JP7403978B2 - W/O composition containing polyion complex and organic UV filter - Google Patents

Description

The present invention relates to a W/O type composition comprising a polyion complex and an organic UV filter.

Generally, UV filters are used to provide protection from UV (ultraviolet) radiation. A large number of sun protection compositions have been proposed to protect the skin from UV-A and/or UV-B.

These antisun compositions contain in varying concentrations one or more insoluble and/or fat-soluble and/or water-soluble, organic and/or inorganic UV filters capable of selectively absorbing harmful UV radiation. It is often in the form of an oil-in-water or water-in-oil emulsion, a gel, or a non-aqueous product containing. These UV filters and their amount are selected depending on the desired sun protection factor (SPF).

Sun Protection Factor (SPF) is the mathematical ratio of the UV radiation dose required to reach the erythema-inducing threshold with a UV-screening agent to the UV radiation dose required to reach the erythema-inducing threshold without a UV-screening agent. represents.

To date, several prior art documents have been published regarding sun protection compositions containing SPF enhancers such as hollow particles to enhance the UV protection effect. For example, WO 2014/203913 states that in a physiologically acceptable medium: (a) at least one UV filter; (b) at least one particle having a refractive index of 1.5 or more; and (c) at least and one SPF enhancer.

However, there is a need for compositions that have a higher sun protection index, which can be expressed by a higher UV absorbance of the composition.

WO 2014/203913 European Patent Application No. 0080976 French Patent No. 2077143 French Patent No. 2393573 French Patent No. 1492597 WO 2005/000903 U.S. Patent No. 4,131,576 U.S. Patent No. 3,589,578 U.S. Patent No. 4,031,307 French Patent No. 2162025 French Patent No. 2280361 French Patent No. 2252840 French Patent No. 2368508 French Patent No. 1583363 U.S. Patent No. 3,227,615 U.S. Patent No. 2,961,347 French Patent No. 2080759 French Patent of Addition No. 2190406 French Patent No. 2320330 French Patent No. 2270846 French Patent No. 2316271 French Patent No. 2336434 French Patent No. 2413907 U.S. Patent No. 2,273,780 U.S. Patent No. 2,375,853 U.S. Patent No. 2,388,614 U.S. Patent No. 2,454,547 U.S. Patent No. 3,206,462 U.S. Patent No. 2,261,002 U.S. Patent No. 2,271,378 U.S. Patent No. 3,874,870 U.S. Patent No. 4,001,432 U.S. Patent No. 3,929,990 U.S. Patent No. 3,966,904 U.S. Patent No. 4,005,193 U.S. Patent No. 4,025,617 U.S. Patent No. 4,025,627 U.S. Patent No. 4,025,653 U.S. Patent No. 4,026,945 U.S. Patent No. 4,027,020 European Patent Application No. 0122324 EP-A-0750899 EP-A-1069172 EP-A-0173109 U.S. Patent No. 3,836,537 French Patent No. 1,400,366 USP 5240975 EP-669,323 U.S. Patent No. 2,463,264 U.S. Patent No. 5,237,071 U.S. Patent No. 5,166,355 GB-2,303,549 DE-19,726,184 EP-893,119 WO 93/04665 DE-19855649 US 4,427,836 US 4,469,825 US 4,594,363 US 4,677,003 US 4,920,160 US 4,970,241 EP267726 EP331421 US 490,229 US 5,157,084 US 5,663,213 EP1092421 JP 3605118

CTFA Dictionary (4th edition, 1991) 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, Vol. 33, No. 10-3694-3704 Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press. Cosmetics and Toiletries, Volume 91, January 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics ASTM Standard 445, Appendix C

Therefore, the aim of the present invention is to provide compositions with higher UV absorbance.

The above object of the present invention is to
(a)
(i) at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(ii) at least one anionic polymer and at least one non-polymeric base or salt thereof having a pKb value of two or more; or
(iii) at least one amphoteric polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more and/or at least one non-polymeric base or salt thereof having a pKb value of two or more; at least one polyion complex comprising;
(b) at least one organic UV filter;
(c) at least one SPF enhancer;
(d) water, preferably a cosmetic composition, more preferably a dermocosmetic composition.

The cationic polymer has at least one selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. may have one positive charge and/or may have a portion with a positive charge.

The anionic polymer has at least one selected from the group consisting of sulfate groups, sulfate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups, phosphate groups, phosphonic acid groups, phosphonate groups, carboxylic acid groups, and carboxylate groups. may have one negative charge and/or may have a portion with a negative charge.

Ampholytic polymers are
Has at least one positive charge selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. a moiety capable of and/or having a positive charge,
and at least one negative charge selected from the group consisting of a sulfate group, a sulfate group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, a phosphonic acid group, a phosphonate group, a carboxylic acid group, and a carboxylate group. and/or may have a portion with a negative charge.

The amount of polymer in the composition according to the invention is from 0.001% to 25% by weight, preferably from 0.01% to 20% by weight, more preferably from 0.1% to 15% by weight, relative to the total weight of the composition. Something can happen.

Non-polymeric acids with pKa values of 2 or more include terephthalylidene dicamphorsulfonic acid and its salts (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts. , and mixtures thereof.

Non-polymeric bases with pKb values of 2 or more include non-polymeric diamines such as ethylene diamine, propylene diamine, pentanediamine, hexane diamine, urea and its derivatives and guanidine and its derivatives, non-polymeric polyamines such as spermine and spermidine, basic Can be selected from the group consisting of amino acids, as well as mixtures thereof.

The amount of non-polymeric acids or salts thereof having a pKa value of two or more or non-polymeric bases or salts thereof having a pKb value of two or more in the composition according to the invention is 0.001 based on the total weight of the composition. It can be from 10% by weight, preferably from 0.01% to 5% by weight, more preferably from 0.1% to 1% by weight.

The amount of (b) organic UV filter in the composition according to the invention is from 10% to 60% by weight, preferably from 20% to 50% by weight, more preferably 30% by weight, relative to the total weight of the composition. to 40% by mass.

(c) The SPF enhancer can be selected from the group consisting of hollow particles, silica particles containing metal oxides, multilayered spherical composite particles, and mixtures thereof.

The amount of (c) SPF improver in the composition according to the invention is from 0.1% to 15% by weight, preferably from 0.5% to 10% by weight, more preferably 1% by weight, relative to the total weight of the composition. to 5% by mass.

The amount of (d) water in the composition according to the invention is from 1% to 50% by weight, preferably from 10% to 40% by weight, more preferably from 20% to 30% by weight, relative to the total weight of the composition. % by mass.

The composition according to the invention may further comprise (e) at least one additional oil.

The present invention also provides a cosmetic method for keratin substrates such as skin, comprising:
The present invention relates to a method comprising applying a composition according to the invention to a keratin substrate.

The present invention also provides
(b) at least one organic UV filter;
(c) at least one SPF enhancer;
(d) for increasing the UV absorbance of the composition in a W/O type composition, preferably a cosmetic composition, more preferably a dermocosmetic composition, comprising water;
(a)
(i) at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(ii) at least one anionic polymer and at least one non-polymeric base or salt thereof having a pKb value of two or more; or
(iii) at least one amphoteric polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more and/or at least one non-polymeric base or salt thereof having a pKb value of two or more; The use of at least one polyion complex comprising:

1 is a graph of UV absorbance of each of the compositions according to Example 1 and Comparative Example 1. 2 is a graph of UV absorbance of each of the compositions according to Example 2 and Comparative Example 2. 3 is a graph of UV absorbance of each of the compositions according to Comparative Examples 3 and 4.

As a result of extensive studies, the present inventors discovered that it is possible to provide a composition with high UV absorbance by using a polyion complex. Therefore, the composition according to the invention
(a)
(i) at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(ii) at least one anionic polymer and at least one non-polymeric base or salt thereof having a pKb value of two or more; or
(iii) at least one amphoteric polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more and/or at least one non-polymeric base or salt thereof having a pKb value of two or more; at least one polyion complex comprising;
(b) at least one organic UV filter;
(c) at least one SPF enhancer;
(d) Contains water.

Compositions according to the invention may have higher UV absorbance. Therefore, compositions according to the invention can have higher SPF values.

Each of the above combinations (i), (ii) and (iii) can form a polyion complex. The polyion complex can be in the form of particles. It may be preferred that the plurality of polyion complex particles be present at the interface between (b) the organic UV filter and (d) water.

