an amount of from 10 to 100 wt.%, in particular from 15 to 50 wt.%, relative to the total weight of the water-insoluble substrate or cloth.

In particular, the water insoluble substrate or cloth may comprise at least one further fiber in an amount of from 0 to 90 wt. -%, especially from 50 to 85 wt. -%, relative to the total weight of the water insoluble substrate or cloth.

More particularly, a suitable nonwoven is made from 20% by weight of calcium alginate fibers and 80% by weight of lyocell fibers, relative to the total weight of the tissue, which is available under the name M762R-40CN from Sanjiang corporation.

Water-insoluble polyvalent metal salt

The substrate may comprise at least one water-insoluble multivalent metal salt.

In particular, the at least one water-insoluble polyvalent metal salt may be present in the form of a powder, granules, fibres or bulk state (bulk state).

For the purposes of the present invention, the term "microparticles" when used with respect to a water-insoluble polyvalent metal salt means that the salt is in particulate form.

According to one embodiment, the first composition of the invention may comprise a content of at least one water-insoluble multivalent metal salt ranging from 20% to 100% by weight, in particular from 20% to 50% by weight, relative to the total weight of the first composition.

In particular, the water-insoluble polyvalent metal salt may be formed from an acid anion and a polyvalent metal cation, especially calcium, strontium, zinc, copper, manganese, aluminum or mixtures thereof. The metal which can be used is preferably calcium, copper or a mixture thereof, more preferably calcium.

The acid providing the acid anion according to the present invention may be any known acid useful for cosmetic products as long as the salt formed from the acid and the polyvalent metal is water-insoluble or sparingly soluble. Typical acids which may be used include various inorganic acids, such as sulfuric acid, carbonic acid, phosphoric acid, meta-aluminic acid, silicic acid, and various organic acids, especially higher saturated or unsaturated fatty acids, especially those having 18 or more carbon atoms, such as stearic acid and oleic acid, or polycarboxylic acids, such as alginic acid, oxalic acid, especially, as long as the salts formed are water-insoluble or sparingly soluble.

More specifically, the at least one water-insoluble polyvalent metal salt may be an alginate salt, preferably selected from calcium alginate, strontium alginate, zinc alginate, copper alginate, manganese alginate or mixtures thereof, preferably calcium alginate or copper alginate, in particular calcium alginate.

The term "alginate" refers in particular to salts of alginic acid. Alginic acid (a natural substance obtained from brown algae or certain bacteria) is composed of two uronic acids linked together via 1, 4-glycosidic linkages: polyuronic acid consisting of beta-D-mannuronic acid (M) and alpha-L-glucuronic acid (G).

Water-insoluble alginates (in which the predominant cation is calcium) are present in particular in the leaves and stems of seaweeds of the class Phaeophyceae, examples of which areFucus vesiculosus (Fucus vesiculosus)Spirulina, spirulina (2)Fucus spiralis）、Ascophyllum nodosum (Schw.) Kuntze （Ascophyllum nodosum）、Macrocystis (Macrocystis pyrifera)Winged algae (c)Alaria esculenta）、Eclonia maxima、Black kelp (Lessonia nigrescens)Leptospira interrogans (Leptospira), Leptospira interrogans (Leptospira interrogans)Lessonia trabeculata）、Kelp (Laminaria japonica)Antarctic Pleurotus ostreatus (A. clarkii)Durvillea antarctica）、North China Kelp (Laminaria hyperborea)、Long-strand brown algae (Laminaria longicroris)、Laminaria digitata (Laminaria digitata) digitata）、Laminaria saccharina (Laminaria saccharonaria)、Kelps (Laminaria cloustoni)And gulfweed: (Saragassum sp）。

Suitable water insoluble alginates have a weight average molecular weight of about 20,000 daltons to about 500,000 daltons. As in Martinsen et al, "comprehensive of Differencen Methods for Determination of Molecular Weights and Molecular Weight Distribution of Alginates" (Carbohydr. Polymer., 15, 171-Bukurad 193, 1991), the Weight average Molecular Weight is calculated by first determining the intrinsic viscosity and then using the Mark-Houwink Sakurad equation.

According to one embodiment, the first composition of the invention may comprise a content of at least one water-insoluble alginate ranging from 10% to 100% by weight, in particular from 15% to 50% by weight, relative to the total weight of the first composition.

Super absorbent material (Superabsorbent material)

According to one embodiment of the invention, the first composition may comprise at least one superabsorbent material.

In particular, the at least one superabsorbent material may be present in the form of a powder, granules, fibres or in the loose state.

Superabsorbent materials advantageously exhibit an extremely high capacity to absorb liquids, and in particular water. In particular, it may exhibit an ability to absorb 15 times, or even 20 to 50 times, for example about 25 to 30 times its own weight of water.

The liquid absorption capacity of the superabsorbent material can be determined by carrying out the following method.

Weighing (M) a sample of superabsorbent material in the dry state in the form of a powder, fibres or in the loose state or arranged as a film or sheet_D). For example, a square nonwoven web having sides of about 1 centimeter (cm) may be used. In the present method, the superabsorbent material is obtained in the "dry" state by treatment in a drying oven at about 50 ℃ for about 4 hours (h).

Water (or any other liquid to be absorbed by the material) is brought into contact with the material. This can be done by immersing the material in a liquid or by pouring a liquid onto the material. For example, the material may be immersed for a duration of about 1 minute (min).

Excess water (or liquid) is used, for example, to completely saturate the material. Excess water (or liquid) is then removed, for example by drip-drying for about 2 minutes, and the liquid-saturated material is weighed (M)_L）。

The difference Δ between the weight of the material when saturated with liquid and the weight of the material when dry represents the amount of liquid absorbed, which weight is compared to the dry weight of the material. The resulting value C indicates the capacity of the superabsorbent material to absorb liquid, for example expressed in grams of liquid absorbed per gram of dry material:

the superabsorbent material may be selected from cellulose derivatives, alginates (excluding the water insoluble alginates and alkali metal alginic acid compounds described herein) and derivatives thereof, such as, inter alia, propylene glycol alginate or a salt thereof, polyacrylic or polymethacrylic acid derivatives, poly (meth) acrylamide derivatives, polyvinylpyrrolidone derivatives, polyvinyl ether derivatives, mixtures thereof, and the like.

In particular, the superabsorbent material may be selected from chemically modified cellulose derivatives. For example, it may be selected from the group consisting of carboxymethyl cellulose, sodium carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, sodium methyl cellulose, microcrystalline cellulose, sodium cellulose sulfate and mixtures thereof.

It may also be selected from alkyl celluloses. These polymers are obtained by grafting alkyl residues onto one or more hydroxyl groups of the cellulose polymer to form hydroxyalkyl derivatives. These alkyl residues may be selected from the following groups: stearyl, isostearyl, lauryl, myristyl, cetyl, isocetyl, cocoyl, palmityl, oleyl, linoleyl (linonyl), ricinoleyl, behenyl and mixtures thereof. These hydroxyalkyl cellulose derivatives may also be subjected to chemical modifications, for example using carboxyl residues.

The superabsorbent material may also be selected from natural polymer derivatives such as, for example, gelatin and glucomannan and galactomannan polysaccharides extracted from seeds, plant fibers, fruits, seaweed, starch, plant resins or even microbial sources. For example, it may be selected from agar gum (agar gum), guar gum, gum tragacanth, carrageenan, konjac gum, locust bean gum, gellan gum, xanthan gum, and mixtures thereof.

In particular, the first composition of the invention may comprise a content of from 0% to 90% by weight, in particular from 50% to 85% by weight, or even the remaining amount, excluding alginate, of at least one superabsorbent material, relative to the total weight of the first composition.

The first composition according to the invention comprises a water-soluble/dispersible active agent, which is preferably in dry form, more preferably in anhydrous form.

Water soluble/water dispersible active agents

An active agent is one that can bring about a cosmetic effect to the user, in particular to the skin, for example the face. Such cosmetic effects may be, for example, whitening, anti-aging, hydrating and/or moisturizing. Active agents conventionally used in cosmetic products may be used in the second composition according to the present invention as long as they are water-soluble/water-dispersible.

For the purposes of the present invention, the compositions of the present invention are particularly suitable for the use of water-soluble/water-dispersible active agents which are unstable in the dissolved/dispersed state.

For the purposes of the present invention, "unstable" means that the component or composition undergoes a significant change in its structure or properties in a solvent or in the dissolved/dispersed state within 2 months or preferably within 1 month. Such changes may be any changes that are undesirable for cosmetic applications, including, but not limited to, color changes, degradation, decomposition, reaction with other substances, significant evaporation, deposition, crystallization, and the like.

According to one embodiment of the invention, the active agent is selected from the group consisting of retinoids (retinoids), vitamin E (tocopherol), vitamin C (ascorbic acid), vitamin B group (e.g. vitamin B5 (panthenol), vitamin B3 (niacinamide), vitamin B1 and vitamin B2), vitamin D, vitamin K, niacin, folic acid, pantothenic acid, ferulic acid, ascorbic acid 2-glucoside and dipalmitoyl hydroxyproline (dipalmitoyl hydroxyproline) or derivatives thereof, such as salts or esters thereof.

Preferably, the water soluble/dispersible active agent is selected from the group consisting of retinoids and ferulic acid, wherein retinoids are retinoic acid, retinol (vitamin a) and esters thereof, such as retinol propionate and retinol acetate, or retinol palmitate.

More preferably, the water soluble/dispersible active agent is retinol or ferulic acid.

Vitamins suitable for use in the present invention may be represented, for example, by the product available from CSPC WEISHENG PHARMACEUTICAL, or sold under the name ascobic ACID 100 MESH available from BASF.

Useful water-soluble vitamin derivatives preferably comprise 3-o-ethyl ascorbic acid, ascorbyl glucoside, or mixtures thereof.

According to one embodiment, the second composition of the invention may comprise at least one water-soluble/water-dispersible active agent in a content ranging from 0.1% to 20% by weight, preferably from 0.5% to 10% by weight, relative to the total weight of the first composition.

Method of forming a first composition

The method of forming the first composition is not particularly limited as long as the water-soluble/water-dispersible active agent can be uniformly distributed in the substrate in an amount sufficient to form a gel.

According to one embodiment, the water soluble active agent is prepared as an aqueous solution. The water-soluble active agent is then loaded onto a substrate, such as a body film tissue, by dipping the substrate into the solution, pouring the solution onto the substrate, spraying the solution onto the substrate, and the like.

According to another embodiment, the water-soluble/dispersible active agent is prepared as a suspension or paste, for example by suspending or mixing the water-soluble/dispersible active agent in or with an aqueous medium other than water to form a suspension or paste thereof. The suspension or paste is then applied to a substrate, such as by coating, spraying, or the like, to uniformly distribute the water-soluble/water-dispersible active agent in the substrate in an amount sufficient to form a gel with the alginate on the substrate.

