CN113194908A

CN113194908A - Set for caring skin

Info

Publication number: CN113194908A
Application number: CN201880100560.0A
Authority: CN
Inventors: 许令玮; 冶玉华
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2018-12-29
Filing date: 2018-12-29
Publication date: 2021-07-30
Anticipated expiration: 2038-12-29
Also published as: CN115192473A; CN113194908B; WO2020133361A1

Abstract

A kit, comprising: (1) a first composition comprising at least one water-insoluble polyvalent metal salt and at least one water-soluble polyhydroxy polymer, and (2) a second composition comprising at least one aqueous phase, and a) optionally, at least one water-soluble polyvalent metal ion sequestering agent, and b) at least one water-soluble gelling agent that can form a gel with polyvalent metal ions. The kit can be used 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.

Description

Set for caring skin

Technical Field

The present invention relates to an alginic system, in particular to an alginic kit for skin care. 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 consumers with highly effective 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, a two-digit market for facial mask type cosmetics is seen in china.

There are generally four types of facial masks, i.e., a cream-type, peel-off, gel-type, and wet-towel type facial mask. Among them, the cream-type and peel-off-type masks are mainly used for cleansing keratin materials, while the gel-type and wet-towel-type masks are more commonly used for skin care. It is known that a gel type mask has good adhesion to the skin and can provide good freshness sensation, but may not sufficiently deliver moisturizing or hydrating effects to the skin, while a wet tissue type mask excels in delivering moisturizing and hydrating effects but withdraws the effects if applied for a long time. Furthermore, adhesion to skin may not be as good as a gel-type mask.

Meanwhile, for a mask, particularly a facial mask of a paper towel type, it is desired that the mask applied on the face is soft to bring a better tactile sensation and a better skin fitting degree.

Based on the above, there is a need for a new mask that combines two or more of the advantages exhibited by known mask types, but does not have one or more of the problems associated therewith.

Object of the Invention

Accordingly, in one aspect, there is a need 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, there is a need to provide a mask that has at least comparable or even greater moisture or active delivery capacity than observed with wet-wipe type masks.

In another aspect, there is a need to provide a mask which has good adhesion to the skin and can provide freshness as a gel type mask.

In another aspect, there is a need to provide a mask which can deliver a moisturizing effect or active to a keratin material for a long period of time without withdrawing the effect, thereby exhibiting further improved, for example, hydration effect as compared to a wet-wipe type mask.

In another aspect, there is a need to provide a mask that is significantly effective in improving fine lines.

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

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

DISCLOSURE OF THE INVENTION

The present inventors have found that one or more of the above requirements can be met by a particular combination comprising: 1) a first composition comprising at least one water insoluble polyvalent metal salt as an ion donor for the polyvalent metal, and at least one water soluble polyhydric polymer; and 2) a second composition comprising at least one aqueous phase, and a) optionally, at least one water-soluble polyvalent metal ion sequestering agent, and b) at least one water-soluble gelling agent capable of forming a gel with polyvalent metal ions.

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

Another subject of the invention is a mask pack 1 comprising: 1) a first composition comprising at least one water-insoluble polyvalent metal salt, at least one hydroxyl-rich fiber, and at least one water-soluble polyhydroxy polymer, and 2) a fourth composition comprising at least one aqueous phase, and b) at least one water-soluble gelling agent capable of forming a gel with polyvalent metal ions; wherein the first composition and the fourth composition are disposed separately from each other.

Another subject of the invention is the use of a second composition as a juice (juice) or part of a juice of a mask product, wherein said mask product comprises, separately from the second composition, a fabric (or a tissue) comprising at least one water-insoluble polyvalent metal salt according to the invention.

Another subject of the invention is the use of a kit according to the invention for the care of keratin materials, in particular the skin. Such use may be represented by a method for treating 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 a kit 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, preventing post-operative adhesion formation or filling or repairing osteochondral defects comprising the steps 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

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term "about", meaning within 10% of the number indicated (e.g., "about 10%" means 9% to 11%, and about "2%" means 1.8% to 2.2%).