Compositions according to the invention may be stable over long periods of time.

The composition according to the invention can be prepared by applying (b) a film containing an organic UV filter to a substrate, preferably a keratin substrate such as skin and hair, more preferably skin, by applying the composition to a substrate, preferably a keratin substrate such as skin and hair, by means of a polyion complex; It can be used to prepare things by drying them.

The films prepared by the compositions according to the invention can have various cosmetic functions.

For example, the films prepared by the compositions according to the invention can have cosmetic effects such as blocking ultraviolet light.

Moreover, the films prepared by the compositions according to the invention can be transparent or translucent, even if the films are relatively thick, and therefore may not be easy to perceive.

Furthermore, the films prepared by the compositions according to the invention can be water-resistant, so that they can be applied to keratin substrates, such as skin, even when the surface of the keratin substrate is wet, for example due to sweat or rain. can remain on top. The coating is therefore waterproof and can exhibit long-lasting UV blocking effects.

Hereinafter, the composition etc. according to the present invention will be explained in more detail.

[Polyion Complex]
The composition according to the invention comprises (a) at least one polyion complex. Two or more different types of (a) polyion complexes may be used in combination. Thus, a single type of (a) polyion complex or a combination of different types of (a) polyion complexes can be used.

The amount of (a) polyion complex in the composition according to the invention can be 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, based on the total weight of the composition.

The amount of (a) polyion complex in the composition according to the invention can be up to 30% by weight, preferably up to 25% by weight, more preferably up to 20% by weight, based on the total weight of the composition.

The amount of (a) polyion complex in the composition according to the invention is from 0.001% to 30% by weight, preferably from 0.01% to 25% by weight, more preferably from 0.1% by weight, relative to the total weight of the composition. It can be 20% by mass.

(a) The polyion complex can be in the form of particles. The particle size of the polyion complex particles can be from 5 nm to 100 μm, preferably from 100 nm to 50 μm, more preferably from 200 nm to 30 μm, even more preferably from 500 nm to 20 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. This particle size may be based on number average diameter.

A plurality of polyion complex particles can be present at the interface between (b) the organic UV filter and (d) water. Therefore, polyion complex particles can form emulsions. In the composition according to the invention, to form a W/O type, (d) water can constitute the dispersed phase and (b) the organic UV filter can constitute the continuous phase.

The above means that (a) the polyion complex itself is amphiphilic and insoluble in oil or water.

(a) The polyionic complex comprises at least one polymer or combination of polymers together with a polyacid or base.

Specifically, (a) the polyion complex is
(i) at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(ii) at least one anionic polymer and at least one non-polymeric base or salt thereof having a pKb value of two or more; or
(iii) at least one amphoteric polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more and/or at least one non-polymeric base or salt thereof having a pKb value of two or more; include.

The types of cationic, anionic and amphoteric polymers are not limited. Combinations of two or more different types of cationic polymers may also be used. Thus, a single type of cationic polymer or a combination of different types of cationic polymers can be used. Combinations of two or more different types of anionic polymers may also be used. Thus, a single type of anionic polymer or a combination of different types of anionic polymers can be used. Combinations of two or more different types of amphoteric polymers may also be used. Thus, a single type of amphoteric polymer or a combination of different types of amphoteric polymers can be used.

The total amount of polymers according to any one of the above (i) to (iii) in the composition according to the invention is at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.01% by weight, relative to the total weight of the composition. It can be 0.1% by mass or more.

The total amount of polymers according to any one of the above (i) to (iii) in the composition according to the invention is not more than 25% by weight, preferably not more than 20% by weight, more preferably not more than 20% by weight, relative to the total weight of the composition. It can be 15% by mass or less.

The total amount of polymers according to any one of the above (i) to (iii) in the composition according to the invention is from 0.001% to 25% by weight, preferably from 0.01% to 20% by weight, relative to the total weight of the composition. % by weight, more preferably from 0.1% to 15% by weight.

(cationic polymer)
Cationic polymers have a positive charge density. The charge density of the cationic polymer can be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g, more preferably from 0.1 to 10 meq/g.

It may be preferable that the molecular weight of the cationic polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, even more preferably 5000 or more.

Unless otherwise defined in the description, "molecular weight" means number average molecular weight.

The cationic polymer has at least one selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. may have one positive charge and/or may have a portion with a positive charge. The term (primary) "amino group" as used herein means an _-NH2 group.

Cationic polymers may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

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

(1) Derived from esters and amides of acrylic acid or methacrylic acid, with the following formula:

(In the formula,
R ₁ and R ₂ may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups;
_R3 may be the same or different and is selected from hydrogen and _CH3 ;
The symbol A may be the same or different and represents a straight-chain or branched alkyl group containing 1 to 6 carbon atoms, such as 2 to 3 carbon atoms, and a straight-chain or branched alkyl group containing 1 to 4 carbon atoms. selected from hydroxyalkyl groups containing carbon atoms;
R ₄ , R ₅ , and R ₆ may be the same or different and are selected from alkyl groups containing 1 to 18 carbon atoms, and benzyl groups, and in at least one embodiment 1 to 6 an alkyl group containing carbon atoms,
X is an anion derived from an inorganic or organic acid, such as a methosulfate anion and a halide ion, such as chloride and bromide)
Homopolymers and copolymers containing at least one unit selected from the following.

Copolymers of family (1) may also contain at least one unit derived from a comonomer, such as acrylamide, methacrylamide, diacetone acrylamide, in which the nitrogen atom is substituted with a (C ₁ -C ₄ ) lower alkyl group. acrylamide and methacrylamide, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

Examples of family (1) copolymers include, but are not limited to:
a copolymer of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide,
Copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, as described for example in European Patent Application No. 0080976;
copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate,
quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylic acid or methacrylate copolymers, as described for example in FR 2077143 and FR 2393573;
dimethylaminoethyl methacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymer,
Vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, and crosslinked methacryloyloxy(C ₁ -C ₄ )alkyl tri(C ₁ -C ₄ )alkylammonium salt polymers, e.g. Homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl or copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, followed by homopolymerization or copolymerization of olefins. Polymers obtained by crosslinking with compounds containing sexual unsaturation, such as methylenebisacrylamide.

Preferably, the copolymers of family (1) have units derived from vinylpyrrolidone. More preferably, the copolymers of family (1) have at least one pendant ring structure derived from vinylpyrrolidone. On the other hand, the copolymers of family (1) preferably do not contain a ring structure in the polymer skeleton.

Copolymers of family (1) with vinylpyrrolidone units can be selected from:
(i) a copolymer comprising vinylpyrrolidone units and dimethylaminoethyl methacrylate units, e.g.
- vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, for example vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (20/80 by weight) sold under the trade name Copolymer 845 by the company ISP;
- vinylpyrrolidone quaternized with diethyl sulfate/dimethylaminoethyl methacrylate copolymer, for example vinylpyrrolidone quaternized with diethyl sulfate, sold under the trade names Gafquat 734, 755, 755S and 755L by ISP /dimethylaminoethyl methacrylate copolymer,
- Vinylpyrrolidone/dimethylaminoethyl methacrylate/hydrophilic polyurethane copolymer, for example vinylpyrrolidone/methacrylic acid sold under the trade name Pecogel GC-310 by the company UCIB or under the tradename Aquamere C1031 and C1511 by the company Blagden Chemicals. dimethylaminoethyl/hydrophilic polyurethane copolymer,
- Quaternized or non-quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate/C ₈ to C ₁₆ olefin copolymers, such as those sold by ISP under the trade names Ganex ACP 1050 to 1057, 1062 to 1069 and 1079 to 1086 , vinylpyrrolidone/dimethylaminoethyl methacrylate/ _C8 - _C16 olefin copolymer,
as well as
- vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam copolymer, for example vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam copolymer sold under the trade name Gaffix VC713 by ISP,
(ii) copolymers comprising vinylpyrrolidone units and methacrylamide propyltrimethylammonium (MAPTAC) units, e.g.
- vinylpyrrolidone/methacrylamidopropyltrimethylammonium copolymers, for example vinylpyrrolidone/MAPTAC copolymers sold under the trade names Gafquat ACP1011 and Gafquat HS100 by ISP,
as well as
- vinylpyrrolidone/methacrylamidopropyltrimethylammonium/vinylcaprolactam terpolymers, for example vinylpyrrolidone/MAPTAC/vinylcaprolactam terpolymers sold under the trade names Polymer ACP 1059, 1060 and 1156 by ISP; and
(iii) copolymers comprising vinylpyrrolidone units and methylvinylimidazolium units, e.g.
- vinylpyrrolidone/methylvinylimidazolium chloride copolymers, for example vinylpyrrolidone/methylvinylimidazolium chloride copolymers sold by BASF under the trade names Luviquat FC370, FC550, FC905 and HM552,
- vinylpyrrolidone/methylvinylimidazolium chloride/vinylimidazole copolymer, for example vinylpyrrolidone/methylvinylimidazolium chloride/vinylimidazole copolymer sold under the trade name Luviquat 8155 by BASF,
as well as
- Vinylpyrrolidone/methylvinylimidazolium methosulfate copolymer, for example vinylpyrrolidone/methylvinylimidazolium methosulfate copolymer sold under the tradename Luviquat MS370 by BASF.

