CN116867472A

CN116867472A - Composition comprising polyion composite particles and filler

Info

Publication number: CN116867472A
Application number: CN202180093616.6A
Authority: CN
Inventors: 光田紫乃布; 大方宽之
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2020-12-14
Filing date: 2021-12-10
Publication date: 2023-10-10
Also published as: JP2022093930A

Abstract

The present invention relates to a composition comprising: (a) At least one particle comprising at least one cationic polymer and at least one anionic polymer, and at least one non-polymeric acid or one or more salts thereof having two or more pKa values; (b) at least one filler; and (c) water. The composition according to the invention may provide an improved moisturising texture, preferably in combination with a mattifying effect.

Description

Composition comprising polyion composite particles and filler

Technical Field

The present invention relates to compositions comprising polyion composite particles and filler, and cosmetic methods of using the same.

Background

It is known that skin that is shiny or greasy due to sebum can exacerbate roughness on the skin. In other words, shiny skin can make skin roughness such as pores and wrinkles more pronounced. Thus, users of cosmetic products wish to achieve a matt appearance of the skin.

There are some powders that can absorb oil. Such powders can be used in cosmetic products to provide a matt effect to the skin by absorbing sebum with these powders.

However, even in cosmetic products containing water, oil absorbing powders often cause an undesirable dry or astringent (squeaky) feel. In other words, it is often difficult to use oil absorbing powders in cosmetic products that contain water for providing a good moisturizing texture.

The above problems are not limited to oil absorbing powders. For example, the use of fillers in cosmetic products can also result in a astringent texture, and good moisturized texture may not be obtained even if the cosmetic product contains water.

DISCLOSURE OF THE INVENTION

Thus, there is a need for compositions that provide improved moisturized texture despite the inclusion of fillers.

It is therefore an object of the present invention to provide a composition which is capable of providing an improved moisturising texture, preferably both an improved moisturising texture and a mattifying effect.

The above object of the present invention can be achieved by a composition comprising:

(a) At least one particle comprising

At least one cationic polymer and at least one anionic polymer,

and

at least one non-polymeric acid having two or more pKa values, or one or more salts thereof;

(b) At least one filler; and

(c) And (3) water.

The cationic polymer may have at least one positively chargeable and/or positively charged group selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidino groups, imidazole groups, imino groups and pyridine groups.

The cationic polymer may be selected from the group consisting of cyclized polymers of alkyl diallylamine and cyclized polymers of dialkyl diallylammonium such as (co) polydiallyl dialkylammonium chloride, (co) polyamines such as (co) polylysine, cationic (co) polyamino acids such as collagen, cationic cellulose polymers, and salts thereof.

The amount of the one or more cationic polymers forming the (a) particles in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

The anionic polymer may be selected from hyaluronic acid and derivatives thereof.

The amount of the one or more anionic polymers forming the (a) particles in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

The non-polymeric acid or one or more salts thereof having two or more pKa values may be an organic acid or one or more salts thereof, preferably a hydrophilic or water-soluble organic acid or one or more salts thereof, and more preferably a phytic acid or a salt thereof.

The amount of non-polymeric acid or one or more salts thereof having two or more pKa values forming the particles of (a) in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

The amount of (a) particles in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

The filler (b) may be selected from hydrophilic oil absorbing powder or hydrophobic oil absorbing powder. The hydrophobic oil absorbing powder may be selected from a powder of hydrophobic silica, preferably a powder of hydrophobic silica aerogel, and more preferably a powder of hydrophobic aerogel of silica silyl (silyl).

The amount of (b) one or more fillers in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

The amount of (c) water in the composition according to the invention may be 50 to 95 wt%, preferably 60 to 90 wt%, and more preferably 70 to 85 wt%, relative to the total weight of the composition.

The composition according to the invention may be a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care cosmetic composition.

The invention also relates to a cosmetic method for keratin materials such as the skin, comprising:

applying the composition according to the invention to keratin materials; and is combined with

The composition is dried to form a cosmetic film on the keratin materials.

Best Mode for Carrying Out The Invention

After diligent research, the inventors have found that it is possible to provide compositions that are capable of providing an improved moisturizing texture, preferably in combination with a matte effect.

Thus, the composition according to the invention comprises:

(a) At least one particle comprising

At least one cationic polymer and at least one anionic polymer,

and

(b) At least one filler; and

(c) And (3) water.

The compositions according to the present invention may provide improved or enhanced moisturization textures, such as better wet feel.

The improvement in the moisturizing texture can be attributed to the presence of (a) particles in the composition according to the invention.

Furthermore, the composition according to the invention may reduce or inhibit the astringent texture.

If the filler is oil absorbing, the composition according to the invention may trap sebum. Thus, the composition according to the invention may reduce the gloss on keratin materials such as the skin and may make roughness such as pores and wrinkles on the skin less noticeable, for example. Thus, the composition according to the invention may provide an optical matt effect while providing an improved moisturising texture. Thus, the composition according to the present invention may provide both improved moisturising texture and optical matting effect. The optical matting effect will be provided immediately after application of the composition according to the invention and/or will last for a long time.

Hereinafter, the composition, method, and the like according to the present invention will be explained in more detail.

[ polyion Complex particles ]

The composition according to the invention comprises (a) at least one particle which is a polyionic complex particle. Two or more different types of (a) particles may be used in combination. Thus, a single type of (a) particles or a combination of different types of (a) particles may be used.

The polyion complex particles may have a size of 5nm to 100 μm, preferably 100nm to 50 μm, more preferably 200nm to 40 μm, and even more preferably 500nm to 30 μm. Particle sizes less than 1 μm can be measured by dynamic light scattering, and particle sizes greater than 1 μm can be measured by optical microscopy. The particle size may be based on a number average diameter.

The amount of (a) one or more particles in the composition according to the invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.

The amount of (a) one or more particles in the composition according to the invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.

The amount of (a) one or more particles in the composition according to the invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

If the composition according to the invention comprises (d) at least one oil as explained below, a plurality of (a) particles may be present at the interface between (c) water and (d) oil. Thus, the (a) particles stabilize the emulsion. For example, if (c) water constitutes the continuous phase and (d) oil constitutes the dispersed phase, the (a) particles may form an O/W emulsion, which may be similar to the so-called pickering emulsion (Pickering emulsion).

Alternatively, a plurality of (a) particles may form a capsule having a hollow. (d) at least one oil may be present in the hollow. In other words, (d) oil may be incorporated into the capsule. The capsule wall may comprise a continuous layer or film formed from the particles of (a). While not wishing to be bound by theory, it is believed that (a) particles may reorganize at the interface of (c) water and (d) oil to spontaneously form capsules having a hollow to contain (d) oil. For example, the continuous phase constituted by (c) water and the dispersed phase constituted by (d) oil in the capsule may form an O/W emulsion, which may also resemble a so-called pickering emulsion.

The above will mean that (a) the particles themselves are amphiphilic. The (a) particles themselves are insoluble in oil or water.

The (a) particles comprise at least one cationic polymer and at least one anionic polymer.

There is no limitation on the type of cationic and anionic polymers. Two or more different types of cationic polymers may be used in combination. Thus, a single type of cationic polymer or a combination of different types of cationic polymers may be used. Two or more different types of anionic polymers may be used in combination. Thus, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

The ratio of the amount of cationic polymer/anionic polymer (e.g., stoichiometric) may be from 0.05 to 18, preferably from 0.1 to 10, and more preferably from 0.5 to 5.0. In particular, it may be preferable that the cationic group number of the cationic polymer/the anionic group number of the anionic polymer be 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0.

The total amount of cationic and anionic polymers in the composition according to the present invention may be 0.1 wt% or more, preferably 0.5 wt% or more, and more preferably 1 wt% or more, relative to the total weight of the composition.

The total amount of cationic and anionic polymers in the composition according to the present invention may be 30 wt% or less, preferably 25 wt% or less, and more preferably 20 wt% or less, relative to the total weight of the composition.

The total amount of cationic and anionic polymers in the composition according to the invention may be from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight, and more preferably from 1% to 20% by weight, relative to the total weight of the composition.

(cationic Polymer)

The cationic polymer has a positive charge density. The cationic polymer may have a charge density of 0.1 to 20meq/g, preferably 0.05 to 15meq/g, and more preferably 0.1 to 10meq/g.

It may be preferred that the cationic polymer has a molecular weight of 500 or more, preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more.

Unless otherwise defined in the specification, "molecular weight" refers to a number average molecular weight.

The cationic polymer may have at least one positively chargeable and/or positively charged group selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidino groups, imidazole groups, imino groups and pyridine groups. The term (primary) "amino" refers herein to-NH ₂ A group.

The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, those obtained from more than two types of monomers such as terpolymers obtained from three types of monomers.

The cationic polymer may be selected from natural cationic polymers and synthetic cationic polymers. Non-limiting examples of cationic polymers are as follows.

(1) Homopolymers and copolymers derived from acrylic or methacrylic acid esters and amides and comprising at least one unit selected from the group consisting of units of the formula:

wherein:

r, which may be identical or different ₁ And R is ₂ Selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl;

r, which may be identical or different ₃ Selected from hydrogen and CH ₃ ；

The symbols a, which may be identical or different, are selected from linear or branched alkyl groups containing from 1 to 6 carbon atoms, for example from 2 to 3 carbon atoms, and hydroxyalkyl groups containing from 1 to 4 carbon atoms;

r, which may be identical or different ₄ 、R ₅ And R is ₆ Selected from alkyl groups containing from 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment, from alkyl groups containing from 1 to 6 carbon atoms; and is also provided with

X is an anion derived from an inorganic or organic acid, such as methyl sulfate anion and a halide ion, such as chloride and bromide.

(1) The copolymer of the class may further comprise at least one unit derived from a comonomer, the comonomer may be selected from acrylamide, methacrylamide, diacetone acrylamide, substituted on the nitrogen atom (C) ₁ -C ₄ ) Lower alkyl substituted acrylamides and methacrylamides, groups derived from acrylic acid or methacrylic acid and esters thereof, vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters.

(1) Examples of copolymers of the class include, but are not limited to:

copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide,

such as the copolymers of acrylamide and methacryloyloxyethyl trimethyl ammonium chloride described in European patent application No.0 080 976,

copolymers of acrylamide and methacryloyloxyethyl trimethylammonium methylsulfate,

such as the quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers described in french patent nos. 2 077 143 and 2 393 573,

Dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers,

vinyl pyrrolidone/methacrylamidopropyl dimethylamine copolymer, quaternized vinyl pyrrolidone/dimethylaminopropyl methacrylamide copolymer, and

crosslinked methacryloyloxy (C) ₁ -C ₄ ) Alkyltris (C) ₁ -C ₄ ) Alkylammonium salt polymers, such as those obtained by homo-or copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, are crosslinked after the homo-or copolymerization with compounds containing olefinic unsaturation, such as methylenebisacrylamide.

(2) Cationic cellulose derivatives, such as cellulose ether derivatives containing quaternary ammonium groups, as described for example in french patent No.1 492 597, such as the polymers sold by the company Union Carbide Corporation under the name "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as hydroxyethyl cellulose quaternary ammonium that has been reacted with epoxides substituted with trimethylammonium groups.

Preferably the cationic cellulose polymer has at least one quaternary ammonium group, preferably a trialkyl quaternary ammonium group, and more preferably a trimethyl quaternary ammonium group.

The quaternary ammonium groups may be present in quaternary ammonium group-containing groups, which groups may be represented by the following formula (I):

wherein the method comprises the steps of

R ₁ And R is ₂ Each of (2) represents C ₁ -C ₃ Alkyl, preferably methyl or ethyl, and more preferably methyl,

R ₃ represent C ₁ -C ₂₄ Alkyl, preferably methyl or ethyl, and more preferably methyl,

X ^- represents an anion, preferably a halide, and more preferably a chloride,

n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0, and

R ₄ represent C ₁ -C ₄ Alkylene, preferably ethylene or propylene.

The leftmost ether linkage (-O-) in formula (I) above may be attached to the saccharide ring of the polysaccharide.