According to another embodiment, the water dispersible active agent is prepared as an aqueous dispersion, e.g., a water insoluble but dispersible active agent. The dispersion is then applied to a substrate, such as by coating, spraying, or the like, to uniformly distribute the water-dispersible active agent in the substrate in an amount sufficient to form a gel with the alginate on the substrate.

In the case of application of water-soluble/dispersible active agents using aqueous solutions, dispersions, suspensions or pastes, the wet substrate loaded with aqueous salt (aquouous salt) is subsequently dried. The method of drying the tissue is not particularly limited. For industrial applications, the wet substrate is dried in an economically efficient manner.

According to yet another embodiment, the water dispersible active agent in solid form, e.g., as a water insoluble salt, is crushed into a powder or particles, e.g., by grinding, crushing, or the like. The powder or particles are then applied uniformly to the substrate. The diameter of the powder or particles is not particularly limited, so long as the water-dispersible active agent can be uniformly distributed in the substrate in an amount sufficient to form a gel on the substrate (e.g., with alginate).

The kit I according to the present invention comprises a second composition in addition to the first composition (e.g. the water-insoluble substrate). After the second composition is dissolved in the aqueous solution, it is dipped, coated or otherwise contacted with the first composition, thereby uniformly distributing the active agent from the second composition onto the substrate.

Preferably, the weight ratio of the first composition (e.g. water insoluble substrate or cloth) to the second composition is from 10:1 to 1:10, preferably from 5:1 to 1:5, or preferably from 2:1 to 1: 2.

Second composition

The second composition of the invention comprises at least a) at least one water-soluble chelating agent for polyvalent metal ions and b) at least one water-soluble gelling agent capable of forming a gel with polyvalent metal ions.

According to the present invention, when the first composition is mixed with the second composition, the water insoluble polyvalent metal ion donor reacts with the salt in solution and releases the polyvalent metal ion, most of which will be captured by the water soluble chelating agent. A few free polyvalent metal ions in solution react with the water-soluble gelling agent and begin to form a gel on the surface of the tissue. As the concentration of free polyvalent metal ions decreases over time, the chelated polyvalent metal ions will be gradually released and then form a gel on the surface of the tissue. After a short time, a transition in the tissue texture and a homogeneous gel on the tissue surface will be observed.

Chelating agents for polyvalent metal ions

The second composition according to the invention comprises at least one water-soluble chelating agent for polyvalent metal ions to promote the texture transformation and especially to at least enhance the moisture or active transfer capacity. The water soluble polyvalent metal ion chelating agent is water soluble.

According to the invention, the water-insoluble polyvalent metal ion donor releases more or less polyvalent metal ions into the solution when the first composition is mixed with the second composition. Both the chelating agent for the polyvalent metal ion and the water-soluble gelling agent are capable of binding the polyvalent metal ion.

Surprisingly, the specific chelating agent according to the invention competes with the gelling agent in competition for binding to the polyvalent metal ion, so that the released polyvalent metal ion is largely captured by the water-soluble chelating agent. There is still a small number of free polyvalent metal ions that react in solution with the water-soluble gelling agent and begin to form a gel on the surface of the tissue. As the concentration of free polyvalent metal ions decreases over time, the chelated polyvalent metal ions will be gradually released and then form a gel on the fiber surface. That is, the specific chelating agent according to the invention acts as a reservoir for polyvalent metal ions that are gelated on the tissue surface.

Useful polyvalent metal ion chelating agents according to the present invention comprise aminocarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, diethylenetriaminepentaacetic acid, and in particular their alkali metal salts, such as the tetrasodium salt of N, N-bis (carboxymethyl) glutamic acid, tetrasodium EDTA, N-bis (carboxymethyl) glutamic acid (glutamic diacetic acid, GLDA); hydroxycarboxylic acids such as citric acid, tartaric acid, glucuronic acid, succinic acid, ethylenediamine disuccinic acid (EDDS), and particularly alkali metal salts thereof; hydroxyaminocarboxylic acids, such as hydroxyethylethylenediaminetriacetic acid (HEDTA), Dihydroxyethylglycine (DEG), in particular their alkali metal salts; polyphosphonic acids, and in particular alkali metal salts thereof; other phosphorus-containing organic acids, such as phytic acid, and in particular alkali metal salts thereof, such as sodium phytate, potassium phytate; polycarboxylic acids, such as polyacrylic acids, polymethacrylic acids, and in particular their alkali metal salts.

In one embodiment, the at least one water-soluble chelating agent for polyvalent metal ions is an alkali metal hydroxypolycarboxylate, which is represented by: alkanes containing 1 to 4 carbon atoms, preferably 2 or 3 carbon atoms, substituted by 1,2 or 3 hydroxyl groups (-OH), preferably by one (1) hydroxyl group, and further substituted by 2,3, 4 or 5 carboxylic acid (salt) groups (-COOM), preferably by 2 or 3 carboxylic acid (salt) groups (-COOM), wherein a plurality of groups M independently represent H or an alkali metal, with the proviso that at least one group M represents an alkali metal, such as Na, K or Li, preferably all groups M represent an alkali metal, such as Na, K or Li, preferably Na. More specifically, the at least one alkali metal hydroxypolycarboxylate may be selected from sodium tartrate, sodium citrate, potassium tartrate, potassium citrate and hydrates thereof, preferably sodium citrate, especially trisodium citrate. Sodium citrate is used herein to denote monosodium citrate, disodium citrate and trisodium citrate, and other alkali metal hydroxypolycarboxylates may be understood in a similar manner.

The alkali metals mentioned above are particularly preferably sodium or potassium, in particular sodium. Accordingly, preferred chelating agents may comprise sodium citrate, tetrasodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate, or mixtures thereof.

In particular, the second composition of the invention may comprise at least one water-soluble polyvalent metal ion chelating agent in a content ranging from 0.1% to 1% by weight, in particular from 0.2% to 0.4% by weight, relative to the total weight of the second composition.

Water-soluble gelling agent

The second composition according to the invention comprises at least one water-soluble gelling agent which can form a gel with the polyvalent metal ion to induce a texture transformation.

In the present application, the term "water-soluble gelling agent" refers specifically to one that can form a gel with the polyvalent metal ion from the first composition.

According to the present invention, the water insoluble polyvalent metal ion donor will release more or less polyvalent metal ions into solution when the first composition is mixed with the second composition. The gelling agent is specifically selected to have a lower ability to bind to the polyvalent metal ion than the chelating agent, such that the gelling agent does not bind to free polyvalent metal ions released directly from the first composition, but rather to polyvalent metal ions subsequently from the reservoir, i.e., chelated polyvalent metal ions. Accordingly, a gel may be formed on the surface of the first composition.

In accordance with the principles of the present invention, the gelling agent may thus be any substance that can form a gel with the polyvalent metal ion, but has a lower ability to bind to the polyvalent metal ion than the chelating agent. Examples of gelling agents may comprise gelatin, pectin, gellan gum, carrageenan, agar, alginic acid compounds, and in particular alkali metal salts of alginic acid, such as sodium alginate and mixtures thereof.

Pectin is a linear polymer of alpha-D-galacturonic acid (at least 65%) linked in the 1 and 4 positions with a proportion of carboxylic acid groups esterified with methanol groups. About 20% of the sugars constituting the pectin molecule are neutral sugars (L-rhamnose, D-glucose, D-galactose, L-arabinose, D-xylose). L-rhamnose residues, which are incorporated into the backbone at the 1,2 position, are found in all pectins.

The uronic acid molecule carries a carboxyl function. Such functionalities are when they are COO^-In form, the pectin is endowed with the ability to exchange ions. Divalent ions (particularly calcium) have the ability to form an ionic bridge between the two carboxyl groups of two different pectin molecules.

In the natural state, a certain proportion of the carboxyl groups are esterified with methanol groups. The natural degree of esterification of pectin can be between 70% (apple, lemon) and 10% (strawberry), depending on the source used. Hydrolysis of-COOCH using pectins having a high degree of esterification₃And (c) a group to obtain a weakly esterified pectin. Depending on the proportion of methylated or unmethylated monomers, the chain is therefore more or less acidic. HM (high methoxyl) pectin is thus defined as having a degree of esterification of more than 50% and LM (low methoxyl) pectin is defined as having a degree of esterification of less than 50%.

In the case of amidated pectins, -OCH₃radical-NH₂And (4) substituting the group.

Pectin is sold in particular by the company Cargill under the name Uninectine ™, CP-Kelco under the name Genu and Danisco under the name Grinsted Pectin.

Carrageenan is an anionic polysaccharide that constitutes the cell wall of various red algae (Rhodophyceae) belonging to the families: gigartinaceae (Gigartinacae), Sargassaceae (Hypneaceae), Furcellaceae (Furcellareae) and Polychaetaceae (Polyideaceae). They are usually obtained by hot water extraction (hot aqueous extraction) from the natural plants of the algae. These linear polymers formed from disaccharide units consist of two D-galactopyranose units alternately linked by α (1,3) and β (1,4) bonds. They are highly sulfated polysaccharides (20-50%) and the α -D-galactopyranosyl residues can be in the 3, 6-anhydro form. Several types of carrageenans are distinguished according to the number and position of sulfate groups on the repeating disaccharide of the molecule, namely: kappa-carrageenan with one sulfate group, iota-carrageenan with two sulfate groups and lambda-carrageenan with three sulfate groups.

Carrageenan consists essentially of potassium, sodium, magnesium, triethanolamine and/or calcium salts of polysaccharide sulfate.

Carrageenan in particular Solagum from SEPPIC^®As a name, Carragel by Gelymar^®、Carralact^®And Carrasol^®Named, Satiagel and Satiaglum ™ by Cargill, and Genulacta by CP-Kelco^®、Genugel^®And Genuvisco^®Sold under the name of Vietnam.

Agar is a galactopolysaccharide contained in the cell walls of some of the red algae (class rhodophyceae) of these species. They are formed of polymer groups whose basic main chains are β (1,3) D-galactopyranose and α (1,4) L3-6 anhydrogalactan chains, these units being regularly and alternately repeated. Differences within the agar family are attributed to the presence or absence of solvated methyl or carboxyethyl groups. These hybrid structures are usually present in variable percentages, depending on the species of algae and the harvest season.

The agar-agar is in the range of 40000 to 300000 g.mol^-1A mixture of high molecular weight polysaccharides (agarose and agar). It is obtained by making an algae extract, generally by autoclaving and by treating these liquids containing about 2% agar-agar to extract the latter.