The copolymers of family (1) are selected from copolymers comprising vinylpyrrolidone units and dimethylaminoethyl methacrylate units, more preferably vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. , more preferably polyquaternium-11.

(2) Cationic cellulose derivatives, such as cellulose ether derivatives containing a quaternary ammonium group, such as those described in French Patent No. 1492597, etc., such as those manufactured by 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 quaternary ammonium hydroxyethylcellulose reacted with an epoxide substituted with trimethylammonium groups.

The cationic cellulose derivatives are quaternary modified with at least one quaternary ammonium group containing at least one fatty chain such as an alkyl, arylalkyl or alkylaryl group containing at least 8 carbon atoms, or mixtures thereof. Hydroxyethylcellulose may be preferred. The alkyl group carried by the quaternary ammonium group may preferably contain from 8 to 30 carbon atoms, especially from 10 to 30 carbon atoms. Aryl groups preferably represent phenyl, benzyl, naphthyl or anthryl groups.

More preferably, the cationic cellulose derivative may contain at least one quaternary ammonium group comprising at least one C ₈ -C ₃₀ hydrocarbon group.

Examples of quaternized alkylhydroxyethyl cellulose containing C ₈ to C ₃₀ fatty chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM- sold by the company Amerchol. X 529-18B (C12 alkyl) and Quatrisoft LM-X 529-8 (C18 alkyl) or Softcat Polymer SL100, Softcat SX-1300X, Softcat SX-1300H, Softcat SL-5, Softcat SL-30, Softcat SL-60, Softcat SK-MH, Softcat SX-400X, Softcat SX-400H, Softcat SK-L, Softcat SK-M, and Softcat SK-H, and products sold by Croda Corporation Crodacel QM, Crodacel, QL (C12 alkyl) and Crodacel QS (C18 alkyl).

It may be preferred that the cationic polymer is selected from the group consisting of polyquaternium-24, polyquaternium-67 and mixtures thereof. Polyquaternium-67 is most preferred.

From another point of view, the cationic cellulose derivative can also be chosen among cationic cellulose ethers containing from 4000 to 10000 anhydroglucose units, said anhydroglucose units being substituted with at least:
(i) one substituent of the formula:
[R ₄ R ₅ R ₆ R ₉ N ⁺ ](X ₂ ^- )
(In the formula,
R ₄ and R ₅ independently represent a methyl or ethyl group,
R ₆ represents a linear or branched C ₈ to C ₂₄ alkyl group, or an aralkyl group in which the linear or branched alkyl moiety is C ₈ to C ₂₄ ;
R ₉ represents a divalent group selected from -(B) _q -CH ₂ -CHOH-CH ₂ - and -CH ₂ CH ₂ -, allowing binding to the anhydroglucose group;
q indicates 0 or 1,
B represents a divalent group -(CH ₂ CH ₂ O) _n' -,
n' is an integer ranging from 1 to 100,
X ₂ ^- represents an anion); and
(ii) one substituent of the formula:
[R ₁ R ₂ R ₃ R ₈ N ⁺ ](X ₁ ^- )
(In the formula,
R ¹ , R ² and R ³ each independently represent a methyl or ethyl group,
R ⁸ represents a divalent group selected from -(A) _p -CH ₂ -CHOH-CH ₂ - and -CH ₂ CH ₂ -, allowing binding to an anhydroglucose group;
p indicates 0 or 1,
A represents a divalent group -(CH ₂ CH ₂ O) _n -,
n is an integer ranging from 1 to 100,
X ₁ ^- represents an anion).

Preferably, substituent (i) of the formula [R ₄ R ₅ R ₆ R ₉ N ⁺ ](X ₂ ⁻ ) is present in an average amount of 0.0003 to 0.08 mol per mole of anhydroglucose units.

Cationic cellulose ethers that can be used in the compositions according to the invention are preferably hydroxyethylcellulose or hydroxypropylcellulose. The cationic cellulose ethers that can be used in the compositions according to the invention preferably contain more than 4500, advantageously more than 5000 and more preferably more than 6000 anhydroglucose units.

Preferably, the cationic cellulose ethers that can be used in the compositions according to the invention preferably contain at most 9000, preferably at most 8000 anhydroglucose units.

These cationic cellulose ethers and methods for their preparation are described in application WO 2005/000903.

According to a preferred variant, the cationic cellulose ethers that can be used in the compositions according to the invention contain at least one unit (IV) and at least one of the following units (I), (II) and (III): One:

formed from, but
The total number of units (I)+(II)+(III)+(IV) is between 4000 and 10000,
The ratio [(III)+(IV)]/[(I)+(II)+(III)+(IV)] ranges from 0.0003 to 0.8;
The ratio [(II)+(IV)]/[(I)+(II)+(III)+(IV)] ranges from 0.02 to 0.9;
integers n and n', independently of each other, range from 0 to 5;
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a methyl or ethyl group,
R ₆ is a linear or branched C ₈ -C ₂₄ , preferably C ₁₀ -C ₂₄ , more preferably C ₁₂ -C ₂₄ , even better C ₁₂ -C ₁₅ alkyl group, or a straight chain represents an aralkyl group in which the shaped or branched alkyl moiety is C ₈ to C ₂₄ ;
X ₁ ^- and X ₂ ^- preferably represent, independently of each other, an anion selected from phosphate, nitrate, sulfate and halide ions (Cl ^- , Br ^- , F ^- , I ^- ) .

According to a particular variant, the cationic cellulose ether that can be used in the composition according to the invention comprises at least one unit (IV) as defined above and at least one of the units (I), (II) or (III). in which R ₆ is a linear dodecyl group.

Among the cationic cellulose ethers that can be used in the compositions of the invention, polymers of the type Softcat SL-5, SL-30, SL-60 and SL-100 sold by the company Amerchol (INCI: Polyquaternium-67) can be mentioned. Particularly preferred cationic cellulose ethers are polymers of the SL-60 and SL-100 types.

(3) Cationic cellulose derivatives, such as cellulose copolymers and cellulose derivatives, such as those described in U.S. Pat. No. 4,131,576, grafted with water-soluble monomers of quaternary ammonium, such as methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and hydroxyalkylcelluloses grafted with salts selected from dimethyldiallylammonium salts, such as hydroxymethyl-, hydroxyethyl-, and hydroxypropylcelluloses.

Commercial products corresponding to these polymers include, for example, the products sold under the names "Celquat® L 200" and "Celquat® H 100" by the company National Starch.

(4) Noncellulosic cationic polysaccharides such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride as described in U.S. Pat. Nos. 3,589,578 and 4,031,307. Salts of 2,3-epoxypropyltrimethylammonium, such as chloride-modified guar gum (guar hydroxypropyltrimonium chloride), can also be used.

Such products are sold, for example, by the company MEYHALL under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17, and JAGUAR® C162.

(5) A divalent alkylene containing a piperazinyl unit and a straight or branched chain optionally interrupted by at least one member selected from oxygen, sulfur, nitrogen, aromatic rings, and heterocyclic rings. or hydroxyalkylene groups, as well as oxidation and/or quaternization products of these polymers. Such polymers are described, for example, in FR 2 162 025 and FR 2 280 361.