The articles "a" and "an" as used herein mean one or more when applied to any feature in embodiments of the present invention described in the specification and claims. The use of "a" and "an" does not limit the meaning to a single feature unless such a limit is specifically indicated. The article "the" preceding singular or plural nouns or noun phrases denotes a particular specified feature or particular specified features and may have a singular or plural connotation depending upon the context in which it is used. The adjective "any" means one, some, or all, with no distinction being made between amounts.

The term "comprising" (and grammatical variants thereof) as used herein is used in an inclusive sense of "having" or "including," and not in an exclusive sense of "consisting only of …. Nevertheless, the skilled person will undoubtedly recognize that, for an embodiment that can be implemented in "comprising" form, "the form" consisting essentially of … and "consisting of …" is naturally a modification of this embodiment and is also within the scope of the invention.

All percentages and ratios are by weight unless otherwise indicated. All percentages are based on the total weight of the composition, unless otherwise indicated. The level of all components or compositions refers to the active level of that component or composition and excludes impurities, such as residual solvents or by-products, that may be present in commercially available sources.

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 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 rinse-off composition, such as water, after a predetermined 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 mentioned otherwise, the contents, parts and percentages are by weight.

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

First composition

First, a first composition according to the present invention comprises at least one water-insoluble polyvalent metal salt and at least one water-soluble polyhydroxypolymer.

Water-insoluble polyvalent metal salt

The term "water-insoluble" means that the salt is insoluble in water, e.g. has a solubility of less than 0.01g/100g of water, or only slightly soluble in water, e.g. has a solubility of less than 0.5g/100g of water, and does not disintegrate into the bulk state when immersed in water.

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

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

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

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

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

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).

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.

Water-soluble polyhydroxy polymers

The term "polyhydroxy polymer" refers to hydroxyl-containing nonionic polysaccharides.

The present inventors have surprisingly found that polymers rich in hydroxyl groups can soften fibers, especially when the fibers are also rich in hydroxyl groups. Herein, hydroxyl-rich fibers refer to fibers having at least 2 hydroxyl groups, preferably at least 3 hydroxyl groups per repeat unit of the polymer of the fiber and having at least one hydroxyl-containing side chain wherein less than 60%, preferably less than 30% or preferably less than 15% of the hydroxyl groups in the side chain are substituted.

Useful water-soluble polyhydroxy polymers include polyhydroxy carboxylic acids, acid esters; a polyhydroxycellulose; and the like.

Some celluloses are known to be useful in promoting gelling behavior. Accordingly, polyhydroxycellulose is preferably usable.

In particular, nonionic polyhydroxycellulose ethers are particularly preferred, among which hydroxyalkyl celluloses, such as hydroxymethylcellulose, Hydroxyethylcellulose (HEC) and Hydroxypropylcellulose (HPC), may be mentioned; and mixed hydroxyalkyl alkylcelluloses such as hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose and hydroxybutylmethylcellulose.

According to one embodiment, the first composition of the invention may comprise said at least one water-soluble polyhydroxypolymer in a content ranging from 0.001% to 1% by weight, in particular from 0.01% to 0.1% by weight, for example from 0.01% to 0.06%, 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 that the material has absorbed, and this 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 water insoluble alginates and alkali metal alginic acid compounds described herein as water soluble gelling agents) 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 gellan gum 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 said at least one superabsorbent material in a content or even in a residual amount (the rest) of from 0% to 80% by weight, in particular from 50% to 80% by weight, relative to the total weight of the first composition.

According to one embodiment of the invention, in particular for facial mask use, the first composition further comprises additional fibers other than the fibers formed by the at least one water-insoluble multivalent metal salt, wherein the at least one water-insoluble multivalent metal salt and the at least one water-soluble polyhydroxy polymer are loaded onto the additional fibers.

For example, according to embodiment 1, the water-insoluble polyvalent metal salt may be present in the form of fibers. The fibers of the at least one water insoluble multivalent metal salt may then be formed into a water insoluble substrate, either alone or with one or more other fibers. A water-soluble polyhydroxy polymer is loaded onto the substrate.

Alternatively, according to embodiment 2, the water-insoluble polyvalent metal salt and the water-soluble polyhydric polymer may be each uniformly distributed in the 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.

