CN113226248A - Set for caring skin - Google Patents

Abstract

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

Description

Set for caring skin

Technical Field

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

Background

The ultimate goal in the cosmetic field has always been to provide products with skin benefits such as hydration, moisturization, whitening, cleansing, and the like.

Among all the compositions used for caring for keratin materials, in particular the skin, facial masks are known to have a high penetration efficacy on keratin materials. Thus, for example, a two-digit market for facial mask type cosmetics is seen in china.

There are generally four types of masks, i.e., a paste type, a peel type, a gel type, and a wet towel type. Among them, the cream-type and peel-off-type are mainly used for cleansing of keratin materials, while the gel-type and wet-towel-type masks are more commonly used for skin care. It is known to incorporate water-soluble active agents in gel or tissue type masks. These masks are said to provide high efficacy to the skin, such as hydration, whitening, etc., due to the permeability capabilities of the mask.

However, these products are still unsatisfactory. Some water-soluble active agents are generally less stable in the dissolved state, e.g., in aqueous solution, than their dry form, thus affecting their cosmetic effect. 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.

Especially in the food and pharmaceutical field, it is known to formulate these types of ingredients in dry form, such as beads, granules, particles, tablets and the like. For example, it is known to produce tablets containing ascorbic acid to keep high amounts of active ingredient from degradation. These tablets were then dissolved in water prior to administration.

However, the inventors have found that these dry form products are still not suitable for use in the cosmetic field, particularly in mask 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 poorly soluble 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 masks, which combine two or more of the advantages exhibited by known mask types, but which do not have one or more of the problems associated with them.

Object of the Invention

Accordingly, in one aspect, it is preferred to provide a composition for the care of keratin materials to more effectively dispense water-soluble 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 mask that is capable of undergoing a texture transition, such as from a paper towel to a gel, to bring about a pleasant consumer experience.

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

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

In another aspect, the inventors have found 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 the facial masks of the above aspects can be broadened to a kit that also exhibits the benefits described herein with respect to these facial masks.

DISCLOSURE OF THE INVENTION

The inventors have found that one or more of the above requirements can be met by a specific combination of: 1) a first composition comprising at least one water insoluble substrate; 2) a second composition comprising a water soluble active agent and a disintegrant in dry form.

One subject of the present invention is therefore to provide a kit 1 comprising a first composition and a second composition placed separately from each other.

Another subject of the invention is another kit 2 comprising a first composition comprising at least one polyvalent metal ion, a second composition comprising at least one water-soluble gelling agent capable of forming a gel with the polyvalent metal ion, and a third composition comprising at least one water-soluble gelling agent capable of forming a gel with the polyvalent metal ion.

Another subject of the invention is the use of a set 1 and/or 2 according to the invention for caring for keratin materials, in particular the skin. Such use may be represented by a method for caring for keratin materials, in particular the skin, comprising the steps of compounding 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 invention is the use of the kit 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 or the like. Such use may be represented by a method for managing skin wounds, for preventing post-operative adhesion formation or for filling or repairing osteochondral defects comprising the step of compounding the first and second compositions of the kit in a predetermined weight ratio and then applying to a site in need of the mixture thus obtained.

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

Preferably, the "keratin material" according to the invention is the skin. By "skin" is meant 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 spread (spread) 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 period of time has been applied 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 a compound which, when introduced into water at 25 ℃ in a concentration by mass equal to 1%, makes it possible to obtain a macroscopically homogeneous and transparent solution, i.e. a solution having a maximum light transmission value of at least 60%, 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 by weight.

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

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 upon immersion in water.

Generally, the substrate may be a woven or non-woven fabric made of fibers selected from natural fibers, such as alginate, 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 can be made in 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 mask, the substrate is typically designed to fit the area of skin to which topical application is desired. 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 mask to the face. Non-limiting examples of substrates that can be used 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 fabric may comprise water-insoluble alginate fibers, in particular calcium alginate fibers, in an amount of from 10 to 100 wt. -%, especially from 15 to 50 wt. -%, relative to the total weight of the water-insoluble substrate or fabric.

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

More particularly, a suitable nonwoven fabric is made of 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 alginates

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

The term "water-insoluble" means that the salt is insoluble in water and does not disintegrate into a bulk state (bulk state) when immersed in water.

In particular, the water-insoluble alginate may be formed from alginic acid and a certain multivalent cation, especially calcium, barium, strontium, zinc, copper, manganese, lead, cobalt, nickel, aluminium or mixtures thereof. More specifically, the at least one water-insoluble alginate may be selected from calcium alginate, barium alginate, strontium alginate, zinc alginate, copper alginate, manganese alginate, lead alginate, cobalt alginate, nickel alginate, aluminium alginate or mixtures thereof, preferably calcium alginate.