(6) Water-soluble polyaminoamides prepared, for example, by polycondensation of acidic compounds with polyamines; these polyaminoamides include epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; bis-unsaturated derivatives; bis-halohydrins; Reactive with members selected from bisazetidiniums; bishaloacyldiamines; bisalkyl halides; bishalohydrins, bisazetidiniums, bishaloacyldiamines, bisalkyl halides, epihalohydrins, diepoxides, and bis-unsaturated derivatives. They may be crosslinked with constituents selected from oligomers obtained by reaction of difunctional compounds, the crosslinking agent being used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; The polyaminoamides of may optionally be alkylated or, if they contain at least one tertiary amine function, quaternized. Such polymers are described, for example, in FR 2 252 840 and FR 2 368 508.

(7) Polyaminoamide derivatives obtained by condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents, e.g. Adipic acid/dialkylaminohydroxyalkyl dialkylene triamine polymers containing 4 carbon atoms and where the alkylene group, such as the ethylene group, contains 1 to 4 carbon atoms. Such polymers are described, for example, in FR 1583363. In at least one embodiment, these derivatives can be selected from adipic acid/dimethylaminohydroxypropyldiethylenetriamine polymers.

(8) A polyalkylene polyamine containing two primary amine groups and at least one secondary amine group is a dicarboxylic acid selected from diglycolic acid and a saturated aliphatic dicarboxylic acid containing from 3 to 8 carbon atoms. A polymer obtained by reacting with The molar ratio of polyalkylene polyamine to dicarboxylic acid may range from 0.8:1 to 1.4:1, whereby the resulting polyaminoamide is combined with epichlorohydrin and the second dicarboxylic acid of epichlorohydrin to polyaminoamide is used. The reaction is carried out at a molar ratio of primary amine groups ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in US Pat. Nos. 3,227,615 and 2,961,347.

(9) Cyclopolymers of alkyldiallylamines and cyclopolymers of dialkyldiallyl-ammoniums, such as those of formulas (Ia) and (Ib) as main constituents of the chain:

(In the formula,
k and t may be the same or different and equal to 0 or 1, the sum k+t is equal to 1,
R ₁₂ is selected from hydrogen and methyl groups,
R ₁₀ and R ₁₁ may be the same or different and may be an alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group contains, for example, 1 to 5 carbon atoms, and a lower ( selected from C ₁ -C ₄ ) amidoalkyl groups, or R ₁₀ and R ₁₁ may together with the nitrogen atom to which they are attached form a heterocyclic group, such as piperidinyl and morpholinyl;
Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, and phosphate)
Homopolymers and copolymers containing at least one unit selected from the following. These polymers are described, for example, in FR 2080759 and its supplementary patent FR 2190406.

In one embodiment, R ₁₀ and R ₁₁ may be the same or different and are selected from alkyl groups containing 1 to 4 carbon atoms.

Examples of such polymers include (co)polydiallyldialkylammonium chloride, such as the dimethyldiallyldiallylammonium chloride homopolymer sold under the name "MERQUAT® 100" by the company CALGON (and of low mass average molecular mass). homologs thereof), as well as a copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".

(10) Formula (II):

[In the formula,
R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ may be the same or different and include aliphatic, cycloaliphatic, and arylaliphatic groups containing 1 to 20 carbon atoms, and lower hydroxy selected from alkylaliphatic groups, or R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ together or separately with the nitrogen atom to which they are attached carry a second heteroatom other than nitrogen; Optionally, R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ may be the same or different and include a nitrile group, an ester group, an acyl group, an amide group, etc. group, -CO-OR ₁₇ -E group, and -CO-NH-R ₁₇ -E group, where R ₁₇ is an alkylene group and E is a quaternary ammonium group. selected from straight-chain or branched C ₁ -C ₆ alkyl groups substituted with at least one group;
A ₁ and B ₁ may be the same or different and are selected from polymethylene groups containing from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated. and at least one selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups, and ester groups. may include one construct linked or inserted into the main chain;
X ^- is an anion derived from an inorganic or organic acid,
A ₁ , R ₁₃ , and R ₁₅ may form a piperazine ring together with the two nitrogen atoms to which they are bonded,
When A ₁ is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B ₁ is
-(CH ₂ ) _n --CO-E'-OC-(CH ₂ ) _n -
can be selected from, where E' is
a) Formula -OZO-{where Z is a linear or branched hydrocarbon group and the following formula:
-(CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ -
-[CH ₂ -CH(CH ₃ )-O] _y -CH ₂ -CH(CH ₃ )-
(where x and y may be the same or different and are integers ranging from 1 to 4 representing a defined unique degree of polymerization, and numbers ranging from 1 to 4 representing the average degree of polymerization (selected from)
a glycol residue selected from the group };
b) bis-secondary diamine residues, such as piperazine derivatives,
c) Formula -NH-Y-NH- (wherein Y is selected from a linear or branched hydrocarbon group and a divalent group -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ - bis-primary diamine residues of
d) selected from ureylene groups of the formula -NH-CO-NH-]
A quaternary diammonium polymer containing at least one repeating unit of.

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

Polymers of this type are disclosed, for example, in French patents 2320330, 2270846, 2316271, 2336434 and 2413907 and in US patents 2,273,780, 2,375,853, 2,388,614, 2,454,547, No. 3,206,462, No. 2,261,002, No. 2,271,378, No. 3,874,870, No. 4,001,432, No. 3,929,990, No. 3,966,904, No. 4,005,193, No. 4,025,617, No. 4,025,627, No. 4,0 No. 25,653, No. 4,026,945, and No. Described in No. 4,027,020.

Non-limiting examples of such polymers include formula (III):

(wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, which may be the same or different, and X ^- is an anion derived from an inorganic or organic acid)
Included are those containing at least one repeating unit of.

(11) Formula (IV):

[In the formula,
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ may be the same or different and each represents hydrogen, methyl group, ethyl group, propyl group, β-hydroxyethyl group, β-hydroxypropyl group, -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH group, where p is selected from an integer ranging from 0 to 6, with the proviso that R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are , but not hydrogen at the same time.
r and s may be the same or different and are selected from integers ranging from 1 to 6;
q is selected from an integer ranging from 0 to 34,
X ^- is an anion, e.g. a halide ion;
A is selected from dihalide and _-CH2 - _CH2 -O- _CH2 - _CH2- group]
Polyquaternary ammonium polymer containing units of.

Such compounds are described, for example, in European Patent Application No. 0122324.

(12) Quaternary polymer of vinylpyrrolidone and vinylimidazole.

Other examples of suitable cationic polymers include cationic proteins and cationic protein hydrolysates, polyalkyleneimines such as polyethyleneimines, polymers containing units selected from vinylpyridine and vinylpyridinium units, polyamines and epichloromethane. These include, but are not limited to, condensates with hydrin, quaternary polyureylenes, and chitin derivatives.

According to one embodiment of the invention, the at least one cationic polymer is a cellulose ether derivative containing quaternary ammonium groups, such as the product sold under the name "JR 400" by the company UNION CARBIDE CORPORATION, cationic Cyclopolymers, such as homopolymers and copolymers of dimethyldiallylammonium chloride, 2,3-epoxypropyl, sold by the company CALGON under the names MERQUAT® 100, MERQUAT® 550, and MERQUAT® S selected from guar gum modified with trimethylammonium salts and quaternary polymers of vinylpyrrolidone and vinylimidazole.

(13) Polyamines As cationic polymers it is also possible to use (co)polyamines which have a plurality of amino groups and may be homopolymers or copolymers. The amino group may be a primary, secondary, tertiary or quaternary amino group. Amino groups may be present in the polymer backbone of the (co)polyamine or in pendant groups if present.

Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridine, such as ( co)poly-1-methyl-2-vinylpyridine, (co)polyimine, e.g. (co)polyethyleneimine, (co)polypyridine, e.g. (co)poly(quaternary pyridine), (co)polybiguanide, e.g. Mention may be made of co)polyaminopropyl biguanide, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof. can.

It is preferable to use (co)polylysine as the (co)polyamine. Polylysine is well known. Polylysine may be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine may be ε-poly-L-lysine, which is typically used as a natural preservative in foods. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water. Polylysine is commercially available in various forms such as poly-D-lysine and poly-L-lysine. Polylysine may be in salt and/or solution form.

(14) Cationic polyamino acids As cationic polymers it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers, having multiple amino and carboxyl groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. Amino groups may be present in the polymer backbone of the cationic polyamino acid or in pendant groups if present. Carboxyl groups may be present in pendant groups when a cationic polyamino acid is present.

Examples of cationic polyamino acids include cationized collagen, cationized gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, and steardimonium hydroxypropyl. Examples include hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, and cocodimonium hydroxypropyl hydrolyzed soy protein.