Embodiment 1:

generally, in this embodiment 1, the substrate may be a woven fabric or a nonwoven fabric made of the fibers of the at least one water-insoluble polyvalent metal salt (hereinafter also referred to as water-insoluble polyvalent metal salt fibers) together with at least one other fiber selected from natural fibers such as cotton, pulp, bamboo and cellulose fibers, semi-natural fibers such as viscose rayon fibers, synthetic fibers such as polyester fibers, polyethylene terephthalate fibers, polyethylene fibers and polypropylene fibers. Two or more selected from other fibers may be used in combination.

The present inventors have surprisingly found that hydroxyl-rich fibers can be easily softened with water-soluble polyhydroxyl polymers. Therefore, fibers rich in hydroxyl groups are preferably used according to the invention. Such fibers may be regenerated cellulose or cotton fibers. Examples of hydroxyl-rich fibers include Viscose (Viscose), Modal (Modal), Lyocell (Lyocell), Cupro (Cupro), Cotton (Cotton), and the like.

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.

According to embodiment 1, the water-insoluble polyvalent metal salt is preferably formed from organic acids, especially highly saturated or unsaturated fatty acids, especially those having 18 or more carbon atoms, such as stearic acid and oleic acid, or polycarboxylic acids, such as alginic acid, oxalic acid, among others.

In particular, the water insoluble substrate or fabric may comprise water insoluble polyvalent metal salt fibers, especially calcium alginate fibers, in an amount of from 10 to 80% by weight, especially from 10 to 40% by weight, relative to the total weight of the water insoluble substrate or fabric. Accordingly, the water insoluble substrate or fabric may comprise the at least one further fiber in an amount of from 10 to 80 wt. -%, in particular from 50 to 80 wt. -%, relative to the total weight of the water insoluble substrate or fabric.

More particularly, suitable nonwoven fabrics comprising calcium alginate fibers are commercially available from Sanjiang under the name M762R-40 CN.

Embodiment 2:

alternatively, according to embodiment 2, the substrate may comprise a woven or non-woven fabric consisting essentially of fibers selected from natural fibers, such as cotton, pulp, bamboo, and cellulose fibers; semi-natural fibers such as viscose rayon fibers; synthetic fibers such as at least one of polyester fibers, polyethylene terephthalate fibers, polyethylene fibers, and polypropylene fibers. For such substrates, the at least one water-insoluble multivalent metal salt is distributed in the substrate as homogeneously as possible.

Accordingly, water-insoluble polyvalent metal salts are prepared as aqueous dispersions, for example for water-insoluble calcium salts. The dispersion is then applied to a substrate, for example by coating, spraying or the like, so that the calcium salt is uniformly distributed in the substrate in an amount sufficient to form a gel with the alginate on the substrate. The wet substrate loaded with the aqueous salt (aquouous salt) is subsequently dried. The method of drying the tissue is not particularly limited. For industrial applications, the wet substrate is dried in an economically efficient manner.

According to another embodiment, the water-insoluble polyvalent metal salt, such as a calcium salt, in solid form, for example as a water-insoluble salt, is crushed into a powder or granules, for example by milling, grinding or the like. The powder or particles are then applied uniformly to the substrate. The diameter of the powder or particles is not particularly limited as long as the water-insoluble multivalent metal salt can be uniformly distributed in the substrate in an amount sufficient to form a gel with the alginate on the substrate.

According to embodiment 2, the water-insoluble polyvalent metal salt is preferably formed from an inorganic acid, for example, one selected from the group consisting of sulfonic acid, carbonic acid, phosphoric acid, meta-aluminate, silicic acid, preferably sulfonic acid.

According to embodiment 2, the water-insoluble substrate or fabric may comprise water-insoluble multivalent metal salts, especially calcium salts, in an amount of from 0.01 to 5 wt. -%, preferably from 0.02 to 1 wt. -% or preferably from 0.04 to 0.5 wt. -%, relative to the total weight of the water-insoluble substrate or fabric.