Agar is, for example, known by the B & V Agar products group as Gold Agar, by the Hispanagar company as Agar and Grand Agar, and by the Setexam company as Agar-Agar, QSA (Quick dissolve Agar) and Puragar.

Gellan gum is an anionic linear heteropolyglycoside based on an oligosaccharidoside unit (tetraglycoside) consisting of 4 sugars. D-glucose, L-rhamnose and D-glucuronic acid in a ratio of 2:1:1 are present in the gellan gum as monomeric elements.

It is sold, for example, by CP Kelco under the name kellogel CG LA.

In one embodiment of the invention, the gelling agent is preferably selected from alkali metal alginic acid compounds. Particularly preferred gelling agents are alginates, such as sodium alginate or potassium alginate, especially sodium alginate.

According to one embodiment, the at least one water-soluble gelling agent is present in the second composition at 0.1% to 0.5% by weight, preferably at 0.1% to 0.3% by weight, relative to the total weight of the second composition.

According to the invention, the amounts of chelating agent and gelling agent are selected such that the molar ratio of the fraction released by the chelating agent that can be chelated with the multivalent cations to the fraction released by the gelling agent that can form a gel with the multivalent cations is from about 10:1 to about 1:1, preferably from about 5:1 to about 2: 1.

Alkali metal alginic acid compound

The term "alkali metal alginic acid compound" especially refers to alkali metal alginates (alginates) or alkali metal salts of alginic acid derivatives. The alkali metal alginic acid compound is water soluble.

Alginic acid (a natural substance obtained from brown algae or certain bacteria) is composed of two uronic acids linked together via 1, 4-glycosidic linkages: polyuronic acid consisting of beta-D-mannuronic acid (M) and alpha-L-glucuronic acid (G).

Alginic acid can form water soluble salts (alginates) with alkali metals such as sodium, potassium or lithium. These alginates are water soluble in aqueous media at pH 4, but dissociate to alginic acid at pH below 4.

Methods for recovering these water-soluble salts, particularly sodium alginate, from natural sources are well known and described, for example, in Green, U.S. Pat. No. 2,036,934 and Le Gloahec, U.S. Pat. No. 2,128,551.

Alginic acid or alginates may be chemically modified, especially with urea or urethane groups, or by hydrolysis, oxidation, esterification, etherification, sulphation, phosphorylation, amination, amidation or alkylation reactions, or by several of these modifications, to form alginic acid derivatives, including salts.

These derivatives may be anionic, cationic, amphoteric or nonionic and are capable of forming water soluble salts with alkali metals, such as sodium, potassium or lithium, to form the alkali metal salts of alginic acid derivatives.

More specifically, alginates can be reacted with alkylene oxides, such as ethylene oxide or propylene oxide, to form polyglycol alginates. The polyglycol segment is bonded to the alginate via one or more carboxyl groups. Typically, alginates react with propylene oxide to form a polypropylene glycol alginate (PPG alginate), and with ethylene oxide to form a polyethylene glycol alginate (PEG alginate). The preparation of polyglycol alginates is disclosed in Strong, U.S. Pat. No. 3,948,881, Pettitt, U.S. Pat. No. 3,772,266, and Steiner, U.S. Pat. No. 2,426,125.

Preferably, the polyglycol alginate has a degree of esterification of from about 40% to about 95%, more preferably from about 70% to 95%.

Suitable alginates have a weight average molecular weight of about 20,000 daltons to about 500,000 daltons. As in Martinsen et al, "comprehensive of Differencen Methods for Determination of Molecular Weights and Molecular Weight Distribution of Alginates" (Carbohydr. Polymer., 15, 171-Bukurad 193, 1991), the Weight average Molecular Weight is calculated by first determining the intrinsic viscosity and then using the Mark-Houwink Sakurad equation.

The weight average molecular weights indicated above also apply to the alkali metal salts of alginic acid derivatives.

A list of various commercially available alginates, their properties, and their source can be found in Shapiro, U.S. patent No. 6,334,968, table 1, column 16, line 49 to column 17, line 18, incorporated herein by reference.

According to one embodiment of the invention, the alkali metal alginic acid compound may be selected from sodium alginate and potassium alginate, preferably sodium alginate.

Representative alkali alginate compounds suitable for use in the present invention may be, for example, Kelcosol, Satialgine, Cecalgum or Algogel, Karma Biopolymer, Protanal, Danisco, Grindsted^®Alginate, Kimica Algin, and Manucol, ISP^®And Manugel^®Is a product sold under the name of the market.

Aqueous phase

The second composition according to the invention comprises at least one aqueous phase.

The at least one aqueous phase comprises water.

The aqueous phase may also comprise water-miscible organic solvents (at room temperature: 25 ℃), for example monoalcohols containing from 2 to 6 carbon atoms, such as ethanol or isopropanol; in particular polyols containing from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, and preferably from 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; glycol ethers (in particular having 3 to 16 carbon atoms), such as mono-, di-or tripropylene glycol (C)₁-C₄) Alkyl ethers, mono-, di-or triethylene glycols (C)₁-C₄) Alkyl ethers and mixtures thereof.

The aqueous phase may also comprise any water-soluble or water-dispersible compound compatible with the aqueous phase, such as hydrophilic gelling agents, preservatives or surfactants and mixtures thereof.

In particular, the second composition of the invention may comprise the at least one aqueous phase in a content ranging from 10% to 99% by weight, in particular from 50% to 99% by weight and more particularly from 70% to 99% by weight, relative to the total weight of the second composition.

Set box II

Kit II according to the present invention comprises 1) a third composition comprising at least one water-insoluble substrate; and 2) a fourth composition in dry form comprising a water-soluble/dispersible active agent that is unstable in its dissolved/dispersed state, and a disintegrant.

Third composition

The third composition comprises at least one water insoluble substrate.

Water insoluble substrate

The water-insoluble substrate of the third composition used in kit II may be the same as that used in the first composition. Alternatively, the water-insoluble substrate may be any conventionally used for cosmetic applications, such as for body films.

Other components described above for the first composition, such as superabsorbent materials, may generally be used in the third composition, as long as the components do not impair the desired effect of the kit II. Thus, no water soluble/dispersible active agent is present in the third composition.

Fourth composition

The fourth composition of kit II comprises a water-soluble/water-dispersible active agent that is unstable in its dissolved/dispersed state and a disintegrant.

Water soluble/water dispersible active agents

The water-soluble/water-dispersible active agents useful in the fourth composition of kit II may be the same as those used in the first composition. Alternatively, the water soluble substrate may be any that is conventionally used for cosmetic applications, such as for body films.

Disintegrating agent

To facilitate disintegration of the one or more water-soluble/dispersible active agents when dissolved in a solvent (e.g., water), a disintegrant is used in the fourth composition. Therefore, it is preferable to uniformly mix the disintegrant with the water-soluble/water-dispersible active agent.

Since both the active agent and the disintegrant are present in dry form in the fourth composition, in order to maintain a homogeneous mixed state, it is preferred that the disintegrant itself is a binder for the active agent, or that additional binders are added, to shape the disintegrant and the active agent together into a combined solid state (integrated solid state), such as particles, granules, spheres (spheres), beads, balls (balls), rods, strips, etc., which are in hollow or solid form. For rapid and consistent disintegration and dissolution of the active agent, forms such as granules, spheres, and the like are preferred.

Accordingly, the disintegrant is preferably selected from starches, such as corn starch, potato starch (tomato starch) or wheat starch; starch derivatives, such as pregelatinized starch, alpha starch, acrylic acid grafted starch, or sodium carboxymethyl starch; sugar or sugar alcohol or mixtures thereof.

Sugars and sugar alcohols

Sugars or sugar alcohols are preferably used as disintegrants according to the invention. More preferably, the sugar or sugar alcohol itself acts as a binder. Useful sugars include monosaccharides, disaccharides, and polysaccharides. The corresponding alcohols of the sugars are also useful.

Among monosaccharides, glucose and fructose may be preferred. Among the disaccharides, sucrose may be preferred. Among the sugar alcohols, sorbitol and mannitol may be preferred.

Representative of sugars suitable for use in the present invention may be, for example, the product sold under the name of perces SEMOULE SURFINE 250.

Formation of the fourth composition

In order to rapidly dissolve the disintegrant with the active agent, the fourth composition comprising them in a combined solid state is preferably made into particles, preferably in the form of granules, spheres, and the like. Methods for producing the combined solid state include fluidized bed methods, extrusion methods, spraying methods, centrifugation methods, and the like. The fluidized bed method is preferred. The fluidized bed process may be carried out at room temperature to an elevated temperature, e.g., about 25 to about 80 ℃, about 30 to 50 ℃, e.g., about 35 ℃.

For the fluidized bed process, the particles in the combined solid state of the active agent and disintegrant are preferably prepared by:

1) providing a solid active agent;

2) dissolving a disintegrant in water; and

3) feeding an aqueous solution of an active agent and a disintegrant to a fluidized bed to produce particles.

Preferably, for step 1), the active agent is provided as particles, for example in the form of powders, granules, spheres or spheres. If an additional binder is used, it is dissolved together with the disintegrant in step 2).

For high utilization of the aqueous solution and uniformity of the particles in the combined solid state, it is preferred to use a centrifugal-fluidized bed synthetic method in which centrifugal force is introduced into the fluidized bed. According to this synthesis method, a container storing an active agent is placed in a fluidized bed, and a rotating plate having a diameter slightly smaller than that of the fluidized bed is installed at the bottom of the fluidized bed to form a gap between the outer edge of the plate and the inner wall of the fluidized bed, through which a fluidizing gas is blown upward. The nozzle is immersed in the particles of active agent. The active agent particles sprayed with disintegrant and optionally binder (bind) move towards the edges of the plate due to centrifugal forces and are fluidized by the fluidizing gas, during which gravity also acts on the particles.

The rotating plate is preferably rotated at a linear velocity at the outer edge of the plate of 100-. When relatively small particles are desired, the high velocity can be increased, for example, to 1000-; when relatively large particles are required, the high velocity can be reduced to, for example, 100-1000 m/min, preferably 200-700 m/min.

The combined state of the disintegrant and the active agent is preferably a particle size having 20 to 40 mesh; a maximum loss on drying of less than 10%, preferably less than 5%, for example about 4%; and/or about 500 to 900kg/m³The bulk density of the particles of (1).

For the purposes of the present invention, the weight ratio of disintegrant to active agent in the fourth composition is from 1:100 to 1:4, preferably from 1:50 to 1:5, or preferably from 1:20 to 1: 10.

Optionally other components

The fourth composition may comprise other cosmetically acceptable components so long as the rapid dissolution of the fourth composition in water is not disturbed. For example, a filler having high water solubility may be added to the fourth composition. Preferably, the filler has a higher dissolution rate than the active agent. In particular, the fourth composition may comprise a binder in addition to and different from the disintegrant used, provided that the rapid dissolution of the fourth composition in water is not disturbed. Examples of the binder may include polyvinyl alcohol, sodium alginate, xanthan gum, and agar.