Cationic polymers include cyclopolymers of alkyldiallylamines and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine, cationic (co)polyamino acids, such as cationized It may be preferred to be selected from the group consisting of collagen, and salts thereof.

Preferably, the cationic polymer is a polyquaternium polymer or a polymeric quaternary ammonium salt.

Polymeric quaternary ammonium salts are cationic polymers containing at least one quaternized nitrogen atom. As polymeric quaternary ammonium salts, mention may be made in particular of polyquaternium products (CTFA name), which primarily contribute to the quality of the foam and the feel of the skin after use, especially the feel of the skin after use. These polymers can preferably be selected from the following polymers:
Polyquaternium-5, for example the product Merquat 5 sold by the company Nalco,
Polyquaternium-6, for example the product Salcare SC 30 sold by BASF and the product Merquat 100 sold by Nalco,
Polyquaternium-7, such as the products Merquat S, Merquat 2200, Merquat 7SPR and Merquat 550 sold by the company Nalco, and the product Salcare SC 10 sold by the company BASF,
Polyquaternium-10, for example the product Polymer JR400 sold by the company Amerchol,
Polyquaternium-11, such as the products Gafquat 755, Gafquat 755N and Gafquat 734 sold by ISP,
Polyquaternium-15, for example the product Rohagit KF 720 F, sold by the company Rohm,
Polyquaternium-16, such as the products Luviquat FC905, Luviquat FC370, Luviquat HM552 and Luviquat FC550 sold by BASF,
Polyquaternium-28, for example the product Styleze CC10 sold by ISP,
Polyquaternium-44, for example the product Luviquat Care, sold by BASF
Polyquaternium-46, for example the product Luviquat Hold, sold by BASF
Polyquaternium-47, such as the product Merquat 2001, sold by the company Nalco, and polyquaternium-67, such as the product Softcat, sold by the company Amerchol.

The amount of cationic polymer in the composition according to the invention can be at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight, relative to the total weight of the composition.

The amount of cationic polymer in the composition according to the invention can be up to 25% by weight, preferably up to 20% by weight, more preferably up to 15% by weight, relative to the total weight of the composition.

The amount of cationic polymer in the composition according to the invention is from 0.001% to 25% by weight, preferably from 0.01% to 20% by weight, more preferably from 0.1% to 15% by weight, relative to the total weight of the composition. %.

(Anionic polymer)
Anionic polymers have a positive charge density. When the anionic polymer is a synthetic anionic polymer, the charge density of the anionic polymer can be from 0.1meq/g to 20meq/g, preferably from 1 to 15meq/g, more preferably from 4 to 10meq/g. , when the anionic polymer is a natural anionic polymer, the average degree of substitution of the anionic polymer can be from 0.1 to 3.0, preferably from 0.2 to 2.7, more preferably from 0.3 to 2.5.

It may be preferable that the anionic polymer has a molecular weight of 1,000 or more, preferably 10,000 or more, more preferably 50,000 or more, and still more preferably 100,000 or more.

The anionic polymer has at least one selected from the group consisting of sulfate groups, sulfate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups, phosphate groups, phosphonic acid groups, phosphonate groups, carboxylic acid groups, and carboxylate groups. may have one negative charge and/or may have a portion with a negative charge.

Anionic polymers may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

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

Anionic polymers may include at least one hydrophobic chain.

The anionic polymer, which may contain at least one hydrophobic chain, is selected from carboxylic acids containing α,β-ethylenic unsaturation (monomer a') and 2-acrylamido-2-methylpropanesulfonic acid (monomer a'') (a) and a non-surface-active monomer (b) containing ethylenic unsaturation other than (a) and/or an acrylic monomer containing α,β-monoethylenically unsaturation or monoethylenically unsaturated. can be obtained by copolymerization with a monomer (c) containing ethylenic unsaturation obtained by reacting an isocyanate monomer containing with a monovalent nonionic amphiphilic component or with a primary or secondary fatty amine. can.

Therefore, anionic polymers with at least one hydrophobic chain can be synthesized by two synthetic routes, namely:
- Monomers (a') and (c), or (a'), (b) and (c), or (a") and (c), or a combination of (a"), (b) and (c) polymerization,
- or monomer (a'), or a copolymer formed from monomers (a') and (b), or (a") and (b), with a monovalent nonionic amphiphilic compound or a primary or It can be obtained either by modification (especially esterification or amidation) with secondary fatty amines.

As a 2-acrylamido-2-methylpropanesulfonate copolymer, in particular the paper "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, Vol. 33, No. 10, pp. 3694-3704" and applications EP-A-0750899 and EP-A-1069172.

The carboxylic acid containing α,β-monoethylenically unsaturated which constitutes the monomer (a') can be selected from a large number of acids, in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. This is preferably acrylic acid or methacrylic acid.

The copolymer can include a monomer (b) containing monoethylenically unsaturated without surfactant properties. Preferred monomers are those that, when homopolymerized, provide water-insoluble polymers. They can be selected, for example, from alkyl acrylates (C ₁ -C ₄ ) and alkyl methacrylates (C ₁ -C ₄ ), such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. More particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers that can be used are, for example, styrene, vinyltoluene, vinyl acetate, acrylonitrile and vinylidene chloride. Non-reactive monomers are preferred, those monomers in which a single ethylenic group is the only group that is reactive under the polymerization conditions. However, monomers containing groups that react under the action of heat, such as hydroxyethyl acrylate, can optionally be used.

Monomer (c) can be an acrylic monomer containing α,β-monoethylenically unsaturated, such as (a), or an isocyanate monomer containing monoethylenically unsaturated, a monovalent nonionic amphiphilic compound or a primary or secondary fatty amines.

Monovalent nonionic amphiphilic compounds or primary or secondary fatty amines used to produce nonionic monomers (c) are well known. Monovalent nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds containing an alkylene oxide that forms the hydrophilic portion of the molecule. Hydrophobic compounds are generally composed of aliphatic alcohols or alkylphenols, in which the carbonaceous chain containing at least 6 carbon atoms constitutes the hydrophobic part of the amphiphilic compound.

Preferred monovalent nonionic amphiphilic compounds have the following 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, and R' is selected from 1 to 4 carbon atoms. selected from alkyl groups containing carbon atoms, where n is an average number ranging from approximately 1 to 150, and m is an average number ranging from approximately 0 to 50, provided that n is at least equal to m. be)
It is a compound with

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

Preferred primary and secondary fatty amines are composed of one or two alkyl chains containing from 6 to 30 carbon atoms.

The monomers used to form the nonionic urethane monomer (c) can be selected from a wide variety of compounds. Any compound containing copolymerizable unsaturation, such as acrylic, methacrylic or allylic unsaturation, can be used. Monomer (c) can be obtained in particular from isocyanates containing monoethylenically unsaturated, such as especially α,α-dimethyl-m-isopropenylbenzyl isocyanate.

Monomers (c) are in particular oxyethylated (1 to 50 EO) acrylates, methacrylates or itaconates of C ₆ to C ₃₀ fatty alcohols, such as steareth-20 methacrylate, oxyethylated (25 EO) behenyl methacrylate, oxyethylated ( 20EO) monocetyl itaconate, oxyethylated (20EO) monostearyl itaconate or polyoxyethylated (25EO) C ₁₂ to C ₂₄ alcohol-modified acrylates, and oxyethylated (1 to 50EO) C ₆ to It can be chosen from dimethyl-m-isopropenylbenzyl isocyanate of C ₃₀ fatty alcohols, such as dimethyl-m-isopropenylbenzyl isocyanate, especially of oxyethylated behenyl alcohols.

According to certain embodiments of the invention, the anionic polymer comprises (a) a carboxylic acid containing α,β-ethylenically unsaturated; (b) a non-surface-active monomer containing ethylenic unsaturation other than (a). , and (c) acrylic terpolymers obtained from nonionic urethane monomers which are the reaction products of monovalent nonionic amphiphilic compounds and isocyanates containing monoethylenically unsaturated.