Method for bonding a polyhydroxy polymer to a substrate

To provide a softened substrate, a water-soluble polyhydroxy polymer is preferably combined with a water-insoluble substrate. The method of combining the water-soluble polyhydroxy polymer with the water-insoluble substrate is not particularly limited as long as the water-soluble polyhydroxy polymer can be uniformly distributed in the substrate in an amount sufficient to soften the substrate to a desired degree.

According to one embodiment, the water-soluble polyhydroxy polymer is prepared as an aqueous solution. The water-soluble polyhydroxy polymer is then loaded onto a substrate, such as a facial mask towel.

According to another embodiment, the water-soluble polyhydroxy polymer is prepared as a suspension or paste, for example, by suspending or mixing the water-soluble polyhydroxy polymer in or with a non-aqueous medium to form a suspension or paste thereof. The suspension or paste is then applied to a substrate, for example by coating, spraying or the like, so that the water-soluble polyhydroxy polymer is uniformly distributed in the substrate in an amount sufficient to form a gel with the alginate on the substrate.

In the case of application of the water-soluble polyhydroxypolymer using an aqueous solution, suspension or paste, the wet substrate loaded with an aqueous salt (aquous salt) is subsequently dried. The method of drying the tissue is not particularly limited. For industrial applications, the wet substrate is dried in an economically efficient manner.

According to yet another embodiment, the water-soluble polyhydroxy polymer in solid form is crushed into a powder or granules, for example by milling, grinding or the like. The powder or particles are then applied uniformly to the substrate. The diameter of the powder or particles is not particularly limited as long as the water-soluble polyhydroxy polymer can be uniformly distributed in the substrate in an amount sufficient to soften the substrate.

According to the present invention, the water-insoluble substrate or fabric may comprise a water-soluble polyhydroxy polymer, such as HEC or HPC, in an amount of from 0.001 to 1 wt. -%, in particular from 0.01 to 0.1 wt. -%, for example from 0.01 to 0.06%, relative to the total weight of the water-insoluble substrate or fabric.

The kit according to the present invention comprises a second composition separate and apart from the first composition (e.g. water insoluble substrate). The second composition is impregnated, coated or otherwise contacted with the first composition as desired to transform the texture of the first composition, for example from a paper towel to a gel.

Preferably, the weight ratio of the first composition (e.g. water insoluble substrate or fabric) to the second composition is from 1:3 to 1:20, preferably from 1:8 to 1:15, in order for sufficient texture transformation to occur.

Second composition

The second composition of the invention comprises at least a) optionally, at least one water-soluble polyvalent metal ion sequestering agent and b) at least one water-soluble gelling agent that forms a gel with polyvalent metal ions.

According to the present invention, when the first composition is mixed with the second composition, the water-insoluble polyvalent metal ion donor reacts with the salt in the solution and releases the polyvalent metal ion. When the second composition does not comprise component a), i.e. the at least one water-soluble multivalent metal ion chelating agent, the multivalent metal ions released into the solution react directly with component b), i.e. the at least one water-soluble gelling agent. When the second composition comprises component a), the polyvalent metal ions released into the solution will be largely captured by the water-soluble chelating agent. A few free polyvalent metal ions react in solution with the water-soluble gelling agent and begin to form a gel on the surface of the tissue. As the concentration of free polyvalent metal ions decreases over time, the chelated polyvalent metal ions will be gradually released and then form a gel on the surface of the tissue. After a short time, a shift in the tissue texture and a homogeneous gel on the tissue surface was observed.

Polyvalent metal ion chelating agent

The second composition according to the present invention comprises optional component a), i.e. 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 solution when the first composition is mixed with the second composition comprising component a). Both the chelating agent for the polyvalent metal ion and the water-soluble gelling agent are capable of binding the polyvalent metal ion.

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

Water-soluble gelling agent

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

In the present application, the term "water-soluble gelling agent" 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 second composition.

The gelling agent, according to the principles of the present invention, can thus be any gelling agent that can form a gel with the polyvalent metal ion. 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. When the second composition comprises component a), i.e. a chelating agent, the gelling agent and the chelating agent are specifically selected, wherein the gelling agent has a lower binding capacity to the polyvalent metal ion than the chelating agent to the polyvalent metal ion, such that the gelling agent does not bind to free polyvalent metal ions released directly from the first composition, but to polyvalent metal ions subsequently released from the reservoir (reservoir), i.e. chelated polyvalent metal ions. Accordingly, a gel may be formed on the surface of the first composition.