Preferably the group containing quaternary ammonium groups is-O-CH ₂ -CH(OH)-CH ₂ -N ⁺ (CH ₃ ) ₃ 。

(3) Cationic cellulose derivatives, such as cellulose copolymers and cellulose derivatives grafted with water-soluble quaternary ammonium monomers, and are described, for example, in U.S. Pat. No.4,131,576, as hydroxyalkyl celluloses, such as hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, grafted with salts selected from methacryloylethyl trimethylammonium, methacrylamidopropyl trimethylammonium and dimethyldiallylammonium salts, for example.

Commercial products corresponding to these polymers include, for example, those sold under the name "by National Starch company"L200 'and' >H100 "product sold.

(4) Non-cellulose-based cationic polysaccharides such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid and dextran hydroxypropyl trimethylammonium chloride are described in U.S. Pat. nos. 3,589,578 and 4,031,307. Guar gum (guar hydroxypropyl trimethylammonium chloride) modified with salts (e.g., chlorides) of 2, 3-epoxypropyl trimethylammonium can also be used.

Such products are for example sold under the trade name MEYHALL companyC13 S、/>C15、C17 and->C162.

(5) Polymers comprising piperazinyl units and divalent alkylene or hydroxyalkylene groups containing linear or branched chains, optionally interrupted by at least one individual selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, and oxidation and/or quaternization products of these polymers. Such polymers are described, for example, in French patent Nos. 2 162 025 and 2 280 361.

(6) Water-soluble polyaminoamides prepared by, for example, polycondensation of acidic compounds with polyamines; these polyaminoamides may be combined with a compound selected from epihalohydrins; a diepoxide; dianhydride; unsaturated dianhydrides; a diunsaturated derivative; dihaloalcohols; bis azetidinium (bisazetidinium); dihaloamide; a dialkylhalide; individual crosslinking of the oligomer resulting from the reaction of a difunctional compound which is reactive with an individual selected from the group consisting of dihaloalcohols, diazaidinium, dihaloacyldiamines, dialkylhalides, epihalohydrins, diepoxides and di-unsaturated derivatives; the crosslinking agent is used in an amount of 0.025 to 0.35mol per amine group of the polyaminoamide; these polyaminoamides are optionally alkylated or, if they contain at least one tertiary amine function, they may be quaternized. Such polymers are described, for example, in French patent Nos. 2 252 840 and 2 368 508.

(7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids and subsequent alkylation with difunctional agents, for example adipic acid/dialkylaminohydroxyalkyl dialkylenetriamine polymers, wherein the alkyl groups contain 1 to 4 carbon atoms, such as methyl, ethyl and propyl groups, and the alkylene groups contain 1 to 4 carbon atoms, such as ethylene. Such polymers are described, for example, in French patent No.1 583 363. In at least one embodiment, these derivatives may be selected from adipic acid/dimethylaminohydroxypropyl diethylenetriamine polymers.

(8) A polymer obtained by the reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids comprising 3 to 8 carbon atoms. The molar ratio of polyalkylene polyamine to dicarboxylic acid may be from 0.8:1 to 1.4:1; the polyaminoamide thus produced is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups of the polyaminoamide of from 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Pat. Nos. 3,227,615 and 2,961,347.

(9) Cyclized polymers of alkyl diallylamine and cyclized polymers of dialkyl diallylammonium, such as homopolymers and copolymers comprising units comprising at least one unit selected from the group consisting of formulae (Ia) and (Ib) as the main component of the chain:

Wherein:

k and t, which may be the same or different, are equal to 0 or 1, and the sum k+t is equal to 1;

R ₁₂ selected from hydrogen and methyl;

r, which may be identical or different ₁₀ And R is ₁₁ Selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups wherein the alkyl group contains, for example, 1 to 5 carbon atoms, and lower (C) ₁ -C ₄ ) Amido alkylThe method comprises the steps of carrying out a first treatment on the surface of the Or R is ₁₀ And R is ₁₁ Heterocyclic groups such as piperidinyl and morpholinyl may be represented together with the nitrogen atom to which they are attached; and is also provided with

Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, sulfate and phosphate. These polymers are described, for example, in French patent No.2 080 759 and in its supplementary certificate 2 190 406.

In one embodiment, R, which may be the same or different ₁₀ And R is ₁₁ Selected from alkyl groups containing 1 to 4 carbon atoms.

Examples of such polymers include, but are not limited to, (co) polydiallyl dialkylammonium chloride, as known by the name "from CALGON company"100' -Dimethyldiallylammonium chloride homopolymer (and homologs thereof of low weight average molar mass) sold under the name ">550 "copolymer of diallyldimethylammonium chloride and acrylamide.

A quaternary diammonium polymer comprising at least one repeating unit of formula (II):

Wherein:

r, which may be identical or different ₁₃ 、R ₁₄ 、R ₁₅ And R is ₁₆ Selected from aliphatic, cycloaliphatic or araliphatic groups containing from 1 to 20 carbon atoms and lower hydroxyalkylaliphatic groups, or R ₁₃ 、R ₁₄ 、R ₁₅ And R is ₁₆ May together or separately form, together with the nitrogen atom to which they are attached, a heterocyclic ring optionally containing a second heteroatom other than nitrogen, or alternatively, R may be the same or different ₁₃ 、R ₁₄ 、R ₁₅ And R is ₁₆ Selected from at least quiltStraight-chain or branched C substituted by one group ₁ -C ₆ Alkyl groups selected from nitrile, ester, acyl, amide, -CO-O-R ₁₇ -E group and-CO-NH-R ₁₇ -E group, wherein R ₁₇ Is alkylene and E is a quaternary ammonium group;

a, which may be the same or different ₁ And B ₁ Selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain at least one member attached to or inserted into the backbone, said member being selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, urea groups, amide groups and ester groups, and

X ^- is an anion derived from an inorganic or organic acid;

A ₁ 、R ₁₃ and R is ₁₅ May form a piperazine ring together with the two nitrogen atoms to which they are attached;

if A ₁ Selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B ₁ May be selected from:

-(CH ₂ ) _n --CO-E′-OC-(CH ₂ ) _n -

wherein E' is selected from:

a) A diol residue of formula-O-Z-O-, wherein Z is selected from the group consisting of a linear or branched hydrocarbon-based group and a group of the formula:

-(CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ -

-[CH ₂ -CH(CH ₃ )-O] _y -CH ₂ -CH(CH ₃ )-

wherein x and y, which may be the same or different, are selected from integers from 1 to 4 representing prescribed and unique degrees of polymerization, and numbers from 1 to 4 representing average degrees of polymerization;

b) Bis-secondary diamine residues, such as piperazine derivatives;

c) Bis-primary diamine residues of formula-NH-Y-NH-, wherein Y is selected from the group consisting of linear or branched hydrocarbon-based groups and divalent groups-CH ₂ -CH ₂ -S-S-CH ₂ -CH ₂ -; and

d) Ureylene of the formula-NH-CO-NH-.

In at least one embodiment, X ^- Is an anion such as chloride or bromide.

For example in French patent No.2 320 330;2 270 846;2 316 271;2 336 434; and 2 413 907 and U.S. Pat. No.2,273,780;2,375,853;2,388,614;2,454,547;3,206,462;2,261,002;2,271,378;3,874,870;4,001,432;3,929,990;3,966,904;4,005,193;4,025,617;4,025,627;4,025,653;4,026,945; and 4,027,020, polymers of this type.

Non-limiting examples of such polymers include those comprising at least one repeating unit of formula (III):

Wherein R, which may be the same or different ₁₃ 、R ₁₄ 、R ₁₅ And R is ₁₆ Selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p, which may be the same or different, are integers of 2 to 20, and X ^- Is an anion derived from an inorganic or organic acid.

(11) A polyquaternary polymer comprising units of formula (IV):

wherein:

r, which may be identical or different ₁₈ 、R ₁₉ 、R ₂₀ And R is ₂₁ Selected from hydrogen, methyl, ethyl, propyl, beta-hydroxyethyl, beta-hydroxypropyl, -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p An OH group, wherein p is selected from integers from 0 to 6, provided that R ₁₈ 、R ₁₉ 、R ₂₀ And R is ₂₁ Not at the same time it is hydrogen,

r and s, which may be the same or different, are selected from integers from 1 to 6,

q is selected from the group consisting of integers from 0 to 34,

X ^- is an anion, e.g. a halide, and

a is selected from the group consisting of dihalogen ions and-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -。

Such compounds are described, for example, in European patent application No.0 122 324.

(12) Quaternary polymers of vinyl pyrrolidone and vinyl imidazole.

Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines such as polyethyleneimine, including those selected from the group consisting of vinylpyridine and vinylpyridineA polymer of units, a condensate of polyamine and epichlorohydrin, ji Juya urea (polyurethanes) and chitin derivatives.

According to one embodiment of the invention, the at least one cationic polymer is chosen from cellulose ether derivatives comprising quaternary ammonium groups, such as the product sold under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic cyclized polymers, such as the product sold under the name "JR 400" by the company CALGON100、/>550 ands, homopolymers and copolymers of dimethyldiallylammonium chloride, guar modified with 2, 3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole (quaternary polymer).

(13) Polyamines

As cationic polymers, (co) polyamines may also be used, which may be homo-or copolymers having a plurality of amino groups. The amino group may be a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary amino group. Amino groups may be present in the polymer backbone or pendant groups (if present) of the (co) polyamine.

As examples of (co) polyamines, mention may be made of chitosan, (co) polyallylamine, (co) polyvinylamine, (co) polyaniline, (co) polyvinylimidazole, (co) dimethylaminoethylene methacrylate, (co) polyvinylpyridine such as (co) poly-1-methyl-2-vinylpyridine, (co) polyimines such as (co) polyethyleneimine, (co) polypyridines such as (co) poly (quaternary pyridine), (co) polybiguanides such as (co) polyaminopropyl biguanide, (co) polylysine, (co) polyornithine, (co) polyarginine, (co) polyhistidine, aminodextran, aminocellulose, amino (co) polyvinylacetal and salts thereof.

As (co) polyamines, it is preferable to use (co) polylysines. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine can be epsilon-poly-L-lysine, which is commonly used as a natural preservative in foods. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water, propylene glycol, and glycerin. Polylysine can be commercially available in various forms such as poly-D-lysine and poly-L-lysine. Polylysine can be in salt and/or solution form.

(14) Cationic polyamino acids

As the cationic polymer, a cationic polyamino acid may be used, which may be a cationic homopolymer or copolymer having a plurality of amino groups and carboxyl groups. The amino group may be a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary amino group. Amino groups may be present in the polymer backbone or pendant groups (if present) of the cationic polyamino acid. Carboxyl groups may be present in pendant groups of the cationic polyamino acid, if present.

As examples of cationic polyamino acids, mention may be made of cationized collagen, cationized gelatin, stearyl dimethyl ammonium hydroxypropyl hydrolyzed wheat protein, cocodimethyl ammonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyl trimethyl ammonium hydrolyzed conchiolin, stearyl dimethyl ammonium hydroxypropyl hydrolyzed soybean protein, hydroxypropyl trimethyl ammonium hydrolyzed soybean protein, cocodimethyl ammonium hydroxypropyl hydrolyzed soybean protein, and the like.

The following description relates to preferred embodiments of the cationic polymer.

It may be preferred that the cationic polymer is selected from cationic starches.

As examples of cationic starches, mention may be made of starches modified with 2, 3-epoxypropyltrimethylammonium salt (e.g. chloride), such as the products known by the INCI nomenclature as hydroxypropyl trimethylammonium chloride of starch, and which are known by Ondeo under the name Sensmer CL-50 or by Ingretion under the name Pencarie ^TM DP 1015.

It may also be preferred that the cationic polymer is selected from cationic gums.

The gum may be selected from, for example, cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, gum arabic and acacia gum.