Use and form of kit II

According to the present invention, kit II comprises a third and a fourth composition. Since the active agent is stored in dry form, it is kept active as high as possible.

In one embodiment of the present invention, the third and fourth compositions are placed separately from each other in the kit II. Immediately prior to use, the second composition is added to an appropriate amount of solvent, e.g., water, to dissolve the active agent. The active agent dissolves very rapidly, facilitated by the disintegrant. A solution of the active agent is then applied to the water insoluble substrate of the first composition, for example by dipping the substrate into the solution, pouring the solution into the substrate, spraying the solution onto the substrate, and the like.

In another embodiment of the invention, the first and second compositions are placed in the same package, as the disintegrant facilitates dissolution of the active agent. Immediately prior to use, the first and second compositions are added together, e.g., immersed in a solvent, e.g., water.

For cosmetic use, in many cases, water cannot be added in an excessive excess, but rather a very fast dissolution rate of the second composition is highly desirable to meet, for example, the requirements of the application for the substantially immediate use of freshly mixed products, such as fresh mixed films. Due to the specific choice of active agent and disintegrant and optionally binder, the second composition can be dissolved very quickly for most cosmetic uses, e.g. within 3 minutes, preferably within 120 seconds, more preferably within 100 seconds.

In another embodiment of the invention, the substrate of the first composition comprises fibers of a water insoluble alginate, such as calcium alginate. Gelation occurs when such a substrate is applied with another gellable alginate, such as sodium alginate. Still because the disintegrant facilitates dissolution of the active agent, dissolution of the active agent will be completed quickly, well before the viscosity increases significantly due to gelation. Thus, even for such gelling systems, it is still possible to dispense the active agent onto the substrate.

Fifth composition

For products in which the third composition according to the present invention comprises a polyvalent metal ion, the fifth composition may further be used in kit II. A fifth composition of the invention comprises at least one aqueous phase, and at least one water-soluble gelling agent that can form a gel with the polyvalent metal ion. More preferably, the fifth composition comprises: a) at least one aqueous phase, and b) at least one water-soluble gelling agent capable of forming a gel with the polyvalent metal ion, and optionally, c) at least one water-soluble chelating agent for the polyvalent metal ion.

According to the present invention, when the first composition is mixed with the fifth composition, the water-insoluble polyvalent metal ion donor reacts with the gelling agent in the solution and releases the polyvalent metal ion, thereby forming a gel.

In the case where the fifth composition comprises both components b) and c) above, when the first composition is mixed with the fifth composition, the water-insoluble polyvalent metal ion donor reacts with the gelling agent in solution and releases polyvalent metal ions, most of which will be captured by the water-soluble chelating agent. A few free polyvalent metal ions react in solution with the water-soluble gelling agent and begin to form a gel on the surface of the tissue. As the concentration of free polyvalent metal ions decreases over time, the chelated polyvalent metal ions will be gradually released and then form a gel on the surface of the tissue. After a short time, a transition in the tissue texture and a homogeneous gel on the tissue surface will be observed.

According to one embodiment of the invention, the aqueous phase may be the same as described for the second composition of the invention.

According to one embodiment of the invention, the gelling agent may be the same as described for the second composition of the invention.

According to one embodiment of the invention, the chelating agent may be the same as described for the second composition of the invention.

Other components described above for the second composition may generally be used in the fifth composition, as long as the components do not impair the desired effect of kit II.

Hydrophilic gelling agent

The second and fifth compositions according to the invention may each comprise optionally at least one additional hydrophilic gelling agent.

For the purposes of the present invention, the term "hydrophilic gelling agent" refers to a compound that is capable of gelling the aqueous phase without binding polyvalent metal ions from the first or third composition.

The gelling agent may be water soluble or water dispersible.

More specifically, the hydrophilic gelling agent may be chosen from synthetic polymeric gelling agents, polymeric gelling agents of natural or natural origin, or mixtures thereof.

Synthetic polymeric gelling agent

For the purposes of the present invention, the term "synthetic" refers to derivatives of polymers which are not naturally occurring or of natural origin.

Synthetic polymeric gelling agents contemplated in accordance with the present invention may or may not be microparticles.

For the purposes of the present invention, the term "microparticles" when used in the synthesis of polymeric gelling agents means that the polymer is in the form of particles, preferably spherical particles.

More specifically, these polymers may be chosen in particular from:

modified or unmodified carboxyvinyl polymers, e.g. Carbopol from Goodrich^®(CTFA name: Carbomer) is a product sold under the name; polyacrylates, polymethacrylates, e.g. Lubrajel from Guardian^™And Norgel as a name or Hispagel by Hispano Chimica^®A product sold under the name; polyacrylamide; 2-acrylamido-2-methylpropanesulfonic acid optionally crosslinked and/or neutralizedAcid polymers and copolymers, e.g. Hostacerin AMPS from Clariant^®Poly (2-acrylamido-2-methylpropanesulfonic acid) sold under the name CTFA (ammonium polypropylenyldimethyltauamide); acrylamide and AMPS^®In the form of a W/O emulsion, e.g. Sepigel from SEPPIC^™305 is the name (CTFA name: polyacrylamide/C)_13-14Isoparaffin/laureth-7) and also with Simulgel^™600 are those sold under the name CTFA (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/Polysorbate 80 (Polysorbate 80)); and mixtures thereof.

Preferably, these polymers may be chosen from acrylates/acrylates C_10-30Alkyl ester cross-linked polymers, e.g. Carbopol^® ultrez 20、Carbopol^® ultrez 21、Permulen^™ TR-1、Permulen^™ TR-2、Carbopol^® 1382、Carbopol^®ETD 2020, Carbomer such as Synthalen^® K、Carbopol^®980. Acryloyldimethyl ammonium taurate/steareth-8 methacrylate copolymers, e.g. Aristoflex^®SNC, acrylate copolymers, e.g. Carbopol^®Aqua SF-1, Acryloyldimethyl ammonium taurate/Steareth-25 methacrylate crosspolymers, e.g. Aristoflex^®HMS, ammonium acryloyldimethyltaurate, e.g. Aristoflex^® AVC。

Preferably, these polymers may be selected from carboxyvinyl polymers, such as Carbopol^®Products (carbomers), e.g. Carbopol sold by Lubrizol^®Ultrez 20 polymer, and Pemulen product (acrylate/acrylic acid C)_10-30Alkyl ester copolymers); polyacrylamides, e.g. SEPPIC under the trade mark Sepigel^™305 (CTFA name: Polyacrylamide/C)_13-14Isoparaffin/laureth-7) or as Simulgel^™600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80); optionally crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, e.g.Hoechst under the trademark Hostacerin AMPS^®(CTFA name: Polyacryloyldimethylammonium taurate) sold poly (2-acrylamido-2-methylpropanesulfonic acid) or SEPPIC sold Simulgel^™800 (CTFA name: sodium polyacryloyldimethyl taurate/polysorbate 80/sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, e.g. the Simulgel sold by SEPPIC^™NS and Sepinov EMT 10; and mixtures thereof.

Preferably, these polymers may be chosen from those available under the trade name Lubrajel^™Glyceryl acrylate/acrylic acid copolymers available from ISP Technologies, Inc. (United Guardian Inc.), particularly known as Lubrajel^™In the form of an oil containing about 1.0% to 1.3% glyceryl acrylate/acrylic acid copolymer in an aqueous glycerol solution (about 40% glycerol). Lubrajel^™The oil also contained approximately 0.6% PVM/MA copolymer (also known as methoxy ethylene/maleic anhydride copolymer).

Polymeric gelling agents of natural or natural origin

For the purposes of the present invention, the term "natural source" is intended to mean a polymeric gelling agent obtained by modification of a natural polymeric gelling agent.

These gelling agents may be particulate or non-particulate.

More specifically, these gelling agents belong to the class of polysaccharides.

In general, the polysaccharides suitable for use in the present invention may be homopolysaccharides, such as fructans, glucans, galactans and mannans, or heteropolysaccharides, such as hemicelluloses.

Similarly, they may be linear polysaccharides, such as pullulan, or branched polysaccharides, such as gum arabic and pullulan, or mixed polysaccharides, such as starch.

Generally, the polysaccharide may be selected from polysaccharides made by microorganisms; polysaccharides isolated from algae, and higher plant polysaccharides, like polysaccharides (homogeneous polysaccharides), in particular cellulose and derivatives thereof or fructans, heteropolysaccharides (heterogeneous polysaccharides), such as gum arabic (gum arabic), galactomannans, glucomannans and derivatives thereof; and mixtures thereof.

In particular, the polysaccharide may be chosen from fructans, gellan (gellan), dextran, amylose, amylopectin, glycogen, pullulan, dextran, cellulose and derivatives thereof, in particular methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, mannan, xylan, lignin, arabinons, galactans, galacturonans (galacturonans), chitin, chitosan, glucuronans, arabinoxylans (araboxylans), xyloglucans, glucomannans, arabinogalactans, glycosaminoglycans (glycoaminoglucans), gum arabic (gum arabic), tragacanth gum, ghatti gum, locust bean gum, galactomannans, such as guar gum and non-ionic derivatives thereof, in particular hydroxypropyl guar gum and ionic derivatives thereof, biopolysaccharide gums of microbial origin (biopolysaccharide gums), in particular scleroglucan or xanthan gum, mucopolysaccharides, in particular chondroitin sulphate, and mixtures thereof. These polysaccharides can be chemically modified, in particular with urea or urethane groups, or by hydrolysis, oxidation, esterification, etherification, sulfation, phosphorylation, amination, amidation or alkylation reactions, or by several of these modifications.

The resulting derivatives may be anionic, cationic, amphoteric or non-ionic.

Advantageously, the polysaccharide may be selected from xanthan gum, scleroglucan gum, guar gum, inulin and pullulan and mixtures thereof.

In general, such compounds useful in the present invention are selected from those described in particular in the following documents: Kirk-Othmer's Encyclopedia of Chemical Technology, third edition, 1982, volume 3, pages 896-900 and 15, pages 439-458; polymers in Nature, published by John Wiley & Sons, Chapter 6, pp 240-328, 1980, by E.A. MacGregor and C.T. Greenwood; a Book entitled Handbook of Water-solvent Gums and Resins, published by McGraw Hill Book Company (1980), and published by Industrial Gums-Polysaccharides and the third derivative, edited by Roy L. Whistler, second edition, Academic Press Inc., by Robert L. Davidson.

More precisely, the polysaccharides suitable for use in the present invention can be distinguished according to whether they are derived from microorganisms, from algae or from higher plants, and are described in detail below.