As anionic polymers containing at least one hydrophobic chain, in particular acrylic acid/ethyl acrylate/alkyl acrylate terpolymers, such as the product sold under the name Acusol 823 by Rohm & Haas as a 30% aqueous dispersion ;acrylate/methacrylic acid steareth-20 copolymers, e.g. the product sold under the name Aculyn 22 by Rohm &Haas; (meth)acrylic acid/ethyl acrylate/oxyethylenated (25EO) behenyl methacrylate terpolymers, e.g. Rohm & Products as aqueous emulsions sold by Haas under the name Aculyn 28; acrylic acid/oxyethylenized (20EO) monocetyl itaconate copolymers, such as 30% aqueous dispersions sold under the name Structure 3001 by National Starch. Products as acrylic acid/oxyethylenated (20EO) monostearyl itaconate copolymers, e.g. products as 30% aqueous dispersions sold under the name Structure 2001 by National Starch; acrylate/polyoxyethylated (25EO) Copolymers of acrylates modified with C ₁₂ -C ₂₄ alcohols, such as the 30-32% copolymer latex sold under the name Synthalen W2000 by the company 3V SA; or dimethyl-meth-acrylates of methacrylic acid/methyl acrylate/ethoxylated behenyl alcohols. Mention may be made of terpolymers of isopropenyl benzyl isocyanate, such as the product disclosed in document EP-A-0173109 as a 24% aqueous dispersion containing 40 ethylene oxide groups.

The anionic polymer may also be polyester-5, such as the product sold by EASTMAN CHEMICAL under the name Eastman AQ™ 55S Polymer, having the chemical formula below.

A: Dicarboxylic acid moiety
G: Glycol part
SO ₃ ^- Na ⁺ :Sodium sulfo group
OH: hydroxyl group

Anionic polymers include polysaccharides such as alginic acid, hyaluronic acid, and cellulose polymers (e.g. carboxymethyl cellulose), anionic (co)polyamino acids such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyglutamic acid, (co)poly(meth)acrylic acid, ) polyamic acid, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, (co)polyfumaric acid, maleic acid (co)polymer, and salts thereof. It may be preferable to select from the group consisting of:

The maleic acid copolymer comprises one or more maleic acid comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing from 2 to 20 carbon atoms, and styrene. But that's fine.

A "maleic acid copolymer" therefore refers to one or more maleic acid comonomers combined with vinyl acetate, vinyl alcohol, vinylpyrrolidone, an olefin containing from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene. , and styrene, the maleic acid comonomer being optionally partially or completely hydrolyzed. Preferably, hydrophilic polymers are used, ie polymers with a water solubility of 2 g/l or more.

In an advantageous embodiment of the invention, the maleic acid copolymer may have a molar fraction of maleic acid units between 0.1 and 1, more preferably between 0.4 and 0.9.

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

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

Preferably, a copolymer of styrene and maleic acid in a 50/50 ratio is used.

For example, a styrene/maleic acid (50/50) copolymer in the form of an ammonium salt at 30% in water sold under the reference SMA1000H® by Cray Valley or SMA1000HNa® by Cray Valley. Styrene/maleic acid (50/50) copolymer in the form of 40% sodium salt in water, sold at

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

The amount of anionic polymer in the composition according to the invention can be at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight, relative to the total weight of the composition.

The amount of anionic polymer in the composition according to the invention can be up to 25% by weight, preferably up to 20% by weight, more preferably up to 15% by weight, relative to the total weight of the composition.

The amount of anionic polymer in the composition according to the invention is from 0.001% to 25% by weight, preferably from 0.01% to 20% by weight, more preferably from 0.1% to 15% by weight, relative to the total weight of the composition. %.

(Ampholytic polymer)
Amphoteric polymers have both positive and negative charge densities.

The positive charge density of the amphoteric polymer can be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g, more preferably from 0.1 to 10 meq/g.

The negative charge density of the amphoteric polymer can be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g, more preferably from 0.1 to 10 meq/g.

It may be preferable that the molecular weight of the amphoteric polymer is 500 or more, preferably 1000 or more, more preferably 2000 or more, even more preferably 5000 or more.

Unless otherwise defined in the description, "molecular weight" means number average molecular weight.

Ampholytic polymers are
Has at least one positive charge selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. a moiety capable of and/or having a positive charge,
and at least one negative charge selected from the group consisting of a sulfate group, a sulfate group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, a phosphonic acid group, a phosphonate group, a carboxylic acid group, and a carboxylate group. and/or may have a portion with a negative charge.

Ampholytic polymers may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

Amphoteric polymers that can be used according to the invention can be selected from polymers containing K and M units randomly distributed in the polymer chain, where K represents at least one basic nitrogen atom. M represents a unit derived from an acidic monomer containing one or more carboxylic acid or sulfonic acid groups, or K and M represent a unit derived from a monomer containing carboxybetaine or sulfobetaine. It may also represent a group derived from a polar ionic monomer. K and M may also represent cationic polymer chains containing primary, secondary, tertiary or quaternary amine groups, at least one of which is linked via a hydrocarbon group. or K and M form part of a chain of a polymer having α,β-dicarboxylic ethylene units, one of the carboxylic acid groups being It has been reacted with a polyamine containing one or more primary or secondary amine groups.

More particularly preferred amphoteric polymers corresponding to the definition given above are selected from the following polymers:

(1) Monomers derived from vinyl compounds bearing carboxylic acid groups, such as more specifically acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and substituted vinyl compounds containing at least one basic atom. Polymers obtained by copolymerization with basic monomers derived from, for example, more particularly methacrylic acid and dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. Mention may also be made of the sodium acrylate/acrylamidopropyltrimethylammonium chloride copolymer sold under the name POLYQUART KE 3033 by the company HENKEL. The vinyl compound may also be a dialkyldiallylammonium salt, such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and the latter monomer are offered by the company Lubrizol under the names MERQUAT 280, MERQUAT 295, MERQUAT 2003 PR, MERQUAT 3330 PR and MERQUAT PLUS 3330.

(2) Polymers containing units derived from:
a) at least one monomer selected from acrylamide or methacrylamide in which nitrogen is substituted with an alkyl group;
b) at least one acidic comonomer containing one or more reactive carboxylic acid groups; and
c) at least one basic comonomer, such as esters of acrylic acid and methacrylic acid with primary, secondary, tertiary and quaternary amine substituents, and dimethyl sulfate or sulfuric acid of dimethylaminoethyl methacrylate; Quaternization product with diethyl.

Most particularly preferred N-substituted acrylamides or methacrylamides according to the invention are groups whose alkyl radicals contain from 2 to 12 carbon atoms, more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert- octylacrylamide, N-octylacrylamide, N-decylacrylamide, and N-dodecylacrylamide, and the corresponding methacrylamide.

Acidic comonomers are more particularly selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, and alkyl monoesters having 1 to 4 carbon atoms of maleic acid or fumaric acid or their anhydrides. selected.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl, and N-tert-butylaminoethyl methacrylate.

Particularly used are copolymers whose CTFA name (4th edition, 1991) is octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, such as the product sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.

(3) Partially or fully alkylated and crosslinked polyaminoamides derived from polyaminoamides of the general formula:
-[-CO-R ₄ -CO-Z-]-
[wherein R ₄ is a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid having an ethylenic double bond, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids, or any of the aforementioned acids 1 and a bis-primary or bis-secondary amine, and Z represents a bis-primary, mono- or bis-secondary polyalkylene. - indicates a polyamine group, preferably represents:
a) 60 to 100 mol% of the following groups:
-NH-[(CH ₂ ) _x -NH-] _p -
(where x=2 and p=2 or 3, or x=3 and p=2, and the group is derived from diethylenetriamine, triethylenetetraamine or dipropylenetriamine) ,
b) in proportions from 0 to 40 mol% of the group (IV) as defined above (where x=2 and p=1, which originates from ethylenediamine) or the following groups derived from piperazine:

c) -NH-(CH ₂ ) ₆ -NH- groups derived from hexamethylene diamine in proportions from 0 to 20 mol %, these polyaminoamines being selected from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives By adding a difunctional crosslinking agent, the polyaminoamide is crosslinked using 0.025 to 0.35 mol of crosslinking agent per amine group, and the alkyl ].

Saturated carboxylic acids are preferably acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid, and ethylene double Acids having a bond are selected from acids such as acrylic acid, methacrylic acid and itaconic acid.

The alkane sultone used in the alkylation is preferably propane or butane sultone, and the salt of the alkylating agent is preferably a sodium or potassium salt.