Water-insoluble alginates in which the main cation is calcium are present in particular in Phaeophyceae (A)Phaeophyceae) In the fronds and stems of the seaweed of (a), an example of the seaweed is Fucus vesiculosus (Fucus vesiculosus)Fucus vesiculosus) Spirulina, spirulina (2)Fucus spiralis) Ascophyllum nodosum (Ascophyllum nodosum.)Ascophyllum nodosum) Giant kelpMacrocystis pyrifera) Winged algae (c)Alaria esculenta）、Eclonia maximaGiant kelp (A) and (B)Lessonia nigrescens）、Lessonia trabeculataSea tangle (A)Laminaria japonica) Antarctic Pleurotus ostreatus (A. clarkii)Durvillea antarctica) Northern sea tangle (Laminaria hyperborea) Brown algae of longstrand (Laminaria longicruris) Laminaria digitata (Laminaria digitata)Laminaria digitata) Sugar-coated kelp (Tangle)Laminaria saccharina) Kelps and kelps (1)Laminaria cloustoni) AndSaragassum 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 intrinsic viscosity is first determined and the Weight average Molecular Weight is then calculated using the Mark-Houwink Sakurad equation.

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

For the purposes of the present invention, the term "microparticles" means that the alginate is in the form of particles.

According to one embodiment, the first composition of the invention may comprise said at least one water-insoluble alginate in a content 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 bulk state (bulk state).

Superabsorbent materials advantageously exhibit an extremely high capacity to absorb liquids, in particular water. In particular, it may exhibit a capacity 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 a superabsorbent material can be determined by carrying out the following method.

Weighing (M) a sample of powder, fibres or superabsorbent material in bulk state or arranged as a film or sheet in dry state_D). For example, a square nonwoven web having sides of about 1 centimeter (cm) may be used. In the context of the present process, 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 soaked 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, particularly derivatives such as propylene glycol alginate or salts thereof, derivatives of polyacrylic or polymethacrylic acid, derivatives of poly (meth) acrylamide, derivatives of polyvinylpyrrolidone, derivatives of polyvinyl ether, 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 (ricinoyl), behenyl and mixtures thereof. These hydroxyalkyl cellulose derivatives may also be subjected to chemical modifications, for example using carboxylic acid residues (carboxylic acid residues).

The superabsorbent material may also be selected from natural polymer derivatives such as 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, tragacanth gum, 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 of the at least one superabsorbent material other than alginate, relative to the total weight of the first composition.

The kit 1 according to the 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 fabric) 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 according to the invention comprises a water-soluble active agent and a disintegrant, both in dry form, preferably in anhydrous form.

Water soluble active agents

Active agents are agents 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. In the second composition according to the present invention, an active agent conventionally usable in cosmetics may be used as long as it is water-soluble.

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

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

Among the non-limiting examples of water-insoluble active agents, water-soluble vitamins may be mentioned.

Water-soluble vitamins

Water soluble vitamins may be used as active agents in the second composition. Examples of vitamins that may be used include vitamin C (ascorbic acid), the B-group of vitamins (e.g. vitamin B5 (panthenol), vitamin B3 (niacinamide), vitamin B1 and vitamin B2), niacin, folic acid, pantothenic acid, derivatives (especially esters) of these vitamins, and mixtures thereof.

Among them, vitamin C and vitamin B group are preferably used. More preferably, vitamin C is used.

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 include 3-o-ethyl ascorbic acid, ascorbyl glucoside, or mixtures thereof.

According to one embodiment, the second composition of the invention may comprise the at least one water-soluble active agent in a content ranging from 20% to 99.9% by weight, preferably ranging from 40% to 95% by weight and in particular ranging from 50% to 90% by weight, relative to the total weight of the second composition.

Disintegrating agent

To facilitate disintegration of the one or more water-soluble active agents when dissolved in a solvent, such as water, a disintegrant is used in the second composition. Therefore, it is preferable to uniformly mix the disintegrant with the water-soluble active agent.

Since both the active agent and the disintegrant are present in the second composition in dry form, in order to maintain a homogeneous mixing state, it is preferred that the disintegrant itself is a binder for the active agent, or that a further binder is added, to shape the disintegrant and the active agent together into an 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 (unitary) 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 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 by TEREOS under the name SURE SEMOULE SURFINE 250.

Formation of the second composition

In order to dissolve the disintegrants rapidly with the active agent, the integrated solid second composition comprising them is preferably made into particles, preferably in the form of granules, spheres, etc. Methods for preparing integrated solids include fluidized bed methods, extrusion methods, spraying methods, centrifugation methods, and the like. The fluidized bed method is preferred. The fluidized bed process can 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 integrated solid particles of active agent and disintegrant are preferably prepared by:

1) providing an active agent in solid form;

2) dissolving a disintegrant in water; and

3) feeding an aqueous solution of an active agent and a disintegrant into 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 integrated solid state, it is preferable 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 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 large particles are required, the high velocity can be reduced to, for example, 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 integrated state of the disintegrant and the active agent is preferably particles having a particle size of 20-40 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 (a) to (b).

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

Optional other Components

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

Suit 1

According to the invention, the kit 1 comprises a first composition and a second composition. Since the active agent is stored in dry form, its activity is maintained as high as possible.

In one embodiment of the invention, the first and second compositions are placed separately from each other in the set 1. 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 in 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. The first and second compositions are added together, e.g., immersed in a solvent, e.g., water, just prior to use.