Examples of cationic gums include cationic polygalactomannan derivatives such as guar gum derivatives and cassia gum derivatives, e.g., CTFA: guar hydroxypropyl trimethyl ammonium chloride, hydroxypropyl guar hydroxypropyl trimethyl ammonium chloride, and cassia gum hydroxypropyl trimethyl ammonium chloride. Guar hydroxypropyl trimethylammonium chloride may be in Jaguar ^TM Trade name series are commercially available from Rhodia Inc. and commercially available from Ashland Inc. under the N-Hance trade name series. The cassia seed gum hydroxypropyl trimethyl ammonium chloride can be obtained by a trademark Sensmemer ^TM CT-250 and Sensmemer ^TM CT-400 is commercially available from Lubrizol Advanced Materials, inc. or under the trademark ClearHance ^TM Commercially available from Ashland Inc.

It may be preferred that the cationic polymer is selected from the group consisting of cyclized polymers of alkyl diallylamine and cyclized polymers of dialkyl diallylammonium such as (co) polydiallyl dialkylammonium chloride, (co) polyamines such as (co) polylysine, cationic (co) polyaminoacids such as cationized collagen, cationic cellulose polymers, and salts thereof.

It may also be preferred that the cationic polymer is selected from chitosan.

It may be more preferred that the cationic polymer is selected from the group consisting of polylysine, polyquaternium (polyquaternium) -4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyl trimethylammonium chloride, cassia seed gum hydroxypropyl trimethylammonium chloride, chitosan, and mixtures thereof.

The amount of the one or more cationic polymers in the composition according to the invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.

The amount of the one or more cationic polymers in the composition according to the invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.

The amount of the one or more cationic polymers in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

(anionic Polymer)

The anionic polymer has a positive charge density. If the anionic polymer is a synthetic anionic polymer, the anionic polymer may have a charge density of 0.1meq/g to 20meq/g, preferably 1 to 15meq/g, and more preferably 4 to 10meq/g, and if the anionic polymer is a natural anionic polymer, the anionic polymer may have an average degree of substitution of 0.1 to 3.0, preferably 0.2 to 2.7, and more preferably 0.3 to 2.5.

It may be preferred that the molecular weight of the anionic polymer may be 300 or more, preferably 1,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, and even more preferably 1,000,000 or more.

The anionic polymer may have at least one negatively chargeable and/or negatively chargeable group selected from the group consisting of sulfate (sulfate group), sulfonate (sulfonate group), phosphate (phosphate group), phosphate (phosphonate group), phosphonate (phosphonate group), carboxylate (carboxilic group) and carboxylate (carboxylate group).

The anionic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

The anionic polymer may be selected from natural and synthetic anionic polymers.

The anionic polymer may comprise at least one hydrophobic chain.

The anionic polymer which may comprise at least one hydrophobic chain may be obtained by copolymerization of a monomer (a) selected from carboxylic acids comprising α, β -ethylenic unsaturation (monomer a ') and 2-acrylamido-2-methylpropanesulfonic acid (monomer a') with a non-surface-active monomer comprising ethylenic unsaturation (b) other than (a) and/or a monomer comprising ethylenic unsaturation (c) resulting from the reaction of an acrylic monomer comprising α, β -monoethylenically unsaturation or an isocyanate monomer comprising monoethylenically unsaturation with a monoanionic amphiphilic component or with a primary or secondary fatty amine.

Thus, anionic polymers having at least one hydrophobic chain can be obtained by two synthetic routes:

By copolymerization of the monomers (a ') and (c), or (a '), (b) and (c), or (a '), (b) and (c),

or by modification (in particular esterification or amidation) of the monomers (a ') or of the copolymers formed from the monomers (a ') and (b), or of (a ') and (b) by a monoanionic amphiphilic compound or a primary or secondary aliphatic amine.

As 2-acrylamido-2-methylpropanesulfonic acid copolymers there may be mentioned in particular those disclosed in the articles "Micelle formation of random copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,2000, volume 33, 10, pages 3694-3704" and in the applications EP-A-0 750 899 and EP-A-1 069 172.

The carboxylic acid comprising an α, β -monoethylenically unsaturated degree constituting the monomer (a') may be selected from the group consisting of a plurality of acids, in particular from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. Preferably the carboxylic acid is acrylic acid or methacrylic acid.

The copolymer may comprise a monomer (b) comprising monoethylenically unsaturated degrees that does not have surfactant properties. Preferred monomers are those which, when they are homopolymerized, give rise to water-insoluble polymers. They may be selected from, for example, acrylic acid C ₁ -C ₄ Alkyl esters and methacrylic acid C ₁ -C ₄ Alkyl esters, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. More particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers which may be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile and vinylidene chloride. Non-reactive monomers are preferred, these monomers being those in which the single alkenyl group is the only reactive group under polymerization conditions. However, monomers containing groups that react under the influence of heat, such as hydroxyethyl acrylate, may optionally be used.

The monomer (c) is obtained by reacting an acrylic monomer containing α, β -monoethylenically unsaturated degree, such as (a), or an isocyanate monomer containing monoethylenically unsaturated degree with a mono-nonionic amphiphilic compound or a primary or secondary aliphatic amine.

The mono-nonionic amphiphilic compounds or primary or secondary fatty amines used for preparing the nonionic monomers (c) are known. The monobasic nonionic amphiphilic compound is typically an alkoxylated hydrophobic compound comprising alkylene oxides constituting the hydrophilic portion of the molecule. The hydrophobic compound is typically composed of an aliphatic alcohol or alkylphenol, with the carbonaceous chain comprising at least 6 carbon atoms in the compound constituting the hydrophobic portion of the amphiphilic compound.

Preferred monobasic nonionic amphiphilic compounds are those having the formula (V):

R-(OCH ₂ CHR’) _m -(OCH ₂ CH ₂ ) _n -OH (V)

wherein R is selected from alkyl or alkylene groups containing from 6 to 30 carbon atoms and alkylaryl groups having alkyl groups containing from 8 to 30 carbon atoms, R' is selected from alkyl groups containing from 1 to 4 carbon atoms, n is an average number from about 1 to 150 and m is an average number from about 0 to 50, provided that n is at least as large as m.

Preferably, in the compounds of formula (V), the R groups are selected from alkyl groups containing from 12 to 26 carbon atoms and wherein alkyl is C ₈ -C ₁₃ An alkylphenyl group of (a); the R' group is methyl; m=0 and n=1 to 25.

Preferred primary and secondary aliphatic amines consist of one or two alkyl chains containing from 6 to 30 carbon atoms.

The monomer used to form the nonionic urethane monomer (c) may be selected from highly variable compounds. Any compound containing copolymerizable unsaturation such as acrylic, methacrylic, or allylic unsaturation may be used. The monomers (c) are obtainable in particular from isocyanates containing monoethylenically unsaturated degrees, in particular, for example, α -dimethyl-m-isopropenylbenzyl isocyanate.

The monomers (C) can be chosen in particular from oxyethylenated (1 to 50 EO) C ₆ -C ₃₀ Acrylic, methacrylic or itaconic esters of fatty alcohols, e.g. stearyl (polyoxyethylene) ether-20 methacrylate, oxyethylenated (25 EO) behenyl methacrylate, oxyethylenated (20 EO) mono-cetyl itaconate, oxyethylenated (20 EO) mono-stearyl itaconate or by polyoxyethylenation (25 EO) C ₁₂ -C ₂₄ Alcohol-modified acrylates and oxyethylenated (1 to 50 EO) C ₆ -C ₃₀ Dimethyl-m-isopropenyl benzyl isocyanate of fatty alcohols, in particular dimethyl-m-isopropenyl benzyl isocyanate of oxyethylenated behenyl alcohol, for example.

According to a specific embodiment of the present invention, the anionic polymer is selected from acrylic terpolymers obtained from (a) carboxylic acids comprising α, β -ethylenic unsaturation, (b) non-surface-active monomers comprising ethylenic unsaturation other than (a), and (c) nonionic urethane monomers, which are the reaction products of a monobasic nonionic amphiphilic compound with isocyanates comprising monoethylenically unsaturation.

As anionic polymers comprising at least one hydrophobic chain, mention may be made in particular of acrylic acid/ethyl acrylate/alkyl acrylate terpolymers, such as those obtained by Rohm&The product sold by Haas under the name Acusol 823 as a 30% aqueous dispersion; acrylate/stearyl (polyoxyethylene) ether-20 methacrylate copolymers, e.g. from Rohm&Haas sold under the name Aculyn 22; behenyl (meth) acrylate/ethyl acrylate/oxyethylenated (25 EO) methacrylate terpolymers, e.g. from Rohm&The product sold by Haas under the name Aculyn 28 as an aqueous emulsion; acrylic acid/oxyethylenated (20 EO) itaconic acid monocetyl ester copolymers such as the product sold under the name Structure 3001 by National Starch as a 30% aqueous dispersion; acrylic acid/oxyethylenated (20 EO) itaconic acid monostearyl ester copolymers, such as the product sold under the name Structure 2001 by National Starch as a 30% aqueous dispersion; acrylic ester/via polyoxyethylenated (25 EO) C ₁₂ -C ₂₄ Alcohol modified acrylate copolymers such as 30-32% copolymer latex sold under the name Synthalen W2000 by 3V SA; or a dimethyl-m-isopropenyl benzyl isocyanate terpolymer of methacrylic acid/methyl acrylate/ethoxylated behenyl alcohol, such as the product disclosed in document EP-A-0 173 109 as a 24% aqueous dispersion and comprising 40 ethylene oxide groups.

The anionic polymer may also be polyester-5, as exemplified by EASTMAN CHEMICAL Eastman AQ ^TM A product sold under the name 55S Polymer, having the formula:

a: dicarboxylic acid groups

G: glycol group

SO ₃ ^- Na ⁺ : sodium sulfo group

OH: hydroxy group

It may be preferred that the anionic polymer is selected from polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (e.g. carboxymethyl cellulose), anionic (co) polyaminoacids such as (co) polyglutamic acid, (co) poly (meth) acrylic acid, (co) polyamic acid, (co) polystyrene sulfonate, (co) poly (vinyl sulfate), dextran sulfate, chondroitin sulfate, (co) polymaleic acid, (co) polyfumaric acid, maleic acid (co) polymers, and salts thereof.

The maleic acid copolymer may comprise one or more maleic acid comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing 2 to 20 carbon atoms and styrene.

Thus, "maleic acid copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic acid comonomers, optionally partially or completely hydrolyzed, and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctene, and styrene. Preference is given to using hydrophilic polymers, i.e.polymers having a solubility in water of greater than or equal to 2 g/l.

In one advantageous aspect of the invention, the maleic acid copolymer may have a mole fraction of maleic acid units of 0.1 to 1, more preferably 0.4 to 0.9.

The weight average molar mass of the maleic acid copolymer may be 1,000 to 500,000, and preferably 1,000 to 50,000.

Preferably, the maleic acid copolymer is a styrene/maleic acid copolymer, and more preferably a sodium styrene/maleic acid copolymer.

It will be preferred to use a copolymer of styrene and maleic acid in a 50/50 ratio.

For example, those labeled by Cray Valley may be usedStyrene/maleic acid (50/50) copolymers in the form of the ammonium salt sold 30% in water, or by Cray Valley under the designation ∈ - >Styrene/maleic acid (50/50) copolymer in the form of its sodium salt in water 40% is sold.

The use of styrene/maleic acid copolymers such as sodium styrene/maleic acid copolymers can improve the wettability of films prepared from the compositions according to the invention.

According to one embodiment of the invention, the anionic polymer is preferably selected from hyaluronic acid and derivatives thereof.

Hyaluronic acid may be represented by the following chemical formula.

In the context of the present invention, the term "hyaluronic acid" covers in particular the basic units of hyaluronic acid of the formula:

this is the smallest part of the hyaluronic acid comprising disaccharide dimers, i.e. D-glucuronic acid and N-acetylglucosamine.

The term "hyaluronic acid or derivative thereof" also includes 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 linkages, said linear polymers having a molecular weight (Mw) which may be between 380 and 13,000,000 daltons. Such molecular weights are largely dependent on the source of the hyaluronic acid obtained and/or the method of preparation.

The term "hyaluronic acid or derivative thereof" also includes hyaluronate in the context of the present invention. As salts, mention may be made of alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

In the natural state, hyaluronic acid is present in the pericellular gel (pericellular gels), in the base material of connective tissue of vertebrate organs, such as dermis and epithelial tissue, and in particular in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord and in the celiac process (crista galli apophysis).