Polysaccharides made from microorganisms

Xanthan gum

Xanthan gum is produced on an industrial scale by the bacterium Xanthomonas campestris（Xanthomonas campestris）The heteropolysaccharide produced by aerobic fermentation of (1). Like cellulose, its structure consists of a backbone of β (1,4) -linked β -D-glucose. One of the two glucose molecules carries a trisaccharide side chain consisting of alpha-D-mannose, beta-D-glucuronic acid and terminal beta-D-mannose. The internal mannose residue is typically acetylated at carbon 6. About 30% of the terminal mannose residues carry pyruvate groups attached in chelated form between carbon 4 and carbon 6. The charged pyruvate and glucuronic acid are ionizable and responsible for the anionic nature of xanthan gum (pH with negative charge as low as equal to 1). The contents of pyruvate residues and acetate residues vary depending on the strain, the fermentation method, the conditions after fermentation and the purification steps. These groups can be used with Na in commercial products⁺、K⁺Or Ca²⁺Ion neutralization (Satia, 1986). The neutralized form can be converted to the acidic form by ion exchange or by dialysis against an acidic solution.

Xanthan gum has a molecular weight between 1000000 and 50000000 and a viscosity (measured at 60 rpm on a Brookfield viscometer (Brookfield viscometer) of LVT type at 25 ℃) between 0.6 and 1.65 pa.s for an aqueous composition containing 1% xanthan gum.

Representative of xanthan gums are, for example, Rhodia Chimie under the name Rhodicare, Cargill texturing Solutions under the name Satiaxane^™Known as Novaxan (for the food, cosmetic and pharmaceutical industries), from ADM^™Kelzan, Nama and CP-Kelco^®And Keltrol^®Is a name ofThe product is sold.

Pullulan polysaccharide

Pullulan is a polysaccharide composed of maltotriose units, known under the name of α (1,4) - α (1,6) -glucan. Three glucose units in maltotriose are linked via α (1,4) glycosidic bonds, while successive maltotriose units are linked to each other via α (1,6) glycosidic bonds.

Pullulan is produced, for example, by the Hayashibara group in japan under the reference Pullulan PF 20.

Dextran and dextran sulfate

Dextran is a neutral polysaccharide without any charged groups, which is biologically inert and is prepared by fermentation of sugar beet sugar containing only hydroxyl groups. Dextran fractions of different molecular weights can be obtained from native dextran by hydrolysis and purification. The dextran may in particular be in the form of dextran sulphate.

Dextran is represented, for example, by products sold under the name Dextran or Dextran T by Pharmacosmos or Dextran 70 Powder by Meito Sangyo co. Dextran sulfate is sold under the name Dextran sulfate by the PK Chemical A/S company.

Succinoglycans

Succinoglycan is a high molecular weight extracellular polymer produced by bacterial fermentation, consisting of octasaccharide repeat units (8-saccharide repeats). Succinoglycans are sold, for example, by the company Rhodia under the name Rheozan.

Scleroglucan

Scleroglucan is a non-ionic branched homopolysaccharide composed of β -D-glucan units. The molecule consists of a linear backbone formed of D-glucose units linked via β (1,3) bonds, and wherein one third are linked to a pendant D-glucose unit via β (1,6) bonds.

A more complete description of scleroglucan and its preparation can be found in patent US 3301848.

Scleroglucan, for example from Alban Miiller, IncAmigel as name or Actigum by Cargill^™CS is sold under the name.

Polysaccharides isolated from algae

Furcellaran

Furcellaran is commercially obtained from the red alga furcellaran (Furcellaria fasztisiata). Furcellaran is produced, for example, by the company Est-Agar.

Polysaccharides of higher plants

This class of polysaccharides can be divided into homopolysaccharides (only one saccharide) and heteropolysaccharides (consisting of several types of saccharides).

a) Homopolysaccharides and derivatives thereof

The polysaccharide according to the invention may be selected from cellulose and derivatives or fructans.

Cellulose and derivatives

The polysaccharide according to the invention can also be cellulose or derivatives thereof, especially cellulose ethers or esters (e.g. methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate, cellulose nitrate, nitrocellulose).

The present invention may also contain cellulose-based associative polymers.

According to the present invention, the term "cellulose-based compound" refers to any polysaccharide compound with a linear sequence of anhydroglucopyranose residues (AGU) linked together via β (1,4) linkages in its structure. The repeating unit is a cellobiose dimer. AGU is in chair conformation and carries 3 hydroxyl functions: 2 secondary alcohols (at positions 2 and 3) and primary alcohols (at position 6). The polymers thus formed are combined together via intermolecular bonds of the hydrogen bond type, thereby providing cellulose with a fibrous structure (about 1500 molecules per fiber).

Depending on the source of the cellulose, the degree of polymerization varies greatly; which may have values of several hundred to several tens of thousands.

The hydroxyl groups of cellulose can be reacted, partially or completely, with various chemical reagents to produce cellulose derivatives with inherent properties. The cellulose derivative may be anionic, cationic, amphoteric or non-ionic. Among these derivatives, cellulose ethers, cellulose esters and cellulose ester ethers are distinguished.

Among the nonionic cellulose ethers, mention may be made of alkyl celluloses, such as methyl cellulose and ethyl cellulose; hydroxyalkyl celluloses such as hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; and mixed hydroxyalkyl alkylcelluloses such as hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose and hydroxybutylmethylcellulose.

Among anionic cellulose ethers, mention may be made of carboxyalkyl celluloses and their salts. For example, carboxymethyl cellulose, carboxymethyl methyl cellulose and carboxymethyl hydroxyethyl cellulose and their sodium salts may be mentioned.

Among the cationic cellulose ethers, mention may be made of crosslinked or non-crosslinked quaternized hydroxyethyl cellulose.

The quaternizing agent may in particular be glycidyltrimethylammonium chloride or a fatty amine, such as laurylamine or stearylamine. Another cationic cellulose ether which may be mentioned is hydroxyethyl cellulose hydroxypropyl trimethylammonium.

Quaternized cellulose derivatives are in particular:

quaternized cellulose modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof,

-quaternized hydroxyethylcellulose modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.

The alkyl groups carried by the above-mentioned quaternized cellulose or hydroxyethylcellulose preferably contain 8 to 30 carbon atoms. Aryl preferably means phenyl, benzyl, naphthyl or anthracenyl.

May indicate the presence of C_8-30Examples of fatty chain quaternized alkyl hydroxyethyl cellulose may include Quatrisoft LM 200, Quatrisoft LM-X529-18-A, Quatrisoft LM-X529-18B (C) products sold by Amerchol₁₂Alkyl) and Quatrisoft LM-X 529-8（C₁₈Alkyl), and the products Crodacel QM, Crodacel QL (C) sold by Croda corporation₁₂Alkyl) and Crodacel QS (C)₁₈Alkyl groups).

Among the cellulose derivatives, mention may also be made of:

cellulose modified with groups comprising at least one fatty chain, for example with groups comprising at least one fatty chain, such as alkyl, especially C_8-22Alkyl-, arylalkyl-and alkylaryl-modified hydroxyethylcellulose, such as the Natrosol Plus Grade 330 CS (C) sold by Aqualon₁₆Alkyl), and

cellulose modified with polyalkylene glycol alkylphenyl ether groups, such as the product Amercell Polymer HM-1500 (nonylphenylpolyethylene glycol (15) ether) sold by the company Amerchol.

Among the cellulose esters are inorganic cellulose esters (cellulose nitrate, cellulose sulfate, cellulose phosphate, etc.), organic cellulose esters (cellulose monoacetate, cellulose triacetate, cellulose amidopropionate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate trimellitate, etc.), and mixed inorganic/organic cellulose esters such as cellulose acetate butyrate sulfate and cellulose acetate propionate sulfate. Among the cellulose ester ethers, mention may be made of hydroxypropylmethylcellulose phthalate and ethylcellulose sulfate.

The cellulose-based compound of the present invention may be selected from unsubstituted cellulose and substituted cellulose. Representative of cellulose and derivatives are, for example, the FMC Biopolymers company Avicel^®The name of (microcrystalline cellulose, MCC), the name of Cekol (carboxymethyl cellulose) by Noviant (CP-Kelco), the name of Akzo Nobel, the name of Akucell AF (sodium carboxymethyl cellulose), the name of Methocel (cellulose ether) and Ethocell (Ethyl cellulose) by Dow, and the name of Aqualon by Hercules Aqualon^®(carboxymethylcellulose and sodium carboxymethylcellulose), Benecel^®(methylcellulose), Blanose [ (carboxymethylcellulose), Culminal [ [ sic ] N-acetyl-L-methyl-L-acetyl-L-methyl-L-^®(methyl cellulose, hydroxypropyl methyl cellulose), Klucel^®(hydroxypropyl cellulose), Polysurf^®(cetyl hydroxyethylcellulose) and Natrosol^®CS (hydroxyethyl cellulose) is a product sold under the name CS.

Fructosan

The polysaccharide according to the invention may in particular be a fructan selected from inulin and its derivatives (in particular dicarboxy inulin and carboxymethyl inulin).

Fructans (Fructans) or Fructans (Fructans) are oligosaccharides or polysaccharides that comprise a sequence of anhydrofructose units optionally combined with several sugar residues other than fructose. The fructans may be linear or branched. The fructan may be a product obtained directly from a plant or microbial source, or it may be a product of: the chain length thereof has been modified (increased or decreased) by fractionation, synthesis or hydrolysis, in particular by enzymatic methods. Fructans typically have a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60.

Three classes of fructans were distinguished. The first class corresponds to products in which the fructose units are mostly linked via β (2,1) bonds. These are substantially linear fructans, for example inulin.

The second class also corresponds to linear fructose, but the fructose units are essentially linked via β (2,6) bonds. These products are levans (levans).

The third class corresponds to mixed fructans, i.e. containing β (2,6) and β (2,1) sequences. These are essentially branched fructans, such as graminans.

The preferred fructan in the composition according to the invention is inulin. Inulin may be obtained, for example, from chicory, dahlia or Jerusalem artichoke (Jerusalem artichoke), preferably from chicory.

In particular, polysaccharides, especially inulin, have a degree of polymerization of from 2 to about 1000, and preferably from 2 to about 60, and a degree of substitution of less than 2 on the basis of one fructose unit.

Representative of inulin for use in the present invention are, for example, Beneo from Orafti^™Inulin as its name, and Frutafit from Sensus^®Is a product sold under the name of the market.

b) Heteropolysaccharide and derivatives thereof

The polysaccharide which may be used according to the invention may be a gum, such as cassia, karaya, konjac, tragacanth, tara, acacia or arabic.