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 pectins, -OCH₃radical-NH₂And (4) substituting the group.

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

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 second composition at 0.1% to 0.5% by weight, preferably at 0.1% to 0.3% by weight, relative to the total weight of the second composition.

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

Alkali metal alginic acid compound

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

Alginic acid, a natural substance obtained from brown algae or 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 second composition according to the invention comprises at least one aqueous phase.

The at least one aqueous phase comprises water.

The aqueous phase may also comprise 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 (especially containing 3 to 16 carbons)Atom), 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 second 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 second composition.

Hydrophilic gelling agent

The second 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 (ammonium polyacryloyldimethyltauride); 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/acryloylSodium dimethyl 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^®(CTFA name: Polyacryloyldimethyltauamonium) sold as poly (2-acrylamido-2-methylpropanesulfonic acid) or SEPPIC sold as Simulgel ™ 800 (CTFA name: sodium polyacryloyldimethyltaurate/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.

According to the invention, hydroxyalkyl cellulose as nonionic cellulose ether belongs to the class of nonionic polysaccharides, so that it can be used as water-soluble polyhydroxyl polymer to soften hydroxyl-rich fibers. Thus, according to one embodiment of the invention, the first composition comprises hydroxyl-rich fibers and the second composition comprises hydroxyalkyl cellulose.

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

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

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) by Dow, and the name of Ethocel (Ethyl cellulose)Plain) as the name and Aqualon from 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, the hydroxyl functions of these gumsFrom 2% to 30% of the energy content carries 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. Furthermore, these products are in particular marketed by Rhodia under the trade names Jaguar EXCEL, Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar CI 62 (guar hydroxypropyltrimonium chloride), by Degussa under Amilan^®Guar (Guar hydroxypropyltrimonium chloride) as name and N-Hance by Aqualon^®3000 (guar hydroxypropyltrimonium chloride) is sold under the name guar gum.

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

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

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 second composition.

Active agent

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

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

When the first composition comprises the at least one 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 second 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 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, also suitable for the uses covered 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 comprises hyaluronic acid esters, in particular those in which all or part of the carboxyl groups of the acid functions are esterified with oxyethylenated alkyl groups or alcohols containing from 1 to 20 carbon atoms, in particular with a degree of substitution at the level of D-glucuronic acid of hyaluronic acid of from 0.5 to 50%.

More specifically, hyaluronic acid or hyaluronate may be reacted with alkylene oxides, such as ethylene oxide or propylene oxide, to form polyglycol hyaluronates. The polyglycol segment is bonded to the hyaluronic acid via a carboxyl group. 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 second 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 second composition according to the invention.

Galenic form (Galenic form)

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

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

1) nonwoven (or tissue) made from hydroxyl-rich fibres comprising from 0.01 to 5 wt. -%, preferably from 0.02 to 1 wt. -% or preferably from 0.04 to 0.5% of calcium sulphate or calcium carbonate and from 0.001 to 1 wt. -%, in particular from 0.01 to 0.1 wt. -%, like from 0.01 to 0.06% of HEC or HPC, relative to the total weight of the nonwoven, and

2) a composition comprising, relative to the total weight of the 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 0.5% by weight, preferably from 0.2% to 0.4% by weight, of sodium citrate,

wherein the weight ratio of the nonwoven fabric to the composition is from 1:3 to 1:20, preferably from 1:8 to 1: 15.

Different embodiments of the suit

Based on the discussion of a kit comprising a first composition and a second composition according to the present invention, it is to be understood that the following embodiments are also within the spirit of the present invention.

Specifically, according to the present invention, there is provided a mask pack 1 comprising:

1) a first composition comprising at least one water-insoluble polyvalent metal salt and at least one water-soluble polyhydroxy polymer, and

2) a fourth composition free of water comprising:

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

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

wherein the first composition and the fourth composition are disposed separately from each other.