For cosmetic use, in many cases water cannot be added in extreme excess, while a very fast dissolution rate of the second composition is highly desirable to meet, for example, the user's demand for substantially immediate use of freshly mixed products, such as freshly mixed masks. Due to the specific choice of active agent and disintegrant and optionally binder, the second composition can dissolve 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 used with another gellable alginate, such as sodium alginate. Still because the disintegrant facilitates dissolution of the active agent, dissolution of the active agent is completed quickly, well before the viscosity increases significantly due to gelation. Thus, even for such gelled systems, the active agent can still be dispensed onto the substrate.

Third composition

For products in which the first composition according to the invention comprises a polyvalent metal ion, the third composition may further be used in the product. The third composition of the present 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 third composition comprises: a) at least one aqueous phase, b) at least one water-soluble gelling agent capable of forming a gel with polyvalent metal ions, and c) at least one water-soluble polyvalent metal ion sequestering agent.

According to the present invention, when the first composition is mixed with the third 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 case the third composition comprises components b) and c) as described above, the water insoluble polyvalent metal ion donor reacts with the gelling agent in the solution and releases polyvalent metal ions, wherein a major part of the polyvalent metal ions will be additionally captured by the water soluble chelating agent, when the first composition is mixed with the third composition. 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 shift in the tissue texture and a homogeneous gel on the tissue surface was observed.

Polyvalent metal ion chelating agent

The third composition according to the invention comprises at least one water-soluble polyvalent metal ion chelating agent to promote the texture transformation, in particular at least to enhance the moisture or active delivery capacity. The water-soluble polyvalent metal ion chelator 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 third composition. Both the polyvalent metal ion chelating agent and the water-soluble gelling agent can bind to 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 surface of the tissue. That is, the specific chelating agent according to the invention acts as a reservoir for the polyvalent metal ions that are used to form the gel on the surface of the tissue.

Useful polyvalent metal ion chelating agents according to the present invention include aminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, diethylenetriaminepentaacetic acid, particularly alkali metal salts thereof such as N, N-bis (carboxymethyl) glutamic acid, tetrasodium EDTA, tetrasodium salt of N, 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), especially alkali metal salts thereof; hydroxyaminocarboxylic acids, such as hydroxyethylethylenediaminetriacetic acid (HEDTA), Dihydroxyethylglycine (DEG), in particular their alkali metal salts; polyphosphonic acids, especially alkali metal salts thereof; other phosphorus-containing organic acids, such as phytic acid, in particular alkali metal salts thereof, e.g. sodium phytate, potassium phytate; polycarboxylic acids, such as polyacrylic acids, polymethacrylic acids, in particular their alkali metal salts.

In one embodiment, the at least one water-soluble polyvalent metal ion chelating agent is an alkali metal hydroxypolycarboxylate, represented by an alkane 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/carboxylate groups (-COOM), preferably by 2 or 3 carboxylic acid/carboxylate 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, in particular trisodium citrate. Sodium citrate is used herein to denote monosodium citrate, disodium citrate and trisodium citrate, other alkali metal hydroxypolycarboxylates being understood in a similar manner.

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

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

Water-soluble gelling agent

The third composition according to the present invention comprises at least one water-soluble gelling agent, which can gel with the polyvalent metal ion to form a gel.

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

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 third composition. Accordingly, a gel is formed between the ions and the gelling agent. Where both a chelating agent and a gelling agent are used, the gelling agent is specifically selected to have a lower ability to bind to the polyvalent metal ion than the chelating agent is to bind to the polyvalent metal ion, so 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 released 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 gelling agent that can form a gel with the polyvalent metal ion but that has a lower ability to bind to the polyvalent metal ion than the chelating agent. Examples of gelling agents may include gelatin, pectin, gellan gum, carrageenan, agar, alginic acid compounds, particularly 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 to 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 are found in all pectins, incorporated into the backbone at positions 1, 2.

The uronic acid molecule carries a carboxyl function. When they are COO^-In form, this functionality confers the pectin 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 pectinsUnder the condition of-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.

Carrageenans are anionic polysaccharides that constitute the cell walls of various red algae (Rhodophyceae) belonging to the families Gigartinaae (Gigartinaae), Sargassaceae (Hypneaceae), Furcellareae (Furcellariaceae) and Polyideaceae (Polyideaceae). They are usually obtained by hot water extraction from natural strains 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 alpha-D-galactopyranosyl residues can be in the 3, 6-anhydro form. Depending on the number and position of sulfate groups on the repeating disaccharide of the molecule, several types of carrageenans are distinguished, 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 sulfates.

Carrageenan is 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 galactose polysaccharide contained in the cell walls of some of the red algae (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 is in the range of 40000 to 300000 g.mol^-1A mixture of high molecular weight polysaccharides (agarose and agar). It is obtained by preparing an algae extract, usually by autoclaving, and by treating these liquids containing about 2% agar to extract the agar.

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 club Agar) and Puragar.

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

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 third composition in a range from 0.1% to 0.5% by weight, preferably from 0.1% to 0.3% by weight, relative to the total weight of the third 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 from certain bacteria, is composed of two uronic acids linked together via a 1, 4-glycosidic bond: 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 are reacted with propylene oxide to form polypropylene glycol alginate (PPG alginate) and ethylene oxide to form polyethylene glycol alginate (PEG alginate). The preparation of polyglycol alginate salts is disclosed in Strong, U.S. patent No. 3,948,881, Pettitt, U.S. patent No. 3,772,266, and Steiner, U.S. patent No. 2,426,125.