Thus, the term "hyaluronic acid or derivative thereof" includes all parts or subunits (sub-units) of hyaluronic acid having a molecular weight in particular within the molecular weight range reviewed hereinabove.

In the case of the present invention, hyaluronic acid having no inflammatory activity is preferably used.

For descriptions of the various hyaluronic acid moieties, reference may be made to document "Hyaluronan fragments: an information-rich system ", R.Stern et al, european Journal of Cell Biology (2006) 699-715, which reviews the listed biological activities of hyaluronic acid based on its molecular weight.

According to a preferred embodiment of the invention, the hyaluronic acid moiety suitable for the uses covered by the invention has a molecular weight of 50,000 to 5,000,000, in particular 100,000 to 5,000,000, especially 400,000 to 5,000,000 da. In this case, the term used is high molecular weight hyaluronic acid.

Alternatively, the hyaluronic acid moiety, which may also be suitable for the uses covered by the invention, has a molecular weight of 50,000 to 400,000 da. In this case, the term used is medium molecular weight hyaluronic acid.

Still alternatively, the hyaluronic acid moiety that may be suitable for use in the applications covered by the invention has a molecular weight of less than 50,000 da. In this case, the term used is low molecular weight hyaluronic acid.

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

Mention may be made in particular of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. Such esters have been described in particular in D.Campoccia et al, "Semisynthetic resorbable materials from hyaluronan esterification", biomaterials 19 (1998) 2101-2127.

The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.

The above molecular weight is also effective for hyaluronic acid esters.

The hyaluronic acid may be, in particular, CPN (MW: 10 to 150 kDa) under the trade name of Hyactive company, cristalanal (MW: 1.1 times 10) under the trade name of Soliance company ⁶ ) Nutra HA (MW: 820 000 Da), nutra AF (MW: 69 000 Da), by Bioland corporation under the name Oligo HA (MW: 6100 Da), or by Vam Farmacos Metica company under the name D Factor (MW: 380 Da) supplied hyaluronic acid.

The amount of the one or more anionic polymers in the composition according to the present invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.

The amount of the one or more anionic polymers in the composition according to the present invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.

The amount of the one or more anionic polymers in the composition according to the invention may be from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

(non-polymeric acids having two or more acid dissociation constants)

The composition according to the invention may comprise at least one non-polymeric acid having two or more pKa values or one or more salts thereof, i.e. at least one non-polymeric acid having two or more acid dissociation constants or one or more salts thereof. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a constant temperature, e.g. 25 ℃.

A non-polymeric acid having two or more pKa values, or one or more salts thereof, may be included in the particles of (a). The non-polymeric acid having two or more pKa values may act as a crosslinker for the anionic polymer and/or the amphoteric polymer.

The term "non-polymeric" herein means that the acid is not obtained by polymerizing two or more monomers. Thus, a non-polymeric acid is not equivalent to an acid obtained by polymerizing two or more monomers, such as a polycarboxylic acid.

Preferably the molecular weight of the non-polymeric acid or one or more salts thereof having two or more pKa values is 1,000 or less, preferably 800 or less, and more preferably 700 or less.

There is no limitation on the type of non-polymeric acid or one or more salts thereof having two or more pKa values. Two or more different types of non-polymeric acids or salts thereof having two or more pKa values may be used in combination. Thus, a single type of non-polymeric acid or salt thereof having two or more pKa values, or a combination of different types of non-polymeric acids or salts thereof having two or more pKa values may be used.

The term "salt" herein refers to a salt formed by adding a suitable base or bases to a non-polymeric acid having two or more pKa values, which salt may be obtained from the reaction of a non-polymeric acid having two or more pKa values with a base or bases according to methods known to those skilled in the art. As the salt, there may be mentioned metal salts, for example, salts with alkali metals such as Na and K, and salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

The non-polymeric acid or one or more salts thereof having two or more pKa values may be an organic acid or one or more salts thereof, preferably a hydrophilic or water-soluble organic acid or one or more salts thereof.

The non-polymeric acid having two or more pKa values may have at least two acid groups selected from the group consisting of carboxylic acid groups, sulfuric acid groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, phenolic hydroxyl groups, and mixtures thereof.

The non-polymeric acid having two or more pKa values may be a non-polymeric polyacid.

The non-polymeric acid having two or more pKa values may be selected from dicarboxylic acids, disulfonic acids, and diphosphoric acids, and mixtures thereof.

The non-polymeric acid having two or more pKa values or one or more salts thereof may be selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid and salts thereof; aspartic acid, glutamic acid and salts thereof; terephthal-xylylene di-camphorsulfonic acid or its salt (Mexoryl SX), benzophenone-9; phytic acid and salts thereof; red 2 (Amaranth), red102 (New Coccine), yellow 5 (Tartrazine), yellow 6 (Sunset Yellow FCF), green 3 (Fast Green FCF), blue 1 (Brilliant Blue FCF), blue 2 (Indigo Carmine), red 201 (Lithol Rubine B), red 202 (Lithol Rubine BCA), red 204 (Lake Red CBA), red 206 (Lithol Red CA), red 207 (Lithol Red BA), red 208 (Lithol Red SR), red 219 (Brilliant Lake Red R), red 220 (Deep Marin), red 227 (Fast Acid Magenta), yellow203 (Quinoline Yellow WS), green 201 (Alizanine Cyanine Green F), green 204 (Pyraine Conc), green 205 (Light Green SF Yellowish), blue 203 (Patent Blue CA), blue 205 (Audio FG), red 401 (Violet R), red 405 (Perol R), red 5 (Red R) and Red (Red) Green P.sub.3 (Red R.502), red (Red P.sub.3, red P.R.sub.36, red P.R.401 (Red P.sub.3, red P.R.sub.R.401); folic acid, ascorbic acid, isoascorbic acid and salts thereof; cystine and salts thereof; EDTA and salts thereof; glycyrrhizic acid and its salts; and mixtures thereof.

It may be preferred that the non-polymeric acid having two or more pKa values or one or more salts thereof is selected from the group consisting of terephthalyl di-camphorsulfonic acid or salts thereof (Mexoryl SX), yellow 6 (Sunset Yellow fcf), ascorbic acid, phytic acid and salts thereof, and mixtures thereof.

The amount of non-polymeric acid having two or more pKa values or one or more salts thereof in the composition according to the invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.

The amount of non-polymeric acid having two or more pKa values, or one or more salts thereof, in the composition according to the invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.

The amount of non-polymeric acid having two or more pKa values or one or more salts thereof in the composition according to the invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

[ Filler ]

The composition according to the invention comprises (b) at least one filler. Two or more fillers may be used in combination. Thus, a single type of filler or a combination of different types of fillers may be used.

The term "filler" is understood to mean colourless or white, inorganic or synthetic particles which are insoluble in the possible liquid components of the composition according to the invention, irrespective of the temperature at which the composition is manufactured.

The (b) filler may be inorganic or organic and may be spherical or oval, regardless of the crystal form (e.g., platelet, cube, hexagonal, rhombohedral, etc.). Mention may be made, without limitation, of talc, mica, silica, silylated silica, kaolin, sericite, calcined talc, calcined mica, calcined sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium bicarbonate and hydroxyapatite, made of polyamidesPoly-beta-alanine powder and polyethylene powder, polyurethane powder, tetrafluoroethylene polymer (/ -for use in the preparation of the composition>) Powder, lauryllysine, starch, hollow microspheres of polymers such as those of poly (vinylidene chloride)/acrylonitrile, for example +.>(Nobel industries) or acrylic copolymers, silicone resin microspheres (e.g., from Toshiba +.>) Particles formed from polyorganosiloxane elastomers, precipitated calcium carbonate, magnesium carbonate, basic magnesium carbonate, hollow silica microspheres, glass or ceramic microcapsules, or metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, such as 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate.

Examples of fillers for the purposes of the present invention include metal oxides, preferably titanium oxide, zinc oxide and mixtures thereof.

Fillers suitable for the present invention may be, for example, fillers whose average particle size is less than 100 μm, in particular between 1 and 50 μm, for example between 4 and 20 μm.

The filler (b) may be selected from hydrophilic oil absorbing powder or hydrophobic oil absorbing powder. The hydrophilic or hydrophobic oil absorbing powder is capable of absorbing (and/or adsorbing) oil or liquid fatty substances, such as sebum (from the skin).

The hydrophilic oil absorbing powder or hydrophobic oil absorbing powder may comprise porous or hollow particles, in particular porous or hollow spherical particles.

(hydrophilic oil-absorbing powder)

For the purposes of the present invention, the term "hydrophilic" oil absorbing powder means that the powder (or particles) is dispersed in water alone in such a way that aggregates do not form.

The hydrophilic oil-absorbing powder may have an oil absorption of 100ml/100g or more, preferably 150ml/100g or more, and more preferably 200ml/100g or more.

The amount of oil absorbed (and/or adsorbed) by the hydrophilic oil absorbing powder can be characterized by measuring the wet point according to the method described below. The oil absorption measured at the wet point (denoted Wp) corresponds to the amount of oil required to be added to 100g of powder to obtain a uniform paste.

The amount of absorbed (and/or adsorbed) oil may be measured according to the method described in standard NF T30-022 for determining oil absorption of powders. Which corresponds to the amount of oil absorbed/adsorbed onto the active surface of the powder by measuring the wet spot.

An amount of powder of m=2 g was placed on a glass plate, followed by dropwise addition of oil (e.g. ester oil and silicone oil). After adding 4 to 5 drops of oil to the powder, mixing was performed using a spatula and the addition of oil was continued until an aggregate of oil and powder was formed. At this point, one drop of oil was added at a time, and the mixture was then developed using a spatula. The addition of oil was stopped when a firm, smooth paste was obtained. Such a paste must be capable of spreading on a glass sheet without cracking or forming lumps. The volume Vs (in milliliters) of oil used was then recorded. The oil absorption corresponds to the ratio Vs/m.

Alternatively, the oil absorption may be measured according to JIS-K6217-4.

The hydrophilic oil absorbing powder may have organic or inorganic properties.

The hydrophilic oil absorbing powder can be selected from cellulose, silica, silicate; perlite; magnesium carbonate; magnesium hydroxide; and derivatives thereof; and mixtures thereof.

According to one embodiment, the cellulose derivative may be selected from cellulose esters and ethers.

In the foregoing and in the following, the term "cellulose ester" refers to a polymer consisting of the alpha (1-4) sequence of a partially or fully esterified anhydroglucose ring obtained by the reaction of all or some of the free hydroxyl functions of said anhydroglucose ring with a linear or branched carboxylic acid or carboxylic acid derivative (acid chloride or anhydride) containing from 1 to 4 carbon atoms. Preferably, the cellulose esters result from the reaction of some of the free hydroxyl functionality of the ring with carboxylic acids containing 1 to 4 carbon atoms. Advantageously, the cellulose ester is selected from the group consisting of cellulose acetate, cellulose propionate, cellulose butyrate, cellulose isobutyrate, cellulose acetobutyrate and cellulose levulinate, and mixtures thereof.

The term "cellulose ether" refers to a polymer consisting of the alpha (1-4) sequence of partially etherified anhydroglucose rings, some of the free hydroxyl functions of the rings being substituted with groups-OR, R preferably being a linear OR branched alkyl group containing from 1 to 4 carbon atoms. The cellulose ether is therefore preferably selected from the group consisting of cellulose alkyl ethers having an alkyl group containing 1 to 4 carbon atoms, such as cellulose methyl ether, cellulose propyl ether, cellulose isopropyl ether, cellulose butyl ether and cellulose isobutyl ether.

Cellulose and its derivatives that may be mentioned include, for example, the following spherical cellulose particles sold by Daito Kasei in japan: cellulobeads USF (oil absorption 250ml/100 g) with particle size of 4 μm (porous cellulose).

Silica powders which may be mentioned include porous silica microspheres, in particular those named by Asahi Glass companyH31 and->H51 (oil absorption equals 150ml/100 g) those sold; MSS-500-3H sold by Kobo Co; amorphous hollow Silica particles, in particular those sold under the name Silica Shells by the company Kobo (oil absorption equal to 550ml/100 g); porous silica microspheres sold by Fuji Silysia Chemical under the name Sylysia 350 (oil absorption equal to 310ml/100 g); and silica powder sold under the name Finesil X35 by Oriental Silycas company (oil absorption equal to 380ml/100 g).