Arabic gum

Gum arabic is a highly branched acidic polysaccharide in the form of a mixture of potassium, magnesium and calcium salts. The monomeric elements of the free acid (arabinonic acid) are D-galactose, L-arabinose, L-rhamnose and D-glucuronic acid.

Galactomannans (guar gum, locust bean gum, fenugreek gum, tara gum) and derivatives (guar phosphate, hydroxypropyl guar, etc.)

Galactomannans are nonionic polyglycosides extracted from the endosperm of leguminous seeds, which constitute storage carbohydrates.

Galactomannans are macromolecules consisting of a backbone of β (1,4) -linked D-galactopyranose units with pendant side branches consisting of single D-galactopyranose units linked α (1,6) to the backbone. The various galactomannans differ firstly in the proportion of alpha-D-galactopyranose units present in the polymer and secondly by a significant difference in the distribution of the galactose units along the mannose chains.

Guar gum has a mannose/galactose (M/G) ratio of about 2, tara gum of 3, and locust bean gum of 4.

Guar gum

Guar gum is characterized by a mannose/galactose ratio of about 2/1. The galactose groups are regularly distributed along the mannose chains.

The guar gums that can be used according to the present invention can be nonionic, cationic or anionic. According to the invention, chemically modified or unmodified non-ionic guar gums can be used.

Unmodified non-ionic guar gums are for example the Vidogum GH, Vidogum G and Vidocrem company of Unipektin, the Jaguar company of Rhodia, the Meypro company of Danisco^®Guir as a name, Viscogum from Cargill^™As the name and Supercol by Aqualon^®Guar gum is a product sold under the name guar gum.

Representative of the hydrolysed non-ionic guar that can be used according to the invention are for example the company Danisco, Meyprodor^®Is a product sold under the name of the market.

The modified nonionic guar gums which can be used according to the invention are preferably selected from C₁-C₆Hydroxyalkyl modification, among which mention may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl.

Such non-ionic guar gums optionally modified with hydroxyalkyl groups are for example available under the trade names Jaguar HP 60, Jaguar HP 105 and Jaguar HP 120 (hydroxypropyl guar) from Rhodia or N-Hance from Aqualon^®HP (hydroxypropyl guar) is sold under the name HP.

The cationic galactomannan gum preferably has a cationic charge density of less than or equal to 1.5 meq./g, more particularly between 0.1 and 1 meq./g. The charge density can be measured by Kjeldahl method. Which typically corresponds to a pH of about 3 to 9.

Generally, for the purposes of the present invention, the term "cationic galactomannan gum" refers to any galactomannan gum containing cationic groups and/or groups that ionize into cationic groups.

Preferred cationic groups are selected from those comprising primary, secondary, tertiary and/or quaternary amine groups.

The cationic galactomannan gum used will generally have a viscosity of from about 500 to 5X 10⁶And preferably between about 10³To 3X 10⁶Weight average molecular mass between.

Cationic galactomannan gums which may be used in accordance with the present invention are, for example, those comprising a tri (C)_1-4) Gums for alkylammonium cationic groups. Preferably, from 2% to 30% of the number of hydroxyl functions of these gums carry trialkylammonium cationic groups.

Among these trialkylammonium groups, mention may be made most particularly of the trimethylammonium and triethylammonium groups.

Even more preferably, these groups represent from 5% to 20% by weight relative to the total weight of the modified galactomannan gum.

According to the invention, the cationic galactomannan gum is preferably a guar gum comprising hydroxypropyl trimethylammonium groups, i.e. a guar gum modified, for example, with 2, 3-epoxypropyltrimethylammonium chloride.

These galactomannan gums, in particular guar gums, modified with cationic groups are products known per se and are described, for example, in patents US 3589578 and US 4031307. Furthermore, these products are in particular marketed by Rhodia under the trade names Jaguar EXCEL, Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar CI 62 (guar hydroxypropyltrimonium chloride), by Degussa under Amilan^®Guar (Guar hydroxypropyltrimonium chloride) as name and N-Hance by Aqualon^®3000 (guar hydroxypropyltrimonium chloride) is sold under the name guar gum.

Anionic guar gums which can be used according to the present invention are polymers comprising groups derived from carboxylic, sulfonic, sulfenic, phosphoric, phosphonic or pyruvic acids. The anionic group is preferably a carboxylic acid group. The anionic groups may also be in the form of acid salts, especially sodium, calcium, lithium or potassium salts.

The anionic guar that can be used according to the invention is preferably a carboxymethyl guar derivative (carboxymethyl guar or carboxymethyl hydroxypropyl guar).

Sophora japonica bean

Locust bean gum is extracted from the seeds of the locust bean tree (carotonia siliqua).

Unmodified locust bean gums useful in the present invention are for example the Viscogon ™ by Cargill, Vidogum L by Unipektin and Grinsted by Danisco^®LBG is sold under the name LBG.

Representative of chemically modified locust bean gums that can be used in the present invention are, for example, the cationic locust bean gums sold under the name Catinal CLB (locust bean hydroxypropyltrimonium chloride) by the company Toho.

Tara glue

Tara gum useful in the context of the present invention is sold, for example, by Unipektin under the name Vidogum SP.

Glucomannan (konjak glue)

Glucomannans are polysaccharides with high molecular weights (500000 < M glucomannan < 2000000) consisting of D-mannose and D-glucose units, which have a branch of about every 50 or 60 units. It is present in wood, but is also the main component of konjac gum. Amorphophallus konjac (Amorphophalus konjac) is a plant of the Araceae family.

Products which can be used according to the invention are, for example, Propol by Shimizu^®And Rheolex^®Sold under the name of Vietnam.

Other polysaccharides

Among other polysaccharides that can be used according to the invention, mention may be made of chitin (poly-N-acetyl-D-glucosamine, β (1,4) -2-acetamido-2-deoxy-D-glucose), chitosan and derivatives (chitosan- β -glycerophosphate, carboxymethylchitin, etc.), such as those sold by the company France-Chitine; glycosaminoglycans (GAGs) such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate and preferably hyaluronic acid; xylan (or arabinoxylan) and derivatives.

Arabinoxylans are polymers of xylose and arabinose, both classified under the name pentosans. Xylans consist of a backbone and side chains of β (1,4) linked D-xylose units, and three substituents are present on the backbone (Rouau & Thibault, 1987): the acid unit, the alpha-L-arabinofuranose unit, may contain arabinose, xylose, galactose and glucuronic acid in the side chain.

According to this variant, the polysaccharide is preferably hyaluronic acid or a salt thereof.

The at least one hydrophilic gelling agent may be present in an amount of, for example, 0.001 to 10 wt. -%, preferably 0.01 to 5 wt. -%, and more preferably 0.05 to 3 wt. -%, relative to the total weight of the third composition.

Active agent

According to one embodiment of the invention, the first composition may comprise at least one additional active agent.

According to one embodiment of the invention, the second composition may comprise at least one additional active agent.

According to one embodiment of the invention, the third composition may comprise at least one additional active agent.

When the first composition comprises at least one active agent, it can be incorporated into the first composition, in particular by means of an alternating electric field. The one or more active agents may be incorporated in particular in the powder state.

Among all the active agents which can be used in the present invention, mention may be made in particular of: alpha-or beta-hydroxy acids, such as lactic acid, glycolic acid, citric acid, 5-octanoylsalicylic acid (5-octanylsalicylic acid), alpha-hydroxydecanoic acid, alpha-hydroxylauric acid, tartaric acid, glucuronic acid, galacturonic acid, acrylic acid, alpha-hydroxybutyric acid, alpha-hydroxyisobutyric acid, malic acid, mandelic acid, phosphoric acid, pyruvic acid, lactobionic acid and salicylic acid.

Anti-acne agents such as salicylic acid or benzoyl peroxide, octopirox (octopirox), dextro-and levorotatory sulphur-containing amino acids, their salts and their N-acetyl derivatives, such as N-acetylcysteine, or agents intended to prevent skin ageing and/or to improve its condition, such as the alpha-and beta-hydroxy acids mentioned above, retinoids such as retinoic acid, retinol and its esters, such as retinol propionate and retinol acetate, or retinol palmitate, niacinamide, allantoin, aloe vera extract, azelaic acid, bisabolol, phytic acid, collagen or agents stimulating collagen formation, vitamins such as vitamin C or its derivatives, such as ascorbyl glucoside, vitamin E or its derivatives, vitamin A or its derivatives, vitamin F or its derivatives, dextro-and levorotatory sulphur-containing amino acids and its derivatives as mentioned above, vitamin A or its derivatives, vitamin F or its derivatives, and the like, Elastin, N-acetyl D-glucosamine, luteolin; or antioxidants, such as green tea or its active ingredients, glycerin, laponite, caffeine, essential aromatic oils (essential oils), colorants, free radical scavengers, moisturizers, depigmenting agents (depigmenting agents), agents for improving the complexion, such as artificial tanning agents of the dihydroxyacetone or tyrosine ester type (artificial-tanning agents), sebum regulators (lipomodulators), softeners, anti-wrinkle agents, keratolytic agents, refreshing agents (fresheners), deodorants, anesthetics, nourishing agents and mixtures thereof. Whitening agents (whitening agents) such as kojic acid, ascorbic acid phosphate, ascorbic acid glucoside, ascorbic acid and mixtures thereof may also be used.

In the case of body membranes, active agents for improving skin condition, such as moisturizers or agents that help improve the natural lipid barrier, such as ceramides, cholesterol sulfate and/or fatty acids and mixtures thereof, may also be used. Enzymes active on the skin, such as proteases, lipases, cerebrosidases and/or melanases and mixtures thereof, may also be used.

As further examples of active agents that may be suitable for use in the practice of the present invention, there are the following agents: drugs, peptides, proteins, detectable labels (detectable labels), contrast agents (contrast agents), analgesics, anesthetics, antimicrobials, anti-yeast agents, antifungals, antivirals, anti-dermatitides, antipruritics, antiemetics, vasoprotectants, antihalation agents, anti-irritants, anti-inflammatory agents, immunomodulators, anti-hyperkeratotic agents (anti-hyperkeratotic agents), dry skin treatments, antiperspirants, anti-psoriatic agents (anti-psoriatic agents), anti-dandruff agents, anti-aging agents, anti-asthmatic and bronchodilators, sunscreens, antihistamines, healing agents (healing agents), corticosteroids, tanning agents, and mixtures thereof.

The content of the at least one active agent in the first composition and/or the third composition may be adjusted according to the intended use of the kit.

Alkali metal hyaluronic acid compound

Hyaluronic acid compounds may also be used as active agents according to the invention. The hyaluronic acid compound is preferably an alkali metal hyaluronic acid compound.

The term "alkali metal hyaluronic acid compound" especially refers to an alkali metal salt of hyaluronic acid (hyaluronate) or a derivative thereof. The alkali metal hyaluronate compound is water soluble.