Preferably, the polyglycol alginate salts have 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 intrinsic viscosity is first determined and the Weight average Molecular Weight is then calculated 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 sources 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 third 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 a water-miscible organic solvent (at room temperature: 25 ℃), for example a monoalcohol 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, 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 tri-propylene glycol (C)₁-C₄) Alkyl ethers, mono-, di-or tri-ethylene 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 third composition of the invention may comprise said at least one aqueous phase in a content ranging from 10% to 99% by weight, in particular from 50% to 99% by weight, more particularly from 70% to 99% by weight, relative to the total weight of the third composition.

Hydrophilic gelling agent

The third composition according to the invention may optionally comprise at least one additional hydrophilic gelling agent.

For the purposes of the present invention, the term "hydrophilic gelling agent" refers to a compound capable of gelling the aqueous phase without binding polyvalent metal ions from the first 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 agents

For the purposes of the present invention, the term "synthetic" means that the polymer is not a naturally occurring or naturally derived derivative of a polymer.

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. the Lubrajel and Norgel names Guardian or Hispagel names Hispamal Chimica^®A product sold under the name; polyacrylamide; optionally crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, for example from Clariant Inc. in Hostacerin AMPS^®Poly (2-acrylamido-2-methylpropanesulfonic acid) sold under the name CTFA (name of polypropylenepolyFA)Ammonium enoyldimethyltaurinate (ammonium polymethylammonium)); acrylamide and AMPS^®In the form of a W/O emulsion, as known by Sepigel ™ 305 from SEPPIC corporation (CTFA name: polyacrylamide/C)_13-14Isoparaffin/laureth-7) and the equivalent of Simulgel ™ (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/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 products (acrylate/acrylic acid C)_10-30Alkyl ester copolymers); polyacrylamide, e.g. SEPPIC under the trademark Sepigel 305 (CTFA name: polyacrylamide/C)_13-14Isoparaffin/laureth-7) or 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, for example Hoechst under the trademark Hostacerin AMPS^®Poly (2-acrylamido-2-methylpropanesulfonic acid) sold under the name CTFA (ammonium polyacryloyldimethyltaurate) or Simulgel-800 (CTFA name: polyacryloylbisSodium methyl taurate/polysorbate 80/sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate, such as the Simulgel ™ NS and Sepinov EMT 10 sold by SEPPIC; and mixtures thereof.

Preferably, these polymers may be selected from the group consisting of glycerol acrylate/acrylic acid copolymers available under the trade name Lubrajel @fromisp Technologies, inc. (United Guardian Inc.), in particular in the form of what is known as Lubrajel @ oil, which contains about 1.0% to 1.3% glycerol acrylate/acrylic acid copolymer in aqueous glycerol solution (about 40% glycerol). Lubrajel oil also included approximately 0.6% PVM/MA copolymer (also known as methoxyethylene/maleic anhydride copolymer).

Polymeric gelling agents of natural or natural origin

For the purposes of the present invention, the term "of natural origin" 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 group of polysaccharides.

In general, the polysaccharides suitable for use in the present invention may be homopolysaccharides, if glycans, 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 produced by microorganisms; polysaccharides isolated from algae, and higher plant polysaccharides such as homopolysaccharides, especially cellulose and its derivatives or fructans, heteropolysaccharides such as gum arabibles, galactomannans, glucomannans and their derivatives; 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, polygalacturonic acid (galacturonan), chitin, chitosan, glucuronoxylan, arabinoxylans, xyloglucans, glucomannans, arabinogalactans, glycosaminoglucans (glycoamidoglucans), gum arable, tragacanth gum, gum ghatti (ghatti gums), locust bean gum, galactomannans, such as guar gum and non-ionic derivatives thereof, in particular hydroxypropyl 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 (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 produced by 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 (a). 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 pyruvic and glucuronic acids are ionizable and thus responsible for the anionic nature of xanthan gum (negative charge down to a pH equal to 1). The contents of pyruvate residues and acetate residues vary depending on the strain, the fermentation process, the conditions after fermentation and the purification steps. These groups can be used as Na in commercial products⁺、K⁺Or Ca²⁺Ion neutralization (Satia, 1986). The neutralized form can be converted to the acid 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 of LVT type at 25 ℃) between 0.6 and 1.65 pa.s for an aqueous composition containing 1% xanthan gum.

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

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 of 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 particularly be in the form of dextran sulfate.

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 is for example sold by Alban Miiller under the name of Amigel or by Cargill under the name of Actigum ™ CS.

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 homogeneous polysaccharides (only one saccharide) and heterogeneous polysaccharides consisting of several types of saccharides.

a) Homogeneous polysaccharides 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 one primary alcohol (at position 6). The polymers thus formed are bound 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 celluloses include Quatrioft LM 200, Quatrioft LM-X529-18-A, Quatrioft LM-X529-18B (C) products sold by Amerchol₁₂Alkyl) and Quatrioft LM-X529-8 (C)₁₈Alkyl), 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, e.g.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.