For such a mask pack 1, the first composition and its components, including the water-insoluble salt and the water-soluble polyhydroxy polymer, and the fourth composition, including the water-soluble chelating agent, the water-soluble gelling agent, and the like, may be substantially the same as the set of the present invention, wherein the fourth composition is substantially equivalent to the second composition except for the absence of water. The construction of the mask pack 1 can also be substantially the same as the kit of the present invention. In addition, the amount of the composition, the components of the composition, and the ratios therebetween of the mask pack 1 can be referenced to the kit of the present invention.

To apply the mask package 1, the fourth composition can be mixed with water to form an aqueous solution of the fourth composition. Obviously, such an aqueous solution substantially corresponds to the second composition of the kit according to the invention. This aqueous solution is then mixed with the first composition, for example with reference to the way of mixing the first and second compositions of the kit according to the invention.

In particular, the mask pack 1 according to the present invention comprises:

1) a nonwoven fabric (or tissue) comprising, relative to the total weight of the nonwoven fabric, 0.01 to 5 wt. -%, preferably 0.02 to 1 wt. -% or preferably 0.04 to 0.5% of calcium sulfate or calcium carbonate and 0.001 to 1 wt. -%, in particular 0.01 to 0.1 wt. -%, like 0.01 to 0.06% of HEC or HPC, and

2) a water-free fourth composition comprising, relative to the total weight of the composition, from 0.1% to 0.5%, preferably from 0.1% to 0.3%, by weight of a water-soluble chelating agent and from 0.1% to 0.5%, preferably from 0.2% to 0.4%, by weight of a water-soluble gelling agent,

wherein the weight ratio of nonwoven to fourth composition is from 1:3 to 1:20, preferably from 1:8 to 1: 15.

Method and use

The first and second/fourth compositions according to the invention can 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 based on his general knowledge, taking into account the nature of the ingredients used, for example their solubility in the vehicle and the use envisaged for the composition or kit.

According to one embodiment, the kit according to the invention can be used for caring for keratin materials, in particular the face. Such use may be represented by a method for caring for keratin materials, in particular the face, 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 as a mask on the keratin materials.

According to one embodiment, the kit according to the invention may 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, preventing post-operative adhesion formation or filling or repairing osteochondral defects comprising the steps of compounding the first and second compositions of the kit in a predetermined weight ratio and then applying as a mask or tampon (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

I. Preparation of

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

TABLE 1

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

Procedure for preparing a second composition using the formulation in table 1: all ingredients were placed in a beaker, heated to 60 ℃ and homogenized until homogeneous, and cooled to room temperature.

The preparation procedure of the facial mask comprises the following steps: 0.75 grams each of formulations a through B and comparative a, respectively, were placed together with a nonwoven fabric weighing 1.3 grams made from 20% by weight calcium alginate fibers and 80% lyocell fibers sold by the company Sanjiang under the name M762R-40 CN.

Evaluation of the inventive mask and comparative mask

The masks of the present invention and the comparative mask were evaluated using the following procedures.

Texture transformation evaluation method

Five panelists visually rated the gelled area on the paper towel and ranked from poor to excellent, based on the average of the ratings into the following four categories: "excellent" (> 50%), "good" (30-50%), "normal" (10-30%) or "poor" (< 10%).

Freshness evaluation method

Five panelists evaluated the degree of greasiness of the skin by tactile means while the face was gently moved to the finger abdomen.

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

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

Skin adhesion evaluation method

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

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

Hydration effect evaluation method

Five panelists evaluated the hydration of the mask based on the fullness (plumpy), fine line improvement and soft skin provided by the formula.

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

Method for evaluating moisture delivery capability

Five panelists visually evaluated the amount of sap left on the skin after removing the mask with a mirror under standardized lighting.

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

The results obtained are detailed in the following table:

TABLE 2

	Formulation A	Formulation B	Comparative formulation A
				Texture transformation	Good effect	Is excellent in	Difference (D)
Adhesion to skin	Is excellent in	Is excellent in	In general
				Sense of freshness	Is excellent in	In general	Good effect
Hydration effect	Good effect	Is excellent in	In general
				Moisture delivery capacity	Is excellent in	In general	Difference (D)

Conclusion III

The mask of the present invention is superior to the comparative mask in beneficial properties such as texture change, hydration effect and moisture delivery ability.