Among the silicates which may be mentioned are aluminum silicates, which are known from the company Kyowa Chemical Industry700PEL (oil absorption equal to 195ml/100 g).

Perlite powders which may be mentioned in particular are those named by the company World Minerals1430OR and +.>2550OR (oil absorption equal to 240ml/100 g).

Magnesium carbonate powder which may be mentioned in particular is a powder prepared from Buschle &Lepper company under the name TipoThe product is sold (oil absorption equal to 214ml/100 g).

Magnesium carbonate/magnesium hydroxide powder which may be mentioned in particular is mgco ₃ -Mg(OH) ₂ -nH ₂ O, sold by Nittesu Mining under the name Mg Tube (oil absorption equal to 250-310ml/100 g).

Preferably, the hydrophilic oil absorbing powder comprises at least one selected from the group consisting of cellulose, silica, perlite, and mixtures thereof.

(hydrophobic oil-absorbing powder)

For the purposes of the present invention, the term "hydrophobic" oil absorbing powder means that the powder (or particles) is individually dispersed in the oil in such a way that no aggregates are formed.

The hydrophobic oil absorbing powder may have an oil absorption of 100ml/100g or more, preferably 150ml/100g or more, and more preferably 200ml/100g or more.

The amount of oil absorbed (and/or adsorbed) by the hydrophobic oil absorbing powder can be determined by the method described above.

The hydrophobic oil absorbing powder may have organic or inorganic properties.

Organic hydrophobic oil absorbing powder:

the organic hydrophobic oil absorbing powder may be selected from polyamide (in particular Nylon-6) powder, acrylic polymer powder, in particular polymethyl methacrylate, polymethyl methacrylate/ethylene glycol dimethacrylate, polyallylmethacrylate/ethylene glycol dimethacrylate, or ethylene glycol dimethacrylate/lauryl methacrylate copolymer powder; and mixtures thereof. The above materials may be crosslinked.

Preferably the organic hydrophobic oil absorbing powder is selected from the group consisting of powders of acrylic polymers, in particular of ethylene glycol dimethacrylate/lauryl methacrylate copolymer.

Examples of the organic hydrophobic oil absorbing powder include the following fillers.

Acrylic polymer powders which may be mentioned include porous polymethyl methacrylate (INCI-name methyl methacrylate cross-linked polymer), such as spheres sold by the company sensor under the name Covabead LH85, porous polymethyl methacrylate/polyethylene glycol dimethacrylate spheres (oil absorption equal to 155ml/100 g) sold by the company Cardinal Health Technologies under the name Microsoft 5640, polyethylene glycol dimethacrylate/lauryl methacrylate cross-linked copolymer powders, in particular Amcol Health&Beauty Solutions Inc. under the name6603 (oil absorption equal to 656ml/100 g), acrylonitrile/methyl methacrylate/vinylidene chloride copolymer sold by the company Akzo Novel under the name Expancel 551DE40D42 (oil absorption equal to 1040ml/100 g).

Polyamide powders which may be mentioned include Nylon-6 powders, in particular those sold under the name Pomp610 by UBE Industries (oil absorption equal to 202ml/100 g).

Inorganic hydrophobic oil-absorbing powder:

the inorganic hydrophobic oil absorbing powder may have at least one inorganic core and at least one hydrophobic coating.

Preferably the inorganic hydrophobic oil absorbing powder is selected from the group consisting of powders of hydrophobic silica, preferably hydrophobic silica aerogel, and more preferably hydrophobic aerogel of silylated silica, and mixtures thereof.

The term "hydrophobic silica" is understood to mean any silica whose surface is treated to be hydrophobic.

The hydrophobic silica, in particular the silylated silica, may be based on silica aerogel, which is a porous material obtained by replacing (by drying) the liquid component of the silica gel with air.

They are usually prepared by means of solsThe gel process is synthesized in a liquid medium and then dried, usually by extraction with supercritical fluid, one of the most commonly used being supercritical CO ₂ . This type of drying makes it possible to avoid shrinkage of the pores and the material. In Brinker cj. And Scherer g.w., sol-Gel Science: new York: the sol-gel process and various drying operations are described in detail in Academic Press, 1990.

Aerogels are materials with high porosity. In this context, silica aerogel refers to solid silica having a porous structure, which is generally obtained by replacing the medium contained in wet silica gel with air by drying them while maintaining the solid network structure of silica. Porosity represents the amount of air contained in the apparent volume of the material in volume percent. The hydrophobic silica aerogel of the present invention can have a porosity of 60% or greater, preferably 70% or greater, and more preferably 80% or greater.

Hydrophobic silica aerogel particles can exhibit

500 to 1,500m ² Per gram, preferably 600 to 1,200m ² /g, and more preferably 600 to 800m ² Per unit weight of specific Surface (SW), and/or

A size expressed as volume-average diameter (D [0.5 ]) of 1 to 1,500 μm, preferably 1 to 1,000 shirt, more preferably 1 to 100 μm, particularly 1 to 30 μm, more preferably 5 to 25 μm, more preferably 5 to 20 μm, and even more preferably 5 to 15 μm.

The specific surface area per unit weight can be determined by a nitrogen adsorption method called the BET (Brunauer-Emmett-Teller) method, which is described in Journal of the American Chemical Society, vol.60, p.309, month 1938, 2 and complies with the international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

The size of the silica aerogel particles can be measured by static light scattering using a MasterSizer model 2000 commercial particle size analyzer from Malvern. Data were processed based on Mie scattering theory. This theory is accurate for isotropic particles, so that the "effective" particle size can be determined in the case of non-spherical particles. This theory is described in particular in the Van de Hulst, H.C. publication, "Light Scattering by Small Particles", chapters 9 and 10, wiley, new York, 1957.

The hydrophobic silica aerogel particles can advantageously exhibit 0.04g/cm ³ To 0.10g/cm ³ And preferably 0.05g/cm ³ To 0.08g/cm ³ Filling density (r).

In the case of the present invention, such a density, called filling density, can be evaluated according to the following scheme:

pouring 40g of powder into a graduated cylinder;

the cylinder was then placed on a Stav 2003 device from a Stampf volume;

the cylinder was then subjected to a series of 2500 fill actions (the operation was repeated until the volume difference between 2 consecutive trials was less than 2%); and

the final volume Vf of the filled powder is then measured directly on a measuring cylinder. The packing density is determined by a ratio w/Vf, in this case 40/Vf (Vf in cm ³ Expressed, w is expressed in g).

For the preparation of hydrophobic silica aerogel particles modified at the surface by silylation, reference can be made to US 7 470 725.

Hydrophobic silica aerogel particles modified at the surface with trimethylsilyl groups will be particularly used.

Inorganic hydrophobic oil-absorbing powders which may be mentioned include polydimethylsiloxane-coated amorphous silica microspheres, in particular under the nameH33 and->H53 (oil absorption equal to 400ml/100 g), precipitated silica powders surface-treated with ceresin wax, such as precipitated silica treated with polyethylene wax, and in particular those sold under the name Acematt OR 412 by Evonik-Degussa company (oil absorption equal to 398ml/100 g), and by Evonik-Degussa company Silylated silica sold by Dow under the name VM-2270 (oil absorption equal to 1,040ml/100 g).

It is preferable to use as inorganic hydrophobic oil absorbing powder a silylated silica sold under the name VM-2270 by Dow, the particles of which exhibit an average size of 5 to 15 μm and 600 to 800m ² Per unit weight specific surface area per gram.

The hydrophobic silica aerogel particles can be characterized as each particle having a spherical shape. Because of the spherical shape, the hydrophobic silica aerogel particles can provide good smoothness to the cosmetic composition. The sphericity of the hydrophobic silica aerogel can be determined by the average circularity (circularity).

The spherical hydrophobic silica aerogel particles can have an average circularity of 0.8 or more, and preferably 0.82 or more. The spherical hydrophobic silica aerogel can have an average circularity of less than 1, preferably 0.99 or less, more preferably 0.98 or less, even more preferably 0.97 or less, still more preferably 0.96 or less, and most preferably 0.95 or less.

The "average circularity" may be determined by an image analysis method. In particular, the "average circularity" may be an arithmetic average of circularities obtained by image analysis of a Scanning Electron Microscope (SEM) image of not less than 2,000 aerogel particles observed at a magnification of 1,000 times by secondary electron detection using a Scanning Electron Microscope (SEM).

The "circularity" of each aerogel particle is a value determined by the formula:

C＝4πS/L ²

where C represents the circularity, S represents the area (projected area) of the aerogel particles in the image, and L represents the outer circumferential length (circumference) of the aerogel particles in the image. As the average circularity approaches 1, the shape of each particle becomes more spherical.

The hydrophobic silica aerogel particles which can be used according to the invention preferably have a silylated silica type (INCI name: silylated silica). Preferably, the hydrophobic silica aerogel particles can be those described in JP-A-2014-088307, JP-A-2014-218433, or JP-A-2018-177620.

Hydrophobic aerogels of silylated silica are preferably used as the inorganic hydrophobic oil absorbing powder.

The hydrophobicity of the hydrophobic aerogel of the silylated silica can be obtained by reacting a hydrophobizing agent with silanol groups present on the surface of the silica represented by the formula:

≡Si-OH

wherein the symbol "three" represents the remaining trivalent of the Si atom,

thereby converting silanol groups into groups represented by the formula:

(≡Si-O-) _(4-n) SiR _n

wherein n is an integer from 1 to 3; each R is independently a hydrocarbyl group; and two or more R may be the same or different from each other, where n is 2 or more.

The hydrophobizing agent may be a silylating agent. Thus, according to a preferred embodiment, in the hydrophobic aerogel of the silylated silica, the silica particles can be surface modified by silylation. As examples of the silylating agent, there may be mentioned a treating agent having one of the following formulas (1) to (3).

Formula (1):

R _n SiX _(4-n)

wherein n represents an integer of 1 to 3; r represents a hydrocarbon group; x represents a group that can leave the molecule (i.e., a leaving group) through cleavage of a bond to a Si atom in a reaction with a compound having a hydroxyl group; each R may be different, wherein n is 2 or greater; and each X may be different, where n is 2 or less.

Formula (2):

wherein R is ¹ Represents an alkylene group; r is R ² And R is ³ Independently replaceA table hydrocarbon group; and R is ⁴ And R is ⁵ Independently represents a hydrogen atom or a hydrocarbon group.

Formula (3):

wherein R is ⁶ And R is ⁷ Independently represents a hydrocarbon group; m represents an integer of 3 to 6; when there are two or more R ⁶ When each R ⁶ May be different; and when there are two or more R ⁷ When each R ⁷ May be different.

In the above formula (1), R is a hydrocarbon group, preferably a hydrocarbon group having a carbon number of 1 to 10, more preferably a hydrocarbon group having a carbon number of 1 to 4, and particularly preferably a methyl group.

As examples of the leaving group represented by X, halogen atoms such as chlorine and bromine; alkoxy groups such as methoxy and ethoxy; from-NH-SiR ₃ (wherein R is as defined for R in formula (1)).

Specific examples of the hydrophobizing agent represented by the above formula (1) include: chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, monomethyl trimethoxysilane, monomethyl triethoxysilane and hexamethyldisilazane.

From the standpoint of favorable reactivity, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane and/or hexamethyldisilazane are more preferably used.

The number of bonds of the Si atom to the silanol group on the silica skeleton varies depending on the number of leaving groups X (4-n). For example, if n is 2, the following bonding will occur:

(≡Si-O-) ₂ SiR ₂ ，

if n is 3, the following bonding will occur:

≡Si-O-SiR ₃ 。

in this way, the silanol groups can be silylated and thus hydrophobized.

In the above formula (2), R ¹ An alkylene group, preferably an alkylene group having a carbon number of 2 to 8, and particularly preferably an alkylene group having a carbon number of 2 to 3, is possible.