In the context of the present invention, the term "hyaluronic acid or derivative thereof" specifically covers the basic unit of hyaluronic acid of the formula:

it is the smallest fraction of hyaluronic acid containing disaccharide dimers (i.e. D-glucuronic acid and N-acetamidoglucose).

The term "hyaluronic acid or derivative thereof" also comprises, in the context of the present invention, linear polymers containing the above-mentioned polymeric units linked together in the chain via alternating β (1,4) and β (1,3) glycosidic bonds, said linear polymers having a molecular weight (Mw) which may be between 380 and 13000000 daltons. Such molecular weight depends to a large extent on the source of the hyaluronic acid obtained and/or the method of preparation.

In the natural state, hyaluronic acid is present in gels (pericellular gels) around cells, in the basic substance of connective tissues of vertebrate organs, such as the dermis and epithelial tissues, and in particular in the epidermis, in the synovial fluid of joints, in vitreous humor, in human umbilical cords and in cockscomb protrusions (crista galli inophyssis).

Thus, the term "hyaluronic acid or derivative thereof" encompasses all fractions or subunits (subbunits) of hyaluronic acid having molecular weights particularly within the molecular weight ranges highlighted above.

By way of illustration of the various hyaluronic acid fractions, reference may be made to the document "Hyaluronan fragments: an information-rich system", R.Stern et al, European Journal of Cell Biology 58 (2006) 699-715, which reviews the listed biological activities of hyaluronic acid on the basis of its molecular weight.

According to a preferred embodiment of the invention, the hyaluronic acid fraction suitable for the uses covered by the invention has a molecular weight of 50000 to 5000000, in particular 100000 to 5000000, especially 400000 to 5000000 Da. In this case, the term used is high molecular weight hyaluronic acid.

Alternatively, the hyaluronic acid fraction, which may also be suitable for the uses contemplated by the present invention, has a molecular weight of 50000 to 400000 Da. In this case, the term used is medium molecular weight hyaluronic acid.

Still alternatively, the hyaluronic acid fraction applicable for the uses contemplated by the present invention has a molecular weight of less than 50000 Da. In this case, the term used is low molecular weight hyaluronic acid.

Finally, the term "hyaluronic acid or derivatives thereof" also comprises hyaluronic acid esters, in particular those in which all or part of the carboxyl groups of the acid functions are esterified with oxyethylenated alkyl groups or alcohols containing from 1 to 20 carbon atoms, in particular with a degree of substitution at the level of D-glucuronic acid of hyaluronic acid of from 0.5 to 50%.

More specifically, hyaluronic acid or hyaluronate may be reacted with alkylene oxides, such as ethylene oxide or propylene oxide, to form polyglycol hyaluronates. The polyglycol segment is bonded to the hyaluronic acid via one or more carboxyl groups. Typically, hyaluronic acid or hyaluronate is reacted with propylene oxide to form polypropylene glycol hyaluronate and ethylene oxide to form polyethylene glycol hyaluronate.

Mention may also be made of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. These esters have been described in particular in D.Campoccia et al, "semi synthetic resinous materials from hydrophilic esterification", Biomaterials 19 (1998) 2101-2127.

The molecular weights indicated above are also effective for hyaluronic acid esters.

Auxiliary agent

In a known manner, the third composition of the invention may also contain adjuvants commonly found in cosmetics and/or dermatology, such as preservatives, antioxidants, pH regulators (acidic or basic), fragrances, fillers, bactericides, odor absorbers, colorants (pigments and dyes), emulsifiers and lipid vesicles.

Needless to say, the person skilled in the art will take care to select this or these optional additional compound(s) and/or the amount thereof such that the contemplated addition does not or substantially does not adversely affect the advantages of the third composition according to the invention.

Pharmaceutical form (Galenic form)

The third composition according to the invention can be in various forms, in particular in the form of an aqueous solution, dispersion or emulsion, such as in particular a water/oil or oil/water emulsion or a multiple emulsion.

The emulsion may have an oily or aqueous continuous phase. Such emulsions may be, for example, inverse (W/O) emulsions or direct (O/W) emulsions, or multiple emulsions (W/O/W or O/W/O).

In the case of emulsions, direct (O/W) emulsions are preferred.

In particular, the third composition according to the invention may be an oil-in-water (O/W) emulsion, a water-in-oil (W/O) emulsion or a multiple emulsion, preferably in the form of an oil-in-water (O/W) emulsion.

The third composition according to the invention is preferably an aqueous solution.

Set box III

According to the present invention, the kit III comprises a third composition comprising a polyvalent metal ion, a fourth composition and an aqueous fifth composition. Since the active agent is preserved in dry form, its activity is maintained as high as possible.

In one embodiment of the present invention, the third, fourth and fifth compositions are placed separately from each other in kit III. Immediately prior to use, the fourth composition is added to an appropriate amount of the aqueous fifth composition to dissolve the active agent. The active agent dissolves very rapidly, facilitated by the disintegrant. A solution of the active agent is then applied to the water insoluble substrate of the third composition, for example by dipping the substrate into the solution, pouring the solution into the substrate, spraying the solution onto the substrate, and the like.

In another embodiment of the invention, the third and fourth compositions are placed in the same package, as the disintegrant facilitates dissolution of the active agent. The third and fourth compositions are added together with the aqueous fifth composition just prior to use. Subsequently, gelation between the third and fifth compositions will occur simultaneously, and the fourth composition will dissolve into the fifth composition. Due to the extremely fast dissolution rate of the fourth composition achieved by the selection of the specific disintegrant and optional binder, the active agent in the fourth composition quickly dissolves into the aqueous phase as early as the completion of gelation, so that the active agent from the fourth composition is uniformly distributed in the finally formed gel.

The kit III according to the present invention may comprise 1 to 10 wt. -%, preferably 2 to 5 wt. -% of the third composition, 0.5 to 20 wt. -%, preferably 1 to 10 wt. -% or 2 to 5 wt. -% of the fourth composition and 70 to 98.5 wt. -%, preferably 75 to 95 wt. -% of the fifth composition, relative to the total weight of the kit III.

According to a preferred embodiment of the present invention, the kit III is present as a body film comprising:

1) a third composition consisting of a nonwoven (or tissue) comprising from 10% to 100% by weight, preferably from 15% to 50% by weight, of calcium alginate fibers, relative to the total weight of the nonwoven,

2) a fourth composition comprising, relative to the total weight of the second composition, from 20 to 99.9 wt. -%, preferably from 40 to 95 wt. -%, especially from 50 to 90 wt. -% of dry particles of at least one water-soluble/dispersible active agent and from 0.1 to 20 wt. -%, preferably from 0.2 to 15 wt. -%, especially from 0.5 to 10 wt. -% of at least one disintegrant,

3) a fifth composition comprising, relative to the total weight of the third composition, from 10% to 99% by weight, preferably from 50% to 99% by weight, of at least one aqueous phase, from 0.1% to 0.5% by weight, preferably from 0.1% to 0.3% by weight, of sodium alginate and from 0.1% to 2% by weight, preferably from 0.2% to 1% by weight, of sodium citrate,

wherein the body film comprises, relative to the total weight of the body film, 1-10 wt. -%, preferably 2-5 wt. -%, the third composition, 0.5-20 wt. -%, preferably 1-10 wt. -% or 2-5 wt. -% of the fourth composition, and 70-98.5 wt. -%, preferably 75-95 wt. -% of the fifth composition.

Method and use

The first to fifth compositions according to the invention can generally be prepared according to the general knowledge of a person skilled in the art. However, it is to be understood that the skilled person may select the method of preparation thereof on the basis of his general knowledge, taking into account the properties of the ingredients used, such as their solubility in the vehicle and the use envisaged for the composition or kit.

According to one embodiment, kits I, II and/or III according to the present invention may be used for conditioning keratin materials, in particular the face. This use may manifest itself as a method of conditioning keratin materials, in particular the face, comprising the steps of admixing the first and second compositions and optionally the third composition of the kit in a predetermined weight ratio, and then applying the mixture thus obtained as a film onto the keratin materials.

According to one embodiment, kits I, II and/or III according to the present invention may be used for managing skin wounds, for preventing post-operative adhesion formation, or for filling or repairing osteochondral defects, etc. This use may manifest itself as a method of managing skin wounds, preventing post-operative adhesion formation, or filling or repairing osteochondral defects, comprising the steps of admixing the first and third compositions of the kit in a predetermined weight ratio, and then applying it to a site in need of the mixture thus obtained as a body membrane or padding (stuffing).

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without thereby limiting its scope.

Examples

The amounts/concentrations of the ingredients in the compositions/formulations described below are expressed in weight% relative to the total weight of each composition/formulation.

I. Preparation of

As a second composition, inventive formulations a and B and comparative formulation a were prepared.

TABLE 1

As a third composition, formulations C and D of the present invention were prepared.

TABLE 2

In table 1, comparative a contains no trisodium citrate, compared to inventive formulation a.

Preparation protocol using the second composition in table 1: all ingredients were placed in a beaker, heated to 60 ℃ and stirred until homogeneous, and cooled to room temperature. As a first composition, a nonwoven fabric made only (100% by weight) of calcium alginate fibers, sold under the name M762R-40CN by the company Sanjiang, was used.

Preparation protocol using the third composition in table 2: all ingredients were placed in a beaker, heated to 60 ℃ and stirred until homogeneous, and cooled to room temperature. As a first composition, for formulation C of the present invention, a nonwoven fabric made of 20% by weight of calcium alginate fibers and 80% by weight of tencel fibers (tencel fiber) was used; for formulation D of the invention, a nonwoven made of 100% tencel fiber (tencel fiber) and treated with calcium stearate was used.

Example E

Tissue 1.5 grams, 20% by weight calcium alginate (containing 5% by weight ferulic acid) + 80% tencel fiber (tencel fiber);

preparation protocol using the first composition in table 1: to the first composition was added 30 grams of water, stirred until completely dissolved, and then mixed with paper towels.

Evaluation of inventive and comparative films

The inventive and comparative films were evaluated using the following protocol.

Texture transformation evaluation method

Five panelists visually rated the gel area on the tissue and rated it from poor to excellent, which was classified into the following four categories based on the average of the ratings: "excellent" (> 50%), "good" (30-50%), "normal" (10-30%) or "poor" (< 10%).

Refreshing feeling evaluation method

Five panelists evaluated the degree of greasiness of the skin by tactile means while gently moving the finger abdomen on the face.

Evaluation method the body membrane was applied to the face for 15 minutes and then removed and massaged on the skin. The greasiness of the skin is perceived by moving the finger belly over the face. Each reviewer then gives scores 0 through 15. The less greasy the feel, the higher the score given.