Example 2:

as a first composition, inventive formulation C and comparative formulations B-D were prepared.

TABLE 3

The preparation procedure of the facial mask comprises the following steps: 0.75 grams of formula A was placed together with a nonwoven fabric weighing 1.3 grams made from formula C and comparative formulas B-D, respectively, to provide mask C and comparative masks B-D, respectively.

Evaluation of the inventive mask and comparative mask

Method for evaluating softness

(1) Five panelists evaluated the gelled area on the tissue by hand and graded from poor to excellent, based on the average of the grades, into the following 3 categories: "excellent" (uniformly softened), "normal" (softened but not uniform), or "poor" (not softened).

TABLE 4

	Face pack C	Comparative mask B	Comparative mask C	Comparative mask D
					Evaluation of	Is excellent in	In general	In general	Difference (D)

(2) The softening effect is indirectly evaluated by measuring the deformation of the mask, since a softened mask causes deformation.

Deformation (%) = ((value measured after fresh mixing) - (initial value))/(initial value).

TABLE 5

	Face pack C	Comparative mask B
			Deformation of	13.80%	8.42%

Conclusion III

The mask of the present invention is superior to the comparative mask in softness.

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

1. A kit, comprising:

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

a) optionally, at least one water-soluble polyvalent metal ion chelating agent, and

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

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

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

3. Kit according to any of the preceding claims, wherein the water-insoluble multivalent metal salt is selected from water-insoluble salts of calcium, strontium, zinc, copper, manganese or mixtures thereof.

4. The kit according to any of the preceding claims, wherein the at least one water-insoluble polyvalent metal salt is a water-insoluble calcium salt selected from the group consisting of calcium alginate, calcium sulfate and calcium carbonate or mixtures thereof.

5. A kit according to any one of the preceding claims wherein the water-soluble polyhydroxy polymer comprises a polyhydroxy carboxylic acid, an acid ester; a polyhydroxycellulose or a mixture thereof, preferably hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose or hydroxybutylmethylcellulose.

6. A kit according to any one of the preceding claims, wherein the first composition of the invention comprises the at least one water-soluble polyhydroxypolymer in a content ranging from 0.001% to 1% by weight, in particular from 0.01% to 0.1% by weight, such as from 0.01% to 0.06%, relative to the total weight of the first composition.

7. The kit according to any one of the preceding claims, wherein the first composition further comprises additional hydroxyl-rich fibers, preferably regenerated cellulose or cotton fibers, wherein the at least one water-insoluble polyvalent metal salt and the at least one water-soluble polyhydroxyl polymer are loaded onto the additional fibers.

8. The kit according to claim 7, wherein the water-insoluble polyvalent metal salt is in the form of a fiber which is formed into a water-insoluble substrate with one or more additional fibers, the water-soluble polyhydric polymer being loaded onto the substrate.

9. Kit according to claim 8, wherein the water insoluble substrate comprises water insoluble polyvalent metal salt fibers in an amount of from 10 to 80 wt. -%, in particular from 10 to 40 wt. -%, and the at least one further fiber in an amount of from 10 to 80 wt. -%, in particular from 50 to 80 wt. -%, relative to the total weight of the water insoluble substrate.

10. The kit of claim 7 wherein one or more additional fibers are formed into a water insoluble substrate to which both the water insoluble multivalent metal salt and the water soluble polyhydroxy polymer are applied.

11. Kit according to claim 10, wherein the water insoluble substrate comprises water insoluble polyvalent metal salt fibers in an amount of from 0.01 to 5 wt. -%, preferably from 0.02 to 1 wt. -% or preferably from 0.04 to 0.5 wt. -%, relative to the total weight of the water insoluble substrate.

12. The kit according to any one of the preceding claims, wherein the polyvalent metal ion chelator comprises an aminocarboxylic acid, a hydroxycarboxylic acid, a hydroxyaminocarboxylic acid, a polyphosphonic acid, another phosphorus-containing organic acid, or a mixture thereof.

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

14. The kit according to any one of the preceding claims, wherein the at least one water-soluble multivalent metal ion chelator is present in the second 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 second composition.