Cellulose esters include inorganic cellulose esters (cellulose nitrate, sulfate, phosphate, etc.), organic cellulose esters (cellulose monoacetate, triacetate, amido propionate, acetate butyrate, acetate propionate, acetate trimellitate, etc.), and mixed organic/inorganic 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-acetyl-L-D-methyl-L-acetyl-L-methyl-L-methyl-cellulose^®(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 in combination with several sugar residues other than fructose. The fructans may be linear or branched. Fructans can be products obtained directly from plant or microbial sources, or products whose chain length 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, preferably from 2 to about 60.

Three classes of fructans were distinguished. The first class corresponds to products whose fructose units are predominantly 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, for example, rye polyfructose (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, in particular inulin, have a degree of polymerization of from 2 to about 1000, preferably from 2 to about 60, and a degree of substitution of less than 2, based on one fructose unit.

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

b) Heteropolysaccharides and derivatives thereof

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

Arabic gum

Gum arabic is a highly branched acidic polysaccharide in the form of a mixture of potassium, magnesium and calcium salts. The monomer units 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 of leguminous seeds.

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 in the 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 has a mannose/galactose (M/G) ratio of 3, and locust bean gum has a mannose/galactose (M/G) ratio 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 Unipectine, the Jaguar company of Rhodia, the Meypro company of Danisco^®Guar as the name, Viscogum ™ by Cargill Inc. and Supercol by Aqualon Inc^®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 ones available from Danisco as mepyrodor^®Is a product sold under the name of the market.

The modified non-ionic guar which can be used according to the invention is 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 determined by the 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 ionizable 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 10⁶Preferably 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 hydroxyl functional number of these gums carry trialkylammonium cationic groups.

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

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. In addition, these productsIn particular under the trade names Jaguar EXCEL, Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar CI 62 (guar hydroxypropyltrimonium chloride) by the company Rhodia, Amilan by the company Degussa^®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).

Locust bean gum

Locust bean gum is extracted from the seeds of the locust bean (Ceratonia 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 useful in the present invention can be, for example, the cationic locust bean gum sold under the name Catinal CLB (locust bean gum hydroxypropyl trimethyl ammonium 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 the other polysaccharides that can be used according to the invention, mention may also 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, preferably hyaluronic acid; xylans (or arabinoxylans) and derivatives.

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

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. -%, 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 further active agent.

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

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

When the first composition comprises at least one further active agent, it may 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, 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, dextro-and levorotatory sulfur-containing amino acids, their salts and their N-acetyl derivatives such as N-acetylcysteine, or agents intended to prevent skin aging and/or to improve the condition thereof, such as the above-mentioned alpha-and beta-hydroxy acids, 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 that stimulate 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 sulfur-containing amino acids and its derivatives, such as mentioned above, may also be used, Elastin, N-acetyl D-glucosamine, luteolin or antioxidants, such as green tea or active fractions thereof, glycerol, laponite, caffeine, essential oils (essential oils), colorants, radical scavengers, moisturizers, depigmenting agents (depigmenting agents), agents for improving the complexion, such as artificial tanning agents of the dihydroxyacetone or tyrosine ester type, sebum regulators (lipomodulators), softeners, anti-wrinkle agents, keratolytic agents, refreshing agents (fresheners), deodorants, anesthetics, nutritional agents and mixtures thereof. Bleaching agents (bleaching agents) such as kojic acid, ascorbyl phosphate, ascorbyl glucoside, ascorbic acid and mixtures thereof may also be used.

In the case of a mask, it is also possible to use active agents for improving the skin condition, such as moisturizers or agents which contribute to improving the natural lipid barrier, such as ceramides, cholesterol sulfates and/or fatty acids and mixtures thereof. 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 are pharmaceutical agents (agents for drugs), peptides, proteins, detectable labels (detectible labels), contrast agents, analgesics, anesthetics, antibacterial agents, anti-yeast agents, antifungal agents, antiviral agents, anti-dermatitis agents, antipruritics, antiemetics, vasoprotectants, anti-motion agents, anti-irritants, anti-inflammatory agents, immunomodulators, anti-hyperkeratotic agents (anti-hyperkeratotic agents), dry skin treatments, antiperspirants, anti-psoriasis agents, anti-dandruff agents, anti-aging agents, anti-asthmatic agents and bronchodilators, sunscreens, antihistamines, healing agents, corticosteroids, tanning agents (tanning agents) and mixtures thereof.

The amount 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 (fraction) containing the disaccharide dimer, D-glucuronic acid and N-acetylglucosamine.

The term "hyaluronic acid or derivative thereof" also comprises, in the context of the present invention, linear polymers comprising the above-mentioned polymeric units linked together in the chain via alternating β (1,4) and β (1,3) glycosidic bonds, the molecular weight (Mw) of 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 pericellular gels (mammalian gels), in the matrix 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 the processes of cockscomb protrusions (crista galli inophyssis).

Thus, the term "hyaluronic acid or derivative thereof" encompasses all fractions or subunits (subbunits) of hyaluronic acid having a molecular weight in particular within the molecular weight range highlighted above.

As an 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 between 50000 and 5000000 Da, in particular between 100000 and 5000000 Da, especially between 400000 and 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 between 50000 and 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 includes 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 are described in particular in D.Campoccia et al, "semi synthetic resinous materials from hydrophilic animal discovery", Biomaterials 19 (1998) 2101-2127.