In the above formula (2), R ² And R is ³ Independently, a hydrocarbon group, and the same preferable groups as those of R in formula (1) can be mentioned. R is R ⁴ Represents a hydrogen atom or a hydrocarbon group, and when it is a hydrocarbon group, the same preferable groups as those of R in the formula (1) can be mentioned. When the gel of silica is treated with a compound (cyclic silazane) represented by formula (2), cleavage of si—n bond will occur by reaction with silanol group, and thus the following bonding will occur on the surface of silica skeleton in the gel:

(≡Si-O-) ₂ SiR ² R ³ 。

In this way, the silanol groups can also be silylated by the cyclic silazanes of formula (2) above and can therefore be hydrophobized.

Specific examples of the cyclic silazane represented by the above formula (3) include hexamethyl cyclotrisilazane and octamethyl cyclotetrasilazane.

In the above formula (3), R ⁶ And R is ⁷ Independently, a hydrocarbon group, and the same preferable groups as those of R in the formula (2) can be mentioned. m represents an integer of 3 to 6. When the gel of silica is treated with the compound (cyclic siloxane) represented by formula (3), the following bonding will occur on the surface of the silica skeleton in the gel:

(≡Si-O-) ₂ SiR ⁶ R ⁷ .

in this way, the silanol groups can also be silylated by the cyclic siloxanes of the above formula (3) and can thus be hydrophobized.

Specific examples of the cyclic siloxane represented by the above formula (3) include hexamethylcyclotrisiloxane, octamethyltetrasiloxane and decamethylcyclopentasiloxane.

The hydrophobic aerogel of the silylated silica can be prepared by the steps of: preparing a sol of silica, converting the sol into a gel, aging the gel, washing the aged gel, replacing water in the washed gel with a solvent, treating the gel with a hydrophobizing agent, and drying the hydrophobized silica.

The hydrophobic aerogel of the silylated silica can have a particle size of 200m ² Per gram or higher, preferably 400m ² /g or higher, and more preferably 500m ² Per gram or higher, and may have a specific surface area measured by BET method of 1,200m ² /g or less, preferably 1,000m ² /g or less, and more preferably 800m ² And/g or less, as determined by BET method.

The hydrophobic aerogel of the silylated silica can have a pore volume as determined by the BJH method of 1ml/g or greater, preferably 2ml/g or greater, and more preferably 3ml/g or greater, and can have a pore volume as determined by the BJH method of 10ml/g or less, preferably 8ml/g or less, and more preferably 7ml/g or less. The hydrophobic silica aerogel of the silylated silica can have a peak pore radius as determined by the BJH method of 5nm or greater, preferably 10nm or greater, and more preferably 12nm or greater, and can have a peak pore radius as determined by the BJH method of 50nm or less, preferably 40nm or less, and more preferably 30nm or less.

The "pore volume measured by the BJH method" means a pore volume derived from a pore having a pore radius of 1nm to 100nm, which is obtained by analyzing adsorption isotherms on the nitrogen adsorption side obtained in the same manner as explained above for the "specific surface area measured by the BET method", by the BJH method (Barrett, e.p.; joyner, l.g.; halenda, P.P., J.Am.Chem.Soc.73, 373 (1951)). The "peak pore radius measured by the BJT method" means a value of the pore radius giving a peak in a pore distribution curve (volume distribution curve) obtained by analyzing an adsorption isotherm of the nitrogen adsorption side obtained in the same manner as above by the BJH method, the pore distribution curve taking the derivative of the cumulative pore volume divided by the logarithm of the pore radius on the vertical axis and the pore radius on the horizontal axis.

The hydrophobic aerogel of the silylated silica can have an average particle size of 0.5 μm or more, preferably 1 μm or more, and more preferably 2 μm or more, and can have an average particle size by image analysis methods of 30 μm or less, preferably 20 μm or less, and more preferably 15 μm or less.

The "average particle size" can be measured here by image analysis methods. In particular, the value of the "average particle size" is an arithmetic average of equivalent circle diameters which can be obtained by, for example, image analysis of a Scanning Electron Microscope (SEM) image of not less than 2,000 aerogel particles observed at a magnification of 1,000 times by secondary electron detection using a Scanning Electron Microscope (SEM). The "equivalent circle diameter" of each aerogel particle is the diameter of a circle having an area equal to the area (projected area) of the aerogel particle in the image.

Preferably, the hydrophobic aerogel of the silylated silica can have an oil absorption measured at the wet point as explained above of 2ml/g or higher, preferably 3ml/g or higher, more preferably 4ml/g or higher, and most preferably 5ml/g or higher, and can have an oil absorption measured at the wet point of 12ml/g or lower, preferably 10ml/g or lower, more preferably 8ml/g or lower, and most preferably 7ml/g or lower.

The amount of (b) one or more fillers in the composition according to the invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.

The amount of (b) one or more fillers in the composition according to the invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.

[ Water ]

The composition according to the invention comprises (c) water.

The amount of (c) water may be 50 wt% or more, preferably 60 wt% or more, and more preferably 70 wt% or more, relative to the total weight of the composition.

The amount of (c) water may be 95 wt% or less, preferably 90 wt% or less, and more preferably 85 wt% or less, relative to the total weight of the composition.

The amount of (c) water may be 50 to 95 wt%, preferably 60 to 90 wt%, and more preferably 70 to 85 wt%, relative to the total weight of the composition.

[pH]

The pH of the composition according to the invention may be from 3 to 9, preferably from 3.3 to 8.5, and more preferably from 3.5 to 8.

At a pH of 3 to 9, the (a) particles may be very stable.

The pH of the composition according to the invention may be adjusted by adding at least one alkaline agent and/or at least one acid in addition to the non-polymeric acid or one or more salts thereof having two or more pKa values to be incorporated into the particles of (a). The pH of the composition according to the invention may also be adjusted by adding at least one buffer.

(alkaline agent)

The composition according to the invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

The alkaline agent may be an inorganic alkaline agent. Preferably the inorganic alkaline agent is selected from ammonia; an alkali metal hydroxide; alkaline earth metal hydroxides; alkali metal phosphates and monohydrogen phosphates such as sodium phosphate or sodium monohydrogen phosphate.

As examples of inorganic alkali metal hydroxides, sodium hydroxide and potassium hydroxide may be mentioned. As examples of alkaline earth metal hydroxides, mention may be made of calcium hydroxide and magnesium hydroxide. As the inorganic alkaline agent, sodium hydroxide is preferable.

The alkaline agent may be an organic alkaline agent. Preferably the organic base agent is selected from monoamines and derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof; oligomers of basic amino acids and derivatives thereof; a basic amino acid and a derivative thereof; urea and derivatives thereof; and guanidine and its derivatives.

As examples of the organic alkali agent, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and isopropanolamine can be mentioned; urea, guanidine and derivatives thereof; basic amino acids such as lysine, ornithine or arginine; and diamines, such as those described in the following structures:

wherein R represents an alkylene group, e.g. optionally hydroxy or C ₁ -C ₄ Alkyl substituted propylene, and R ₁ 、R ₂ 、R ₃ And R is ₄ Independently represents a hydrogen atom, an alkyl group or C ₁ -C ₄ Hydroxyalkyl groups, which may be exemplified by 1, 3-propanediamine and derivatives thereof. Arginine, urea and monoethanolamine are preferred.

Depending on their solubility, the one or more alkaline agents may be used in a total amount of 0.01 to 15 wt%, preferably 0.02 to 10 wt%, more preferably 0.03 to 5 wt%, relative to the total weight of the composition.

(acid)

The composition according to the invention may comprise at least one acid. Two or more kinds of acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.

As the acid, any inorganic acid or organic acid commonly used in cosmetic products may be mentioned, with inorganic acids being preferred. Monoacids and/or polyacids may be used. Monoacids such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferred.

Depending on their solubility, the one or more acids may be used in a total amount of 0.01 to 15 wt%, preferably 0.02 to 10 wt%, more preferably 0.03 to 5 wt%, relative to the total weight of the composition.

(buffering agent)

The composition according to the invention may comprise at least one buffer. Two or more buffers may be used in combination. Thus, a single type of buffer or a combination of different types of buffers may be used.

As buffers, mention may be made of acetate buffers (e.g. acetic acid+sodium acetate), phosphate buffers (e.g. sodium dihydrogen phosphate+disodium hydrogen phosphate), citrate buffers (e.g. citric acid+sodium citrate), borate buffers (e.g. boric acid+sodium borate), tartrate buffers (e.g. tartaric acid+sodium tartrate dihydrate), tris buffers (e.g. Tris (hydroxymethyl) aminomethane) and Hepes buffers (4- (2-hydroxyethyl) -1-piperazine ethanesulfonic acid).

[ oil ]

The composition according to the invention may comprise (d) at least one oil. If two or more oils (d) are used, they may be the same or different.

Here, "oil" refers to a fatty compound or substance that is in the form of a liquid or paste (non-solid) at room temperature (25 ℃) at atmospheric pressure (760 mmHg). As the oil, those generally used in cosmetics may be used alone or in combination thereof. These oils may be volatile or non-volatile.

The oil may be a nonpolar oil such as hydrocarbon oil, silicone oil, etc.; polar oils such as vegetable or animal oils and ester or ether oils; or a mixture thereof.

The oil may be selected from oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

As examples of vegetable oils, mention may be made of, for example, apricot oil, linseed oil, bitter tea oil (camellia oil), macadamia nut oil, corn oil, mink oil (mink oil), olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil and mixtures thereof.

As examples of animal oils, there may be mentioned, for example, squalene and squalane.

As examples of synthetic oils, alkane oils such as isododecane and isohexadecane, ester oils, ether oils and artificial triglycerides may be mentioned.

The ester oil is preferably saturated or unsaturated, linear or branched C ₁ -C ₂₆ Aliphatic mono-or polyacids with saturated or unsaturated, linear or branched C ₁ -C ₂₆ Liquid esters of aliphatic monohydric or polyhydric alcohols having a total number of carbon atoms greater than or equal to 10.

Preferably, for esters of monohydric alcohols, at least one of the alcohols and acids from which the esters of the invention are derived is branched.

Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dioctyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl pivalate and isostearyl pivalate.

C can also be used ₄ -C ₂₂ Di-or tricarboxylic acids with C ₁ -C ₂₂ Esters of alcohols and mono-, di-or tricarboxylic acids with non-sugar C ₄ -C ₂₆ Esters of dihydric, trihydric, tetrahydroxy or penta-hydroxy alcohols.

Mention may be made in particular of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis (2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis (2-ethylhexyl) adipate; diisostearyl adipate; bis (2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glycerol trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleate citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As the ester oil, C can be used ₆ -C ₃₀ And preferably C ₁₂ -C ₂₂ Sugar esters and diesters of fatty acids. Review the term "sugar" refers to an oxygen-bearing hydrocarbon-based compound containing several alcohol functionalities, with or without aldehyde or ketone functionalities, and the compound contains at least 4 carbon atoms. These sugars may be mono-, oligo-or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or sucrose), glucose, galactose, ribose, trehalose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, in particular alkyl derivatives such as methyl derivatives, for example methyl glucose.

The sugar esters of fatty acids may in particular be selected from esters or ester mixtures of the sugars previously described with linear or branched, saturated or unsaturated C ₆ -C ₃₀ And preferably C ₁₂ -C ₂₂ Esters or ester mixtures of fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from mono-, di-, tri-, tetra-and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates or mixtures thereof, such as, inter alia, oleates and palmitostearates, and pentaerythritol tetraethylhexanoate.

More particularly, mono-and di-esters are used, and in particular sucrose, glucose or methyl glucose mono-or di-oleate, stearate, behenate, oil palmitate, linoleate, linolenate and oil stearate.

One example which may be mentioned is by the name Amerchol companyDO, which is a methyl glucose dioleate.

As examples of preferred ester oils there may be mentioned, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl caproate, ethyl laurate, cetyl caprylate, octyldodecyl caprylate, isodecyl pivalate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl caprylate, 2-ethylhexyl capryl/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dioctyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, tris (2-ethylhexanoate), pentaerythritol tetrakis (2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, for example, decyl octyl glyceride, trimyristate glyceride, tripalmitin, trilineate glyceride, trilaurin glyceride, tricaprate glyceride, tricaprylate glyceride, tri (capric/caprylic) glyceride and tri (capric/caprylic/linolenic) glyceride.