(4) Polymers containing zwitterionic units of the following formula:

(In the formula, R ₅ represents a polymerizable unsaturated group, such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R ₆ and R ₇ represent a hydrogen atom, represents methyl, ethyl or propyl, and R ₈ and R ₉ represent a hydrogen atom or an alkyl group such that the sum of carbon atoms in R ₈ and R ₉ does not exceed 10).

Polymers containing such units may also contain units derived from non-zwitterionic monomers, such as dimethyl or diethylaminoethyl acrylic acid or methacrylate or alkyl acrylic acid or methacrylates, acrylamide or methacrylamide or vinyl acetate. .

As an example, mention may be made of the copolymers of butyl methacrylate/dimethylcarboxymethylammonioethyl methacrylate, such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

(5) Polymers derived from chitosan containing monomer units corresponding to the following formulas (VI), (VII), and (VIII):

[(VI) units are present in a proportion of 0 to 30%, (VII) units are present in a proportion of 5 to 50%, (VIII) units are present in a proportion of 30 to 90%; In the unit (VIII), R ₁₀ is of the following formula:

(In the formula,
When q=0, R ₁₁ , R ₁₂ and R ₁₃ are the same or different and each represents a hydrogen atom, methyl, hydroxyl, acetoxy or amino residue, monoalkylamine residue or dialkylamine residue (1 optionally interrupted by one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic acid groups), or whose alkyl group is an amino residue represents an alkylthio residue having , in which at least one of the R ₁₁ , R ₁₂ and R ₁₃ groups is a hydrogen atom,
Alternatively, when q=1, R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom)
and the salts formed with these compounds with bases or acids].

(6) Polymers obtained by N-carboxyalkylation of chitosan, such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by JAN DEKKER.

(7) Polymers corresponding to general formula (IX), such as those described in French Patent No. 1,400,366:

[In the formula, R ₁₄ represents a hydrogen atom, CH ₃ O, CH ₃ CH ₂ O, or a phenyl group, R ₁₅ represents hydrogen or a lower alkyl group, such as methyl or ethyl, and R ₁₆ represents hydrogen or a lower represents an alkyl group, such as methyl or ethyl, R ₁₇ is a lower alkyl group, such as methyl or ethyl, or has the formula: -R ₁₈ -N(R ₁₆ ) ₂ (R ₁₈ is -CH ₂ -CH ₂ -, - CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH(CH ₃ )- group, R ₁₆ has the above-mentioned meaning);
and higher homologues of these groups containing up to 6 carbon atoms].

(8) -DXDX-type amphoteric polymer selected from:
a) Polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds containing at least one unit of the following formula:
-DXDXD- (X)
(In the formula, D is the following group

, X stands for the symbol E or E', E or E' being the same or different and indicating a divalent radical, which is a straight radical containing up to 7 carbon atoms in the main chain. an alkylene radical with a chain or a branch, unsubstituted or substituted with hydroxyl groups, in addition to oxygen, nitrogen or sulfur atoms, from 1 to 3 aromatic and/or heterocyclic rings and the oxygen, nitrogen and sulfur atoms may contain ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, or hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide , alcohol, ester and/or urethane groups).
b) Polymers of the following formula:
-DXDX- (XI)
(In the formula, D is the following group

, X represents the symbol E or E', at least once E', E has the meaning given above, and E' is a divalent radical, which can contain up to 7 A linear or branched alkylene group with carbon atoms in the main chain, unsubstituted or substituted with one or more hydroxyl groups, and containing one or more nitrogen atoms. , the nitrogen atom of which is substituted with an alkyl chain optionally interrupted by an oxygen atom, necessarily containing one or more carboxyl functions or one or more hydroxyl functions, chloroacetic acid or chloroacetic acid Betained by reaction with sodium).

(9) By semiamidation with N,N-dialkylaminoalkylamines such as N,N-dimethylaminopropylamine or by semiesterification with N,N-dialkanolamines. (C ₁ -C ₅ )alkyl vinyl ether/maleic anhydride copolymer modified by These copolymers may also contain other vinyl comonomers, such as vinyl caprolactam.

Particularly preferred amphoteric polymers according to the invention are those of family (1), especially those containing dialkyl diallylammonium salts as cationic monomers.

The amphoteric polymer can be selected from polyquaternium-22, polyquaternium-39, polyquaternium-53, polyquaternium-64, polyquaternium-51, polyquaternium-61 and mixtures thereof. More preferred are polyquaternium-39 and polyquaternium-53, such as the products Merquat 3330 PR and Merquat 2003 PR sold by the company Lubrizol.

The amount of amphoteric polymer in the composition according to the invention can be at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight, relative to the total weight of the composition.

The amount of amphoteric polymer in the composition according to the invention can be up to 25% by weight, preferably up to 20% by weight, more preferably up to 15% by weight, based on the total weight of the composition.

The amount of amphoteric polymer in the composition according to the invention is from 0.001% to 25% by weight, preferably from 0.01% to 20% by weight, more preferably from 0.1% to 15% by weight, relative to the total weight of the composition. can be.

(non-polymeric acids with acid dissociation constants of 2 or more)
The composition according to the invention may comprise at least one non-polymeric acid or a salt thereof having a pKa value of two or more, i.e. at least one non-polymeric acid or a salt thereof having an acid dissociation constant of two or more. good. pKa values (acid dissociation constants) are well known to those skilled in the art and should be determined at a constant temperature, for example 25°C.

Non-polymeric acids or salts thereof having pKa values of two or more can be incorporated into (a) the polyion complex. Non-polymeric acids with pKa values of two or more can function as crosslinkers for cationic or amphoteric polymers.

The term "non-polymeric" herein means that the acid is not obtained by polymerizing two or more monomers. Therefore, non-polymeric acids do not correspond to acids obtained by polymerizing two or more monomers, such as polycarboxylic acids.

The molecular weight of the non-polymeric acid or its salt having two or more pKa values is preferably 1000 or less, preferably 800 or less, more preferably 700 or less.

The type of non-polymeric acid or salt thereof having two or more pKa values is not limited. 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 acids or salts thereof having two or more pKa values or a combination of non-polymeric acids or salts thereof having two or more pKa values of different types can be used.

As used herein, the term "salt" refers to a salt formed by adding a suitable base to a non-polymeric acid having a pKa value of 2 or more, according to methods known to those skilled in the art. It can be obtained by reacting a non-polymeric acid with a base with a pKa value of 3 or more. As salts, mention may be made of 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 salt thereof having two or more pKa values can be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof.

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

A non-polymeric acid with a pKa value of two or more can be a non-polymeric polyacid.

Non-polymeric acids with pKa values of two or more can be selected from the group consisting of dicarboxylic acids, disulfonic acids, and diphosphonic acids, and mixtures thereof.

Non-polymeric acids or their salts with pKa values of 2 or more include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid Acids, citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and their salts; aspartic acid, glutamic acid, and their salts; terephthalylidene dicamphorsulfonic acid or its salts (Mexoryl SX), benzophenone-9; phytic acid, and its salts Salt; Red No. 2 (Amaranth), Red No. 102 (New Coccin), Yellow No. 4 (Yellow 5) (Tartrazine), Yellow No. 5 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue 1 No. (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Red No. 201 (Rysole Rubin B), Red No. 202 (Rysole Rubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Rysole Red CA), Red No. 207 (Resol Red BA), Red No. 208 (Resol Red SR), Red No. 219 (Brilliant Lake Red R), Red No. 220 (Deep Maroon), Red No. 227 (Fast Acid Magenta), Yellow No. 203 (Quinoline Yellow) WS), Green No. 201 (Alizarin Cyanine Green F), Green No. 204 (Pyranine Conch), Green No. 205 (Light Green SF Yellow), Blue No. 203 (Patent Blue CA), Blue No. 205 (Alphazurin FG), Red No. 401 (Violamine R), Red No. 405 (Permanent Red F5R), Red No. 502 (Ponceau 3R), Red No. 503 (Ponceau R), Red No. 504 (Ponceau SX), Green No. 401 (Naphthol Green B), Green No. 402 (Guinea Green B), and black No. 401 (naphthol blue black); folic acid, ascorbic acid, erythorbic acid, and their salts; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts; and mixtures thereof. It can be selected from the following group.

Non-polymeric acids or salts thereof having pKa values of two or more include terephthalylidene dicamphorsulfonic acid and its salts (Mexoryl SX), Yellow No. 5 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salts, and mixtures thereof.