The molecular weights indicated above also apply to the 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 further compounds and/or the amounts thereof such that the contemplated addition does not or substantially does not adversely affect the benefits of the third composition according to the invention.

Galenic 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) 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 in the form of an oil-in-water (O/W) emulsion, a water-in-oil (W/O) emulsion or a multiple emulsion, preferably an oil-in-water (O/W) emulsion.

The third composition of the present invention is preferably an aqueous solution.

Suit 2

According to the invention, kit 2 comprises a first composition comprising a polyvalent metal ion, a second composition and an aqueous third composition. Since the active agent is stored in dry form, its activity is maintained as high as possible.

In one embodiment of the invention, the first, second and third compositions are placed separately from each other in the kit 2. Immediately prior to use, the second composition is added to an appropriate amount of the aqueous third 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 first composition, for example by dipping the substrate in 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. The first and second compositions are added with the aqueous third composition just prior to use. Subsequently, gelation between the first composition and the third composition occurs simultaneously, and the second composition is dissolved into the third composition. Due to the extremely fast dissolution rate of the second composition achieved by the selection of the specific disintegrant and optional binder, the active agent in the second composition quickly dissolves into the aqueous phase as early as the completion of gelation, so that the active agent from the second composition is uniformly distributed in the finally formed gel.

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

According to a preferred embodiment of the invention, the set 2 is presented as a mask comprising:

1) a first composition consisting of a non-woven fabric (or towel) 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 non-woven fabric,

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

3) a third 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 mask comprises 1-10 wt%, preferably 2-5 wt%, of the first composition, 0.5-20 wt%, preferably 1-10 wt% or 2-5 wt%, of the second composition and 70-98.5 wt%, preferably 75-95 wt%, of the third composition, relative to the total weight of the mask.

Method and use

The first, second and third compositions according to the invention may generally be prepared according to the general knowledge of a person skilled in the art. However, it will be appreciated that the skilled person can select a method of preparation thereof on the basis of his general knowledge, taking into account the nature of the ingredients used, for example their solubility in the vehicle, and the uses envisaged for the composition or kit.

According to one embodiment, the kit 1 and/or 2 according to the invention can be used for conditioning keratin materials, in particular the face. Such use may be represented by a method for conditioning keratin materials, in particular the face, comprising the steps of compounding 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 mask on the keratin materials.

According to one embodiment, the kit 1 and/or 2 according to the invention can be used for managing skin wounds, for preventing post-operative adhesion formation or for filling or repairing osteochondral defects or the like. Such use may be represented by a method for managing skin wounds, for preventing post-operative adhesion formation or for filling or repairing osteochondral defects comprising the steps of compounding the first and third compositions of the kit in a predetermined weight ratio and then applying as a cover film (mask) or wadding (stuffing) to the site where the mixture thus obtained is needed.

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.

Example 1 preparation of example

Examples of the invention and comparative examples of a second composition of the invention were prepared, wherein each disintegrant also served as a binder. The compositions are provided in table 1 below:

TABLE 1

The preparation procedure is as follows:

the second compositions (inventive a to D and comparative F) were prepared according to the following method:

1) providing a disintegrant in powder form;

2) dissolving a disintegrant in water to obtain a disintegrant solution of 65% content; and

3) the powder of disintegrant was placed in a rotating-fluidized bed at a rotational speed of 1500 rpm/min (rotating plate with a diameter of 0.2m to produce a linear velocity of about 1884 m/min at the outer edge of the plate);

starting the spraying device of the fluidized bed and spraying the solution of disintegrant obtained from step 2) into the powder of disintegrant in the tangential direction of the plate to bind the powder to form particles;

monitoring the particle size and stopping spraying when the particle size reaches a desired value; and

the particles are dried.

Composition E according to the invention is prepared according to the following method:

1) premixing ascorbic acid and sucrose with sufficient water to form a dough-like paste;

2) the mixture is placed in an extrusion-spheronizer to form particles of the desired size according to conventional extrusion methods.

One example of preparing a third composition of the present invention, the composition of which is shown in table 2 below:

TABLE 2 composition III

INCI	Weight% relative to the total weight of composition III
		Propylene glycol	5
Pentanediol	2
		Glycerol	4
Phenoxyethanol	0.1
		EDTA disodium salt	0.1
Chlorophytidine ester	0.1
		Phycocolloid	0.15
Hydroxyethyl cellulose	0.1
		Hyaluronic acid sodium salt	0.05
Citric acid sodium salt	0.8
		Water (W)	QS to 100

The preparation procedure is as follows:

the ingredients listed in table 2 were mixed at 75 ℃ until homogeneous.

Finally, examples of mask products were prepared.

0.75G of each of compositions A to G were placed together as package 1 with a nonwoven fabric weighing 1.3G made of 20% by weight of calcium alginate fibres and 80% of lyocell fibres, sold under the name M762R-40CN by Sanjiang, respectively, and 33G of composition III was placed separately as package 2. The mask product was as follows:

table 3:

example 2 evaluation of examples

Each of the mask products a-G was evaluated for ease of use (as evidenced by the dissolution rate of the second composition during application), juice uptake (juice uptake), and delivery ability.

The dissolution rate was measured by mixing package 2 with package 1 (T0), rubbing the mixture by hand until the second composition dissolved (T1) and measuring the duration (T1-T0).