As examples of the silicone oil, there may be mentioned, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogen polysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, and the like; and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, in particular liquid Polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.

These silicone oils may also be organically modified. Organomodified silicones which can be used according to the invention are silicone oils as defined above and comprising in their structure one or more organofunctional groups linked via hydrocarbon-based groups.

Organopolysiloxane is defined in more detail in the Academic Press, chemistry and Technology of Silicones by Walter Noll (1968). They may be volatile or non-volatile.

When they are volatile, the silicones are more particularly selected from those having a boiling point of 60 ℃ to 260 ℃, and even more particularly from:

(i) Cyclic polydialkylsiloxanes comprising 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, in particular the name Volatile by Union Carbide7207 or by Rhodia under the name +.>70045 Octamethyl cyclotetrasiloxane sold by V2 under the name Volatile by Union Carbide>7158 and by Rhodia under the name +.>70045 Decamethylcyclopenta-siloxane sold under the name Silsoft 1217 by V5, and dodecamethylcyclopenta-siloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclic copolymers of the type such as dimethylsiloxane/methylalkylsiloxane, such as Silicone sold by Union CarbideFZ 3109 having the formula: />

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as mixtures of octamethyltetrasiloxane and tetrakis (trimethylsilyl) pentaerythritol (50/50), and mixtures of octamethyltetrasiloxane and oxo-1, 1' -bis (2, 2', 3' -hexamethylsiloxy) neopentane; and

(ii) Containing 2 to 9 silicon atoms and having a silicon atom number of less than or equal to 5X 10 at 25 DEG C ^-6 m ² Linear volatile polydialkylsiloxane of viscosity/s. One example is decamethyltetrasiloxane sold under the name SH 200, particularly by Toray Silicone company. Silicones belonging to this class are also described in Cosmetics and Toiletries, volume 91, month 1 of 76, pages 27-32, todd&In article Volatile Silicone Fluids for Cosmetics published by Byers. The viscosity of the silicone was measured at 25 ℃ according to ASTM standard 445 appendix C.

Nonvolatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, by way of non-limiting example, of the following commercial products:

-series 47 and 70 047 sold by RhodiaOil or->Oils, such as oil 70 047V 500 000;

sold by Rhodia companyA series of oils;

200 series of oils from Dow Corning company, e.g. having 60 000mm ² DC200 of viscosity per second; and

-from General ElectricOils and certain oils from the SF series from General Electric (SF 96, SF 18).

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the 48 series of oils from Rhodia corporation.

Among the aryl-containing silicones, mention may be made of polydiarylsiloxanes, in particular polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oils.

The phenyl silicone oil may be selected from phenyl silicones of the formula:

wherein the method comprises the steps of

R ₁ To R ₁₀ Are independently of each other saturatedAnd or unsaturated, linear, cyclic or branched C ₁ -C ₃₀ Hydrocarbon-based groups, preferably C ₁ -C ₁₂ Hydrocarbon-based groups, and more preferably C ₁ -C ₆ Hydrocarbon-based groups, in particular methyl, ethyl, propyl or butyl, and

m, n, p and q are each independently an integer from 0 to 900 inclusive, preferably from 0 to 500 inclusive, and more preferably from 0 to 100 inclusive,

provided that the sum of n+m+q is not 0.

Examples that may be mentioned include products sold under the following names:

70 series 641 from RhodiaAn oil;

-from Rhodia70 633 and 763 series of oils;

oil from Dow Corning 556Cosmetic Grade Fluid;

silicones from the Bayer PK series, such as product PK20;

certain oils from the SF series of General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (phenyl trimethicone) (in the above formula, R ₁ To R ₁₀ Is methyl; p, q and n=0; m=1).

The organomodified liquid silicone may contain, inter alia, polyethyleneoxy and/or polypropyleneoxy groups. Thus, mention may be made of silicone KF-6017 by Shin-Etsu and oils from Union Carbide companyL722 and L77.

The hydrocarbon oil may be selected from:

-linear or branched, optionally cyclic, C ₆ -C ₁₆ Lower alkanes. Example packages that may be mentionedIncluding hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane; and

straight-chain or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petroleum jelly, polydecene and hydrogenated polyisobutene, such asAnd squalane.

As preferable examples of the hydrocarbon oil, for example, straight-chain or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum (petrolatum), naphthalene, and the like; hydrogenated polyisobutene, isoeicosane and decene/butene copolymers; and mixtures thereof.

The term "fat" in fatty alcohols is meant to encompass relatively large numbers of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are included in the range of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohol may have the structure R-OH, wherein R is selected from saturated and unsaturated, straight and branched groups containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be selected from C ₁₂ -C ₂₀ Alkyl and C ₁₂ -C ₂₀ Alkenyl groups. R may or may not be substituted with at least one hydroxy group.

As examples of fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenol, myristyl alcohol, octyldodecyl alcohol, hexyldecyl alcohol, oleyl alcohol, linoleyl alcohol, palmitoleic alcohol, arachidonic alcohol, erucyl alcohol and mixtures thereof.

Preferably the fatty alcohol is a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from linear (straight) or branched, saturated or unsaturated C ₆ -C ₃₀ Alcohols, preferably linear or branched saturated C ₆ -C ₃₀ Alcohols, andmore preferably C, linear or branched, saturated ₁₂ -C ₂₀ An alcohol.

The term "saturated fatty alcohol" as used herein refers to an alcohol having a long aliphatic saturated carbon chain. Preferably the saturated fatty alcohol is selected from any linear or branched, saturated C ₆ -C ₃₀ Fatty alcohols. In straight-chain or branched, saturated C ₆ -C ₃₀ Among fatty alcohols, linear or branched, saturated C can be preferably used ₁₂ -C ₂₀ Fatty alcohols. Any straight or branched, saturated C may be more preferably used ₁₆ -C ₂₀ Fatty alcohols. Branched C may even more preferably be used ₁₆ -C ₂₀ Fatty alcohols.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenol, myristyl alcohol, octyldodecyl alcohol, hexyldecyl alcohol and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (e.g., cetostearyl alcohol), and behenyl alcohol may be used as the saturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in the composition according to the invention is preferably chosen from octyldodecanol, hexyldecanol and mixtures thereof.

According to the present invention, (d) the oil may be surrounded by a plurality of (a) particles, or (d) the oil may be present in the hollow of the capsule formed by (a) particles. In other words, (d) oil may be covered by (a) particles, or a capsule formed by (a) particles contains (d) oil in the hollow of the capsule.

The (d) oil enclosed by the (a) particles or present in the hollow of the capsule formed by the (a) particles cannot directly come into contact with keratin materials such as the skin. Thus, even if (d) the oil has a tacky or greasy feel in use, the composition according to the invention will not provide a tacky or greasy feel in use.

The amount of the (d) one or more oils in the composition according to the invention may be 0.1 wt% or more, preferably 0.5 wt% or more, and more preferably 1 wt% or more, relative to the total weight of the composition.

The amount of the (d) one or more oils in the composition according to the invention may be 50 wt% or less, preferably 40 wt% or less, and more preferably 30 wt% or less, relative to the total weight of the composition.

The amount of (d) one or more oils in the composition according to the invention may be from 0.1 to 50 wt%, preferably from 0.5 to 40 wt%, and more preferably from 1 to 30 wt%, relative to the total weight of the composition.

"optional additives

In addition to the aforementioned components, the composition according to the present invention may contain components commonly used in cosmetics, particularly surfactants (particularly nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents, hydrophilic or hydrophobic UV filters, silicones and silicone derivatives other than the (d) oil, natural extracts derived from animals or vegetables, waxes, and the like, within a range not impairing the effects of the present invention.

The composition according to the invention may comprise one or more of the above optional additives in an amount of 0.01 to 50 wt%, preferably 0.05 to 30 wt%, and more preferably 0.1 to 10 wt%, relative to the total weight of the composition.

[ composition ]

The composition according to the invention may be intended for use as a cosmetic composition. Thus, the cosmetic composition according to the invention may be intended for application to keratin materials. Keratin materials herein refer to materials containing keratin as a main constituent, and examples of the keratin materials include skin, scalp, nails, lips, hair, and the like. The cosmetic composition according to the invention is therefore preferably used in a cosmetic process for keratin materials, in particular the skin.

Thus, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin color cosmetic composition, and more preferably a skin care composition.

The composition according to the invention may be prepared by mixing the above essential and optional ingredients according to any method known to the person skilled in the art.

The above basic components or optional components may be heated if desired. Thus, when the above basic components and optional components are mixed, heating may be performed.

If the composition according to the invention comprises (d) one or more oils, the composition may be in the form of an emulsion, an O/W emulsion or a W/O emulsion. Preferably the composition according to the invention is in the form of an O/W emulsion, as it can provide a fresh feel due to the (c) water forming its external phase.

[ film ]

The composition according to the present invention can be used to easily prepare a film. (a) the particles may aggregate and integrate into a continuous film.

Thus, the present invention may also relate to a process for preparing a film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 μm, more preferably 1.5 μm or more, and even more preferably 2 μm or more, comprising:

applying the composition according to the invention to a substrate, preferably a keratin material, more preferably skin; and is combined with

The composition is dried.

The upper limit of the thickness of the above film is not limited. Thus, for example, the thickness of the above film may be 1mm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.

Since the method for preparing a film, which may be related to the present invention, comprises a step of applying the composition according to the present invention onto a substrate, preferably keratin materials, and more preferably skin, and a step of drying the composition, the method does not require any spin coating or spray coating, and thus, even a relatively thick film may be easily prepared. Thus, the method for producing a film, which can be related to the present invention, can produce a relatively thick film without any special equipment such as spin coaters and spray coating machines.

Although the film prepared by the above method is relatively thick, it is still thin and may be transparent and thus may not be easily perceived. Therefore, the film can be preferably used as a cosmetic film.

If the substrate is not a keratin substance such as skin, the composition according to the invention may be applied to a substrate made of any material other than keratin. The material of the non-keratin substrate is not limited. Two or more materials may be used in combination. Thus, a single type of material or a combination of different types of materials may be used. In any case, it is preferred that the substrate be soft or elastic.

If the substrate is not a keratinous material, it is preferred that the substrate be water soluble, as the film may be left by washing the substrate with water. As examples of the water-soluble material, poly (meth) acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, and the like can be mentioned. PVA is preferred.

If the non-keratin substrate is in the form of a sheet, it may have a thickness greater than that of the film prepared by the above method, so that the film attached to the substrate sheet is easy to handle. The thickness of the non-keratin base sheet is not limited, but may be 1 μm to 5mm, preferably 10 μm to 1mm, and more preferably 50 to 500 μm.

More preferably, the film prepared by the above method is peelable from a non-keratin substrate. The peeling mode is not limited. Thus, the film prepared by the above method may be peeled from the non-keratin substrate, or by dissolving the substrate sheet in a solvent (such as water).

Thus, the invention may also relate to:

(1) A film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 μm, more preferably 1.5 μm or greater, and even more preferably 2 μm or greater, the film being prepared by a process comprising the steps of:

applying the composition according to the invention to a substrate, preferably to keratin materials, and more preferably to the skin; and is combined with

The composition is dried and the composition is dried,

and

(2) A film, preferably a cosmetic film, optionally having a thickness preferably greater than 0.1 μm, more preferably 1.5 μm or greater, and even more preferably 2 μm or greater, the film comprising:

at least one cationic polymer and at least one anionic polymer; and

at least one non-polymeric acid having two or more pKa values or one or more salts thereof,

and

optionally at least one oil.

The above explanations regarding the cationic and anionic polymers and the non-polymeric acids having two or more pKa values or one or more salts thereof, and the above oils, are applicable to those in the above films (1) and (2).

The film obtained above may thus be free-standing. The term "free standing" herein means that the film may be in the form of a sheet and may be handled as a stand-alone sheet without the aid of a substrate or support. Thus, the term "free standing" may have the same meaning as "self-supporting".

Preferably the above film is hydrophobic.