Evaluation indexes are as follows: we graded from poor to excellent, which are classified into the following four categories based on score: "excellent" (> 12), "good" (8-12), "general" (4-8), and "poor" (0-4).

Skin adhesion evaluation method

Five panelists visually evaluated the degree of body membrane attachment to the face, the amount of blisters around the eyes, nose and mouth, with a mirror under standardized lighting.

Evaluation method the body membrane was applied to the face and the amount of bubbles around the eyes, nose and mouth was observed. Each reviewer then gives scores 0 through 15. The fewer bubbles, the higher the score given.

Hydration effect evaluation method

Five panelists evaluated the hydration of the body membranes in terms of fullness, fine line improvement and soft skin provided by the formula.

Evaluation method the body membrane was applied to the face for 15 minutes and then removed and the skin massaged. The degree of wrinkles on the forehead and nasolabial folds were observed, the cheeks were touched with the index finger and middle finger, and skin softness was perceived by touch, and the degree of fine lines on the cheeks was observed. Each panelist gave a score of 0 to 15. The more full the skin, the higher the score given.

Method for evaluating moisture transferability

Five panelists visually evaluated the amount of sap left on the skin after removal of the body membranes under standardized lighting using a mirror.

Evaluation method the body membrane was applied to the face for 15 minutes and then removed. The amount of juice left on the skin was visually observed. Each reviewer then gives scores 0 through 15. The more juice left on the skin, the higher the score given.

The results obtained are detailed in the following table:

	invention A	Invention B	Comparison A
				Texture transformation	Good effect	Is excellent in	Difference (D)
Adhesion to skin	Is excellent in	Is excellent in	In general
				Refreshing feeling	Is excellent in	In general	Good effect
Hydration effect	Good effect	Is excellent in	In general
				Water transfer capacity	Is excellent in	In general	Difference (D)

Conclusion III

The inventive films are superior to comparative films in beneficial properties such as texture change, hydration effect and water transport ability.

The term "comprising" (and grammatical variations thereof) as used herein is used in an open sense as "having" or "including" rather than in an exclusive sense as "consisting only of …". The terms "a" and "an" and "the" as used herein are to be understood as including the plural as well as the singular.

The foregoing specification illustrates and describes the present disclosure. Additionally, the disclosure shows and describes only the preferred embodiments of the disclosure, but as mentioned above, it is to be understood that it is capable of changes or modifications within the scope of the concept as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art. The previous description is further intended to explain the best mode known of practicing the disclosure and to enable others skilled in the art to utilize the disclosure in such, or other, embodiments and with the various modifications required by the particular applications or uses disclosed herein. Accordingly, the description is not intended to limit the disclosure to the form disclosed herein. It is also intended that the appended claims be construed to include alternative embodiments.

All publications, patents, and patent applications cited in this specification are herein incorporated by reference as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated by reference and were set forth in its entirety herein for any and all purposes. In the event of inconsistencies, the present disclosure controls.

Claims

1. Kit I, comprising:

1) a first composition in dry form comprising a water-insoluble substrate comprising at least one water-insoluble multivalent metal salt and optionally, a water-soluble/dispersible active agent that is unstable in a dissolved/dispersed state, and

2) a second composition comprising at least one aqueous phase, and

a) at least one water-soluble chelating agent for polyvalent metal ions, and

b) at least one water-soluble gelling agent capable of forming a gel with the polyvalent metal ion;

wherein the first composition and the second composition are placed apart from each other; and is

Wherein the water-soluble/water-dispersible active agent is homogeneously distributed in the substrate.

2. The kit I according to claim 1, wherein the gelling agent is specifically selected to have a lower ability to bind to polyvalent metal ions than the chelating agent.

3. Kit I according to claim 1 or 2, wherein the at least one water-insoluble polyvalent metal salt is a water-insoluble alginate selected from calcium alginate, strontium alginate, zinc alginate, copper alginate, manganese alginate or mixtures thereof, preferably calcium alginate.

4. Kit I according to any one of the preceding claims, wherein the first composition is a woven or non-woven fabric made from fibers of the at least one water-insoluble alginate alone or together with one or more other fibers selected from natural fibers, such as cotton, pulp, bamboo and cellulose fibers, semi-natural fibers, such as viscose rayon fibers, synthetic fibers, such as polyester fibers, polyethylene terephthalate fibers, polyethylene fibers and polypropylene fibers or mixtures thereof.

5. Kit I according to any one of the preceding claims, wherein the at least one water-insoluble multivalent metal salt is present in the first composition in an amount of from 20 wt. -% to 100 wt. -%, preferably from 20 wt. -% to 50 wt. -%, relative to the total weight of the first composition.

6. Kit I according to any of the preceding claims, wherein the active agent is selected from the group consisting of retinoids, vitamin E (tocopherol), vitamin C (ascorbic acid), vitamin B group (e.g. vitamin B5 (panthenol), vitamin B3 (niacinamide), vitamin B1 and vitamin B2), vitamin D, vitamin K, niacin, folic acid, pantothenic acid, ferulic acid, ascorbic acid 2-glucoside, dipalmitoyl hydroxyproline or derivatives thereof, such as salts or esters thereof.

7. Kit I according to any of the preceding claims, wherein the water-soluble/water-dispersible active agent is selected from retinoic acid, retinol (vitamin a) and esters thereof, such as retinol propionate and retinol acetate, or retinol palmitate.

8. The kit I according to any of the preceding claims, wherein the water-soluble/water-dispersible active agent is retinol or ferulic acid.

9. Kit I according to any one of the preceding claims, wherein the at least one water-soluble chelating agent is selected from the group consisting of sodium citrate, disodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate, potassium phytate and mixtures thereof.

10. Kit I according to any one of the preceding claims, wherein the at least one water-soluble chelating agent for polyvalent metal ions is present in the second composition in an amount of from 0.1% to 1% by weight, preferably from 0.2% to 0.4% by weight, relative to the total weight of the second composition.

11. Kit I according to any of the preceding claims, wherein the gelling agent is selected from alkali metal alginates, alkali metal salts of alginic acid derivatives or mixtures thereof, preferably from sodium alginate, potassium alginate, lithium alginate, sodium polyethylene glycol alginate, potassium polyethylene glycol alginate, lithium polyethylene glycol alginate or mixtures thereof.

12. Kit I according to any one of the preceding claims, wherein the at least one water-soluble gelling agent is present in the second composition in an amount of from 0.1% to 0.5% by weight, preferably from 0.1% to 0.3% by weight, relative to the total weight of the second composition.

13. Kit I according to any one of the preceding claims, wherein the at least one aqueous phase is present in the second composition in an amount of from 10% to 99% by weight, preferably from 50% to 99% by weight, relative to the total weight of the second composition.

14. Kit I according to any of the preceding claims, wherein the weight ratio of the first composition to the second composition is from 1:3 to 1:20, preferably from 1:8 to 1: 1.

15. A kit II, comprising:

1) a third composition comprising at least one water insoluble substrate; and

2) a fourth composition in dry form comprising a water-soluble/dispersible active agent that is unstable in a dissolved/dispersed state, and a disintegrant.

16. The kit II according to claim 15, wherein the water-insoluble substrate comprises water-insoluble alginate fibers, in particular calcium alginate fibers, in an amount of from 10 to 100 wt. -%, particularly from 15 to 50 wt. -%, relative to the total weight of the water-insoluble substrate or cloth.

17. The kit II according to any of claims 15-16, wherein the weight ratio of the third composition to the fourth composition is from 10:1 to 1:10, or from 2:1 to 1: 2.

18. The kit II according to any of claims 15-17, wherein the water-soluble/water-dispersible active agent is selected from the group consisting of retinoids, vitamin E (tocopherol), vitamin C (ascorbic acid), vitamin B group (e.g. vitamin B5 (panthenol), vitamin B3 (niacinamide), vitamin B1 and vitamin B2), vitamin D, vitamin K, niacin, folic acid, pantothenic acid, ferulic acid, ascorbic acid 2-glucoside, dipalmitoyl hydroxyproline or derivatives thereof, such as salts or esters thereof.

19. The kit II according to any of claims 15-18, wherein the water soluble/water dispersible active agent is selected from retinoic acid, retinol (vitamin a) and esters thereof, such as retinol propionate and retinol acetate, or retinol palmitate.

20. The kit II according to any of claims 15-18, wherein the water-soluble/water-dispersible active agent is retinol or ferulic acid.

21. The kit II according to any of claims 15-20, wherein the disintegrant is selected from the group consisting of monosaccharides, preferably glucose and fructose; disaccharides, preferably sucrose; and sugar alcohols, preferably sorbitol and mannitol.

22. The kit II according to any of claims 15-21, wherein the weight ratio of disintegrant to active agent in the fourth composition is from 1:100 to 1:4, preferably from 1:50 to 1:5, or preferably from 1:20 to 1: 10.

23. The kit II according to any of claims 15-22, wherein the disintegrant and the active agent are shaped together into a combined solid state, such as particles, including granules, spheres, rods, strips, etc.

24. The kit II according to any of claims 15-23, wherein a binder other than and different from the disintegrant is added to form a combined solid state, wherein the binder is selected from the group consisting of polyvinyl alcohol, sodium alginate, xanthan gum and agar-agar.

25. The kit II according to any of claims 15-24, wherein the third composition comprises a polyvalent metal ion; and is

The kit II further comprises a fifth composition comprising:

a) at least one aqueous phase, and

wherein the gelling agent is selected from alkali metal alginates, alkali metal salts of alginic acid derivatives or mixtures thereof, preferably selected from sodium alginate, potassium alginate, lithium alginate, sodium polyethylene glycol alginate, potassium polyethylene glycol alginate, lithium polyethylene glycol alginate or mixtures thereof.

26. The kit II according to claim 25, wherein the at least one water-soluble gelling agent is present in the fifth composition at from 0.1 to 0.5 wt. -%, preferably from 0.1 to 0.3 wt. -%, relative to the total weight of the fifth composition.

27. The kit II according to any one of claims 25-26, wherein the fifth composition further comprises:

c) at least one water-soluble chelating agent for polyvalent metal ions;

wherein the at least one water soluble chelating agent is selected from the group consisting of sodium citrate, disodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate, potassium phytate, and mixtures thereof.

28. The kit II according to any of claims 25-27, wherein the at least one water soluble chelating agent for polyvalent metal ions is present in the fifth composition in an amount of from 0.1% to 1% by weight, preferably from 0.2% to 0.4% by weight, relative to the total weight of the fifth composition.

29. The kit II according to any one of claims 25-28, wherein the at least one aqueous phase is present in the fifth composition in an amount of from 10% to 99% by weight, preferably from 50% to 99% by weight, relative to the total weight of the fifth composition.