15. The kit according to any one of the preceding claims, wherein the at least one gelling agent comprises gelatin, pectin, gellan gum, carrageenan, agar, alkali metal salts of alginic acid and mixtures thereof.

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

17. The kit according to claim 16, 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.

18. The kit according to claim 16, wherein the alkali metal alginic acid compound is selected from the group consisting of sodium alginate and potassium alginate, more preferably sodium alginate.

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

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

21. Kit according to any one of the preceding claims, wherein the weight ratio of the first composition to the second composition is from 1:3 to 1:20, preferably from 1:8 to 1: 15.

22. Kit according to any one of the preceding claims, wherein the second composition comprises at least one hydrophilic gelling agent and/or at least one active agent.

23. The kit according to any one of the preceding claims, wherein the second composition comprises the water-soluble polyhydroxy polymer.

24. Kit according to any of the preceding claims, presented as a mask, comprising:

1) nonwoven fabric made from hydroxyl-rich fibers comprising from 0.01 to 5 wt. -%, preferably from 0.02 to 1 wt. -% or preferably from 0.04 to 0.5% of calcium sulfate or calcium carbonate, and from 0.001 to 1 wt. -%, in particular from 0.01 to 0.1 wt. -%, like from 0.01 to 0.06% of HEC or HPC, relative to the total weight of the nonwoven fabric, and

2) a composition comprising, relative to the total weight of the 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 a water-soluble chelating agent and from 0.1% to 0.5% by weight, preferably from 0.2% to 0.4% by weight, of a water-soluble gelling agent,

25. Kit according to any one of the preceding claims, wherein the amounts of the chelating agent and the gelling agent are selected such that the molar ratio of the part released by the chelating agent that can be chelated with multivalent cations to the part released by the gelling agent that can form a gel with multivalent cations is from about 10:1 to about 1:1, preferably from about 5:1 to about 2: 1.

26. 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.

27. 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 step of compounding a first and a second composition of a kit according to any one of the preceding claims in a weight ratio of the first to the second composition of from 1:3 to 1:20, preferably from 1:8 to 1:15, then applying to the site where the mixture thus obtained is required.

28. Use of a second composition as claimed in any one of the preceding claims as part of the juice or sap of a mask product, wherein the mask product comprises, separately from the second composition, a fabric or tissue comprising the at least one water-insoluble multivalent metal salt.

29. A mask package 1 comprising:

1) a first composition comprising at least one water-insoluble polyvalent metal salt, at least one hydroxyl-rich fiber, preferably regenerated cellulose or cotton fiber, and at least one water-soluble polyhydroxyl polymer, wherein said at least one water-soluble polyhydroxyl polymer is homogeneously loaded onto said hydroxyl-rich fiber, and

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

wherein the first composition and the fourth composition are placed separately from each other.

30. The mask pack 1 according to claim 29 wherein said water insoluble polyvalent metal salt is calcium alginate, calcium sulfate or calcium carbonate.

31. A mask pack 1 according to claim 29 or 30 wherein said water soluble polyhydroxy polymer comprises polyhydroxy carboxylic acid, acid ester; a polyhydroxycellulose or a mixture thereof, preferably hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose or hydroxybutylmethylcellulose.

32. A mask pack 1 according to any one of the preceding claims 29 to 31 wherein said at least one hydroxyl rich fibre is selected from the group consisting of viscose, modal, lyocell, cuprammonium, cotton and mixtures thereof.

33. A mask pack 1 according to any one of the preceding claims 29 to 31 wherein said water soluble polyhydroxy polymer is hydroxyethyl cellulose or hydroxypropyl cellulose or mixtures thereof and said at least one hydroxyl rich fiber is selected from the group consisting of viscose, modal, lyocell, cuprammonium, cotton and mixtures thereof.

34. A mask pack 1 according to any one of the preceding claims 29 to 33 wherein said at least one gelling agent comprises gelatin, pectin, gellan gum, carrageenan, agar, alkali metal salts of alginic acid and mixtures thereof, preferably selected from the group consisting of sodium alginate and potassium alginate, more preferably sodium alginate.