The juice uptake and delivery capacity was measured by weighing the mask product before, during and after application on a skin model (skin mangenquin). By "juice" is meant a mixture of the second composition (compositions a to G, respectively) and the third composition (composition III).

Juice absorption (g) shows the amount of juice on the towel after package 1 and package 2 are mixed; delivery Capacity (mg/cm)²) The amount of juice on the surface of the skin model is displayed.

More specifically, evaluation was performed according to the following method:

1. mixing pack 1 and pack 2 (T0), rubbing the mixture by hand until compositions a to G dissolve (T1);

2. applying the mask to the skin model, allowing it to remain for 20 minutes, and removing the mask;

3. wiping off the sap on the skin model and measuring the weight;

。

the evaluation results were as follows:

table 4:

examples	Dissolution Rate(s)	Skin feel
			Mask A of the present invention	90	Is excellent in
Mask B of the invention	180	Is somewhat heavy but acceptable
			Mask C of the invention	90	Is excellent in
Mask D of the invention	90	Is excellent in
			Mask E of the invention	120	Is excellent in
Comparative mask F	Insoluble in water	/
			Comparative mask G	N/A, composition G is too brittle to form granules	/
Mask A 'of the present invention'	90	Good effect

Table 5:

examples	Dissolution Rate(s)	Juice absorption	Delivery capability
				Mask A of the present invention	90	26.38	3.06
Comparative mask F	Insoluble in water	N/A, composition F is insoluble	N/A, composition F is insoluble
				Comparative mask G	N/A, composition G is too brittle to form granules	N/A, no formation of particles	N/A, no formation of particles
Mask A 'of the present invention'	90	20.17	2.28

Conclusion III

The mask of the present invention is excellent in beneficial properties, such as ease of use, as evidenced by the dissolution rate of the second composition during application within 180 seconds. More surprisingly, the inventors found that the present invention is also excellent in absorbing more juice and delivering more juice to the face, which means that more active agents such as ascorbic acid are permeable to provide high efficacy compared to the comparative mask.

In addition, the masks a to E of the present invention also exhibit a unique use experience: texture transition from paper towel to gel. This transformation further enhances the technical effects of the present invention, such as better juice absorption and delivery capacity, and in addition superior skin feel.

The foregoing description 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 variations or modifications can be made which are within the scope of the concepts 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 for any and all purposes as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated by reference. In the event of inconsistencies, the present disclosure controls.

Claims (37)

1. A kit, comprising:

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

2) a second composition comprising a water soluble active agent and a disintegrant in dry form.

2. A set according to claim 1, wherein the water-insoluble substrate is made of fibres selected from natural fibres, such as cotton, pulp, bamboo and cellulose fibres, semi-natural fibres, such as viscose rayon fibres, charcoal viscose fibres, bamboo charcoal viscose fibres, synthetic fibres, such as polyester fibres, polyethylene terephthalate fibres, polyethylene fibres and polypropylene fibres.

3. Kit according to any one of the preceding claims, wherein the water-insoluble substrate comprises water-insoluble alginate fibres, in particular calcium alginate fibres, in an amount of from 10% to 100% by weight, in particular from 15% to 50% by weight, relative to the total weight of the water-insoluble substrate or fabric.

4. A kit according to any preceding claim, wherein the weight ratio of the first composition to the second composition is from 10:1 to 1:10, or from 2:1 to 1: 2.

5. The kit according to any one of the preceding claims, wherein the water-soluble active agent is unstable in its dissolved state.

6. The kit according to any one of the preceding claims, wherein the water-soluble active agent is a water-soluble vitamin selected from the group consisting of vitamin C (ascorbic acid), the B-family of vitamins (e.g. vitamin B5 (panthenol), vitamin B3 (niacinamide), vitamin B1 and vitamin B2), niacin, folic acid, pantothenic acid, esters of these vitamins and mixtures thereof.

7. The kit according to any one of the preceding claims, wherein the water-soluble active agent is vitamin C.

8. The kit according to any one of the preceding claims, wherein the disintegrant is selected from the group consisting of starches, such as corn starch, potato 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.

9. The kit according to any one of the preceding claims, 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.

10. The kit according to any of the preceding claims, wherein the weight ratio of disintegrant to active agent in the second composition is from 1:100 to 1:4, preferably from 1:50 to 1:5, or preferably from 1:20 to 1: 10.

11. The kit according to any of the preceding claims, wherein the disintegrant and the active agent are shaped together into an integrated solid state, such as particles, including granules, spheres, rods, strips, etc.

12. The kit according to claim 11, wherein the second composition comprising the integrated solid state is prepared as particles having a particle size of 20-40 mesh; a maximum loss on drying of less than 10%, preferably less than 5%; and/or 500 to 900kg/m³The bulk density of (a) to (b).

13. Kit according to any of claims 11 to 12, wherein the integrated solid state is prepared by a fluidized bed process, an extrusion process, a spraying process and/or a centrifugation process.

14. The kit according to any one of claims 11 to 13, wherein the integrated solid state is prepared by a centrifugal-fluidized bed synthesis process, wherein centrifugal force is introduced into the fluidized bed.

15. The kit according to any one of claims 11 to 14, wherein a binder other than and different from the disintegrant is added to form an integrated solid state.