The amount of non-polymeric acid or its salt having two or more pKa values in the composition according to the invention is at least 0.001% by weight, preferably at least 0.01% by weight, more preferably 0.1% by weight, based on the total weight of the composition. % by mass or more.

The amount of non-polymeric acids or salts thereof having two or more pKa values in the composition according to the invention is not more than 10% by weight, preferably not more than 5% by weight, more preferably not more than 1% by weight, based on the total weight of the composition. % by mass or less.

The amount of non-polymeric acids or salts thereof having two or more pKa values in the composition according to the invention is from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, relative to the total weight of the composition. %, more preferably from 0.1% to 1% by weight.

(non-polymeric bases with base dissociation constants of 2 or more)
The composition according to the invention may comprise at least one non-polymeric base or salt thereof having a pKb value of two or more, i.e. at least one non-polymeric base or salt thereof having a base dissociation constant of two or more. good. pKb values (base dissociation constants) are well known to those skilled in the art and should be determined at a constant temperature, for example 25°C.

A non-polymeric base or salt thereof having a pKb value of more than one can be incorporated into (a) the particles. Non-polymeric bases with pKb values of two or more can function as crosslinkers for anionic or amphoteric polymers.

The term "non-polymeric" herein means that the base is not obtained by polymerizing two or more monomers. Therefore, a non-polymeric base does not correspond to a base obtained by polymerizing two or more monomers, such as polyallylamine.

The molecular weight of the non-polymeric base or its salt having two or more pKb values is preferably 1000 or less, preferably 800 or less, more preferably 700 or less.

The type of non-polymeric base or salt thereof having two or more pKb values is not limited. Two or more different types of non-polymeric bases or salts thereof having two or more pKb values may be used in combination. Thus, a combination of non-polymeric bases or salts thereof having two or more pKb values of a single type or non-polymeric bases or salts thereof having two or more pKb values of different types can be used.

As used herein, the term "salt" refers to a salt formed by adding a suitable acid to a non-polymeric base having a pKb value of 2 or more, according to methods known to those skilled in the art. It can be obtained by reacting an acid with a non-polymeric base having a pKb value of 1 or more. As salts, mention may be made of ammonium salts, for example salts with inorganic acids such as HCl and _HNO3 , and salts with organic acids such as carboxylic acids and sulfonic acids.

The non-polymeric base or salt thereof having two or more pKb values can be an organic base or salt thereof, preferably a hydrophilic or water-soluble organic base or salt thereof.

Non-polymeric bases with pKb values of two or more have at least two basic groups selected from the group consisting of amino groups, guanidine groups, biguanide groups, imidazole groups, imino groups, pyridyl groups and mixtures thereof. It's okay.

Non-polymeric bases with pKb values of 2 or more include non-polymeric diamines such as ethylene diamine, propylene diamine, pentanediamine, hexane diamine, urea and its derivatives and guanidine and its derivatives, non-polymeric polyamines such as spermine and spermidine, basic Can be selected from the group consisting of amino acids, as well as mixtures thereof.

The non-polymeric base or salt thereof having two or more pKb values can be selected from the group consisting of arginine, lysine, histidine, cysteine, cystine, tyrosine, tryptophan, ornithine, and mixtures thereof.

It may be preferred that the non-polymeric base or salt thereof having two or more pKb values is selected from the group consisting of arginine, lysine, histidine, and mixtures thereof.

The amount of non-polymeric base or salt thereof having two or more pKb values in the composition according to the invention is at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight, relative to the total weight of the composition. % by mass or more.

The amount of non-polymeric base or salt thereof having two or more pKb values in the composition according to the invention is not more than 10% by weight, preferably not more than 5% by weight, more preferably not more than 1% by weight, relative to the total weight of the composition. % by mass or less.

The amount of non-polymeric base or salt thereof having two or more pKb values in the composition according to the invention is from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, relative to the total weight of the composition. %, more preferably from 0.1% to 1% by weight.

[Organic UV filter]
The composition according to the invention comprises (b) at least one organic UV filter. When using two or more types of (b) organic UV filters, they may be the same or different.

(b) Organic UV filters may be hydrophobic or water-insoluble. (b) Organic UV filters can function as oil-based components. Therefore, (b) the organic UV filter can form the continuous or external phase of the W/O composition according to the invention.

(b) The organic UV filter may be active in the UV-A and/or UV-B region. (b) Organic UV filters may be lipophilic or oil-soluble.

(b) Organic UV filters may be solid or liquid. The terms "solid" and "liquid" refer to solid and liquid, respectively, at 1 atm and 25°C.

(b) Organic UV filters include anthranilic acid compounds; dibenzoylmethane compounds; cinnamic acid compounds; salicylic acid compounds; camphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate Compounds; benzimidazole compounds; imidazoline compounds; bis-benzazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; shielding polymers and shielding silicones; derived from α-alkylstyrenes dimer; 4,4-diarylbutadiene compounds; guaiazulene and its derivatives; rutin and its derivatives; and mixtures thereof.

(b) As examples of organic UV filters, mention may be made of those indicated below by their INCI names, and mixtures thereof.
- Anthranilic acid compound: Menthyl anthranilate, sold under the trademark "Neo Heliopan MA" by Haarmann and Reimer.
- Dibenzoylmethane compounds: in particular butylmethoxydibenzoylmethane, sold under the trademark "Parsol 1789" by the company Hoffmann-La Roche; and isopropyldibenzoylmethane.
- Cinnamic acid compounds: ethylhexyl methoxycinnamate, especially marketed under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; marketed under the trademark "Neo" by Haarmann and Reimer; Cinoxate (2-ethoxyethyl-4-methoxycinnamate); DEA methoxycinnamate; diisopropyl methyl cinnamate; and glyceryl ethylhexanoate dimethoxycinnamate, commercially available as ``Heliopan E 1000''.
- Salicylic acid compounds: Homosalate (homomenthyl salicylate), sold under the trademark "Eusolex HMS" by Rona/EM Industries; Ethylhexyl salicylate, sold under the trademark "Neo Heliopan OS" by Haarmann and Reimer; Glycol salicylate; Butyl salicylate octyl; phenyl salicylate; dipropylene glycol salicylate, sold under the trademark "Dipsal" by Scher; and TEA salicylate, sold under the trademark "Neo Heliopan TS" by Haarmann and Reimer.
- Camphor compounds, in particular benzylidenecamphor derivatives: 3-benzylidenecamphor manufactured by Chimex under the trademark "Mexoryl SD"; 4-methylbenzylidenecamphor marketed by Merck under the trademark "Eusolex 6300"; trademark by Chimex benzylidene camphor sulfonic acid manufactured by “Mexoryl SL”; camphorbenzalkonium methosulfate manufactured by Chimex under the trademark “Mexoryl SO”; and polyamide manufactured by Chimex under the trademark “Mexoryl SW”. Acrylamidomethylbenzylidene camphor.
- Benzophenone compounds: Benzophenone-1 (2,4-dihydroxybenzophenone), marketed by BASF under the trademark "Uvinul 400"; Benzophenone-2 (tetrahydroxybenzophenone), marketed by BASF under the trademark "Uvinul D50" benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone, marketed by BASF under the trade mark "Uvinul M40"; benzophenone-4 (hydroxymethoxybenzophenone), marketed by BASF under the trade mark "Uvinul MS40"; benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxydimethoxybenzophenone) sold under the trademark "Helisorb 11" by Norquay; under the trademark "Spectra-Sorb UV-24" by American Cyanamid. benzophenone-9 (disodium dihydroxydimethoxybenzophenone disulfonate), sold under the trademark "Uvinul DS-49" by BASF; benzophenone-12, and n-hexyl 2-(4 -diethylamino-2-hydroxybenzoyl)benzoate (UVINUL A+ by BASF).
- β,β-diphenylacrylate compounds: octocrylene, especially marketed by BASF under the trademark "Uvinul N539"; and ethocrylene, especially marketed by BASF under the trademark "Uvinul N35".
- Triazine compounds: diethylhexylbutamide triazone, marketed under the trademark "Uvasorb HEB" by the company Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, CIBA GEIGY Bis-ethylhexyloxyphenolmethoxyphenyltriazine, sold under the trademark "TINOSORB S" by BASF, and ethylhexyltriazine, sold under the trademark "UVINUL T150" by BASF.
- benzotriazole compounds, especially phenylbenzotriazole derivatives: branched and linear 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylpheno; and those described in USP 5240975.
- benzalmalonate compounds: 