The term "hydrophobic" in this specification means that the solubility of the polymer in water (preferably having a volume of 1 liter) is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, relative to the total weight of the polymer, at 20 ℃ to 40 ℃, preferably 25 ℃ to 40 ℃, and more preferably 30 ℃ to 40 ℃. Most preferably the polymer is insoluble in water.

If the above film is hydrophobic, the film may have water-resistant properties and thus may remain on keratin-based materials such as skin even if the surface of the keratin materials is wet due to, for example, sweat and rain. Thus, when the film provides any cosmetic effect, the cosmetic effect may last for a long time.

On the other hand, the above film can be easily removed from keratin materials such as skin under alkaline conditions, such as pH of 8 to 12, preferably 9 to 11. Thus, the above-described film is difficult to remove with water, however it can be easily removed with soaps that provide such alkaline conditions.

The above film may comprise at least one biocompatible and/or biodegradable polymer layer. Two or more biocompatible and/or biodegradable polymers may be used in combination. Thus, a single type of biocompatible and/or biodegradable polymer or a combination of different types of biocompatible and/or biodegradable polymers may be used.

The term "biocompatible" polymer in this specification means that the polymer does not have excessive interactions with cells in a living body (including skin), and the polymer is not recognized as a foreign substance by the living body.

The term "biodegradable" polymer in this specification means that the polymer can be degraded or decomposed in a living body due to, for example, metabolism of the living body itself or metabolism of microorganisms that can exist in the living body. The biodegradable polymer may also be degraded by hydrolysis.

If the above film comprises biocompatible and/or biodegradable polymers, it is less or non-irritating to the skin and does not cause any rash. Furthermore, the above films can adhere well to the skin due to the use of biocompatible and/or biodegradable polymers.

The above film can be used for cosmetic treatment of keratin materials, preferably skin, in particular the face. The above film may be of any shape or form. For example, it may be used as a full face patch, or a patch for a portion of the face (such as the cheek, nose, and periocular region).

If the above film comprises at least one hydrophilic or water-soluble UV filter, the film may provide a UV screening effect derived from the hydrophilic or water-soluble UV filter. In general, hydrophilic or water-soluble UV filters can be removed from the surface of keratinous substrates (e.g., skin) by water (e.g., perspiration and rain). However, since a hydrophilic or water-soluble UV filter is contained in the above film, the hydrophilic or water-soluble UV filter is difficult to remove by water, thus resulting in a durable UV shielding effect.

Cosmetic method and use

The invention also relates to:

cosmetic process for keratin materials such as the skin, comprising:

applying the composition according to the invention to keratin materials; and drying the composition to form a cosmetic film on the keratin materials,

and

use of the composition according to the invention for the preparation of a cosmetic film on keratin materials such as the skin.

Cosmetic methods herein refer to non-therapeutic cosmetic methods for the surface care and/or make-up of keratinous materials, such as skin.

In both the above method and use, the above cosmetic film is resistant to water having a pH of 7 or less, and can be removed with water having a pH of higher than 7, preferably 8 or higher, and more preferably 9 or higher.

In other words, the above cosmetic film may be waterproof under neutral or acidic conditions such as pH in the range of 7 or less, preferably 6 or more to 7 or less, and more preferably in the range of 5 or more to 7 or less, whereas the above cosmetic film may be removed under alkaline conditions such as pH higher than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.

Thus, the above cosmetic film may be water-resistant, and thus may remain on keratin materials (such as skin) even if the surface of the keratin materials is wet due to, for example, sweat and rainwater. On the other hand, the above cosmetic film can be easily removed from keratin materials such as skin under alkaline conditions. Therefore, the above cosmetic film is difficult to remove with water, however, it can be easily removed with soap capable of providing alkaline conditions.

If the above cosmetic film comprises a UV filter which may be present in the composition according to the invention, the above cosmetic film may protect keratin materials such as the skin from UV rays, thus limiting the darkening of the skin, improving the color and uniformity of the skin tone, and/or treating the aging of the skin.

Furthermore, due to the nature of the polyion complex particles in the cosmetic film, the above cosmetic film may have a cosmetic effect, such as absorbing or adsorbing malodors and/or protecting keratinous materials from, for example, dirt or contaminants, even if the cosmetic film does not contain any cosmetically active ingredient.

Furthermore, even if the cosmetic film does not contain any cosmetically active ingredient, the above cosmetic film can instantaneously change or modify the appearance of the skin by changing the light reflection on the skin or the like. Thus, the above cosmetic film can cover skin imperfections, such as pores or wrinkles. In addition, the above cosmetic film can instantaneously change or modify skin feel by changing surface roughness on the skin, etc. In addition, the above cosmetic film can immediately protect the skin by covering the skin surface and protecting the skin from environmental pressure (such as pollutants, impurities, etc.) as a barrier.

The above cosmetic effects can be adjusted or controlled by changing the chemical composition, thickness and/or surface roughness of the above cosmetic film.

If the cosmetic film described above comprises at least one additional cosmetically active ingredient other than the (d) oil, the cosmetic film may have the cosmetic effect provided by the additional cosmetically active ingredient or ingredients. For example, if the cosmetic film comprises at least one cosmetically active ingredient selected from the group consisting of anti-aging agents, anti-sebum agents, deodorants, antiperspirants, whitening agents, and mixtures thereof, the cosmetic film may treat skin aging, absorb sebum on skin, control odors on skin, control perspiration on skin, and/or whiten skin.

The make-up cosmetic composition may also be applied to the above cosmetic film or sheet after the above cosmetic film or sheet has been applied to the skin.

Examples

The present invention will be described in more detail by way of examples. However, they should not be construed as limiting the scope of the invention.

Examples 1 to 11 and comparative examples 1 to 13

[ preparation ]

Each of the compositions according to examples 1 to 11 and comparative examples 1 to 13 was prepared by mixing the ingredients shown in tables 1 to 5 according to the following steps 1 to 7.

1. The ingredients of phase A were mixed and homogenized at 75 ℃ +/-5 ℃ to obtain a mixture of phase A.

2. The ingredients of phase B were added to the mixture of phase A at 75 ℃ +/-5 ℃ and homogenized to obtain a mixture of phases A and B.

3. The ingredients of phase C were added to the above mixture of phases a and B obtained by step 2 at 75 ℃ +/-5 ℃ and homogenized to obtain a mixture of phases A, B and C.

4. The ingredients of phase D were added to the above mixture of phases A, B and C obtained by step 3 at 75 ℃ +/-5 ℃ and homogenized to obtain a mixture of phases A, B, C and D.

5. The ingredients of phase E were mixed and homogenized at 75 ℃ +/-5 ℃ to obtain a mixture of phase E.

6. The mixture of phase E obtained by step 5 was added to the above mixture of phases A, B, C and D obtained by step 4 at 75 ℃ +/-5 ℃ and homogenized to obtain a mixture of phases A, B, C, D and E.

7. The ingredients of phase F were added to the above mixture of phases A, B, C, D and E obtained by step 6 at 75 ℃ +/-5 ℃ and homogenized, followed by cooling to room temperature.

The amounts of the ingredients in tables 1-5 are all based on "% by weight" as active material.

TABLE 1

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TABLE 2

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TABLE 3 Table 3

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TABLE 4 Table 4

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TABLE 5

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[ evaluation ]

(moisturizing texture)

Three panelists evaluated the texture of each of the compositions according to examples 1-11 and comparative examples 1-13 with respect to moisturizing feel during and after application of the composition. Specifically, each panelist applied each composition to his or her hand and spread it to evaluate the moisturizing feel and rated from 1 (low) to 5 (high). They are then classified into the following three categories based on the average of the grades:

and (3) good: 4 to 5

Generally: greater than 2 and less than 4

The difference is: 1 to 2

The results are shown in Table 6.

TABLE 6

Table 6 shows that the compositions according to the present invention can provide improved moisturization.

On the other hand, table 6 also shows that compositions lacking any essential ingredients in the compositions according to the invention can only provide limited or relatively poor moisturizing effects.

(optical matte effect)

The dulling effect of the compositions according to examples 3, 5 and 9-11 and comparative example 1 was evaluated by in vitro dulling tests. Specifically, each composition was spread on a control sheet by an automatic film coater to form a 100 μm layer, and dried at 37 ℃ for 24 hours. Thereafter, an artificial sebum/sweat composition having the formulation shown in table 7 below was sprayed onto the above layer on the control card at room temperature. The amounts of artificial sebum/sweat composition sprayed on each of the above layers are the same as each other.

TABLE 7

After 6 minutes, the reflectance on the above layer was measured as a 60 ° gloss value by a gloss meter (GM-268,Konika Minolta).

The anti-gloss index is determined by the following equation:

anti-gloss index = { (reflectance on upper layer 6 minutes after spraying) - (reflectance of negative control) }/{ (reflectance of positive control 6 minutes after spraying) - (reflectance of negative control) } 100

In the above equation, the reflectance was set to 0 for the negative control and 100 for the positive control 6 minutes after spraying.

The determined anti-gloss index (%) was classified according to the following criteria:

excellent: 70 or more

And (3) good: 50 or more and less than 70

The difference is: less than 50

The results are shown in table 8.

TABLE 8

Table 8 shows that the compositions according to the invention can provide excellent or good dulling effects. It is preferable to use a silylated silica as the filler (b) to provide excellent matting effect.

On the other hand, table 8 also shows that the composition lacking the oil absorbing powder as the (b) filler does not provide a matting effect.

Claims

1. A composition comprising:

(a) At least one particle comprising

At least one cationic polymer and at least one anionic polymer,

And

(b) At least one filler; and

(c) And (3) water.

2. The composition of claim 1, wherein the cationic polymer has at least one positively chargeable and/or positively charged group selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidino groups, imidazole groups, imino groups and pyridine groups.

3. The composition according to claim 1 or 2, wherein the cationic polymer is selected from the group consisting of cyclized polymers of alkyl diallylamine and of dialkyl diallylamine such as (co) polydiallyldialkylammonium chloride, (co) polyamines such as (co) polylysine, cationic (co) polyaminoacids such as collagen, cationic cellulose polymers, and salts thereof.

4. A composition according to any one of claims 1 to 3, wherein the amount of the one or more cationic polymers forming the (a) particles in the composition is from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

5. The composition according to any one of claims 1 to 4, wherein the anionic polymer is selected from hyaluronic acid and derivatives thereof.

6. The composition of any one of claims 1 to 5, wherein the amount of the one or more anionic polymers forming the (a) particles in the composition is from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

7. The composition of any one of claims 1 to 6, wherein the non-polymeric acid or one or more salts thereof having two or more pKa values is an organic acid or one or more salts thereof, preferably a hydrophilic or water-soluble organic acid or one or more salts thereof, and more preferably a phytic acid or a salt thereof.

8. The composition of any one of claims 1 to 7, wherein the amount of the non-polymeric acid or one or more salts thereof having two or more pKa values forming the (a) particles in the composition is from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

9. The composition according to any one of claims 1 to 8, wherein the amount of the (a) particles in the composition is from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

10. The composition of any one of claims 1 to 9, wherein the (b) filler is selected from hydrophilic oil absorbing powder or hydrophobic oil absorbing powder.

11. The composition according to claim 10, wherein the hydrophobic oil absorbing powder is selected from the group consisting of a powder of hydrophobic silica, preferably a powder of hydrophobic silica aerogel, and more preferably a powder of hydrophobic aerogel of silylated silica.

12. The composition of any one of claims 1 to 11, wherein the amount of the (b) one or more fillers in the composition is from 0.01 to 15 wt%, preferably from 0.05 to 10 wt%, and more preferably from 0.1 to 5 wt%, relative to the total weight of the composition.

13. The composition according to any one of claims 1 to 12, wherein the amount of (c) water in the composition is 50 to 95 wt%, preferably 60 to 90 wt%, and more preferably 70 to 85 wt%, relative to the total weight of the composition.

14. The composition according to any one of claims 1 to 13, wherein the composition is a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care cosmetic composition.

15. A cosmetic method for keratinous materials such as skin, the cosmetic method comprising:

applying the composition according to any one of claims 1 to 14 to the keratin materials; and is combined with

Drying the composition to form a cosmetic film on the keratin materials.