16. The kit according to any one of claims 11 to 15, wherein the binder is selected from polyvinyl alcohol, sodium alginate, xanthan gum and agar.

17. The kit according to any one of claims 11 to 14, wherein no additional adhesive is added to the second composition.

18. A kit according to any one of the preceding claims, wherein the first and second compositions are placed separately from each other in the kit.

19. A kit according to any one of the preceding claims, wherein the first composition and the second composition are placed in the same package.

20. The kit according to any one of the preceding claims, wherein the first composition comprises a polyvalent metal ion; and is

The kit further comprises a third composition comprising:

a) at least one aqueous phase, and

b) at least one water-soluble gelling agent that can form a gel with the polyvalent metal ion.

21. The kit of claim 20, wherein the at least one gelling agent comprises gelatin, pectin, gellan gum, carrageenan, agar, alkali metal alginic acid compounds, and mixtures thereof.

22. Kit according to any one of claims 20 to 21, wherein the gelling agent is selected from alkali metal alginic acid compounds.

23. The kit according to claim 22, wherein the alkali metal alginic acid compound 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.

24. The kit according to claim 22, wherein the alkali metal alginic acid compound is selected from the group consisting of sodium alginate and potassium alginate, preferably sodium alginate.

25. Kit according to any one of claims 20 to 24, wherein the at least one water-soluble gelling agent is present in the third 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 third composition.

26. The kit according to claim 20, wherein the third composition further comprises:

c) at least one water-soluble polyvalent metal ion chelating agent.

27. The kit of claim 26, wherein the polyvalent metal ion chelator comprises an aminocarboxylic acid, hydroxycarboxylic acid, hydroxyaminocarboxylic acid, polyphosphonic acid, other phosphorus-containing organic acid, or a mixture thereof.

28. The kit according to any one of claims 26 to 27, wherein the at least one water-soluble multivalent metal ion chelating agent is an alkali metal hydroxypolycarboxylate salt, represented by an alkane containing 1 to 4 carbon atoms, preferably containing 2 or 3 carbon atoms, substituted by 1,2 or 3 hydroxyl (-OH), preferably by one hydroxyl group, and further substituted by 2,3, 4 or 5 carboxylic acid/carboxylate groups (-COOM), preferably by 2 or 3 carboxylic acid/carboxylate 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, said alkali metal hydroxypolycarboxylate salt preferably being selected from the group consisting of sodium tartrate, sodium citrate, potassium tartrate, potassium citrate and hydrates thereof, sodium citrate, especially trisodium citrate, is preferred.

29. The kit according to any one of claims 26 to 28, 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.

30. The kit according to any one of claims 26 to 29, wherein the at least one water-soluble multivalent metal ion chelator is present in the third composition in an amount of from 0.1 wt.% to 1 wt.%, preferably from 0.2 wt.% to 0.4 wt.%, relative to the total weight of the third composition.

31. Kit according to any one of claims 20 to 30, wherein the at least one aqueous phase is present in the third composition in a range from 10% to 99% by weight, preferably from 50% to 99% by weight, relative to the total weight of the third composition.

32. The kit according to any one of claims 20 to 31, wherein the first composition, the second composition and the third composition are placed separately from each other in the kit.

33. The kit according to any one of claims 20 to 31, wherein the first and second compositions are placed in the same package, while the third composition is placed in another package.

34. Kit according to any one of claims 20 to 33, wherein the kit comprises, relative to the total weight of the kit:

i) 1-10 wt.%, preferably 2-5 wt.% of a first composition,

0.5-20 wt.%, preferably 1-10 wt.% or 2-5 wt.% of a second composition, and

iii) 70-98.5 wt.%, preferably 75-95 wt.% of a third composition.

35. A mask, comprising:

1) a first composition consisting of a non-woven fabric 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 non-woven fabric;

2) a second composition comprising dry particles of from 20 to 99.9 wt. -%, in particular from 50 to 90 wt. -% of at least one water-soluble active agent and from 0.1 to 20 wt. -%, in particular from 0.5 to 10 wt. -% of at least one disintegrant, relative to the total weight of the second composition;

3) a third composition comprising from 10% to 99% by weight, preferably from 50% to 99% by weight, of at least one aqueous phase, relative to the total weight of the third composition; 0.1 to 0.5% by weight, preferably 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 mask comprises 1-10 wt%, preferably 2-5 wt%, of the first composition, 0.5-20 wt%, preferably 1-10 wt% or 2-5 wt%, of the second composition and 70-98.5 wt%, preferably 75-95 wt%, of the third composition, relative to the total weight of the mask.

36. Use of a kit according to any one of the preceding claims for caring for keratin materials, in particular the skin, for managing skin wounds, for preventing post-operative adhesion formation or for filling or repairing osteochondral defects.

37. Method for caring for keratin materials, in particular the skin, for managing skin wounds, for preventing post-operative adhesion formation or for filling or repairing osteochondral defects, comprising the steps of:

i) mixing the first and second compositions of the kit according to any one of claims 20 to 34 and then mixing them with the third composition, or

Mixing the second and third compositions of the kit according to any one of claims 20 to 34 prior to mixing them with the first composition; and

to the location where the mixture thus obtained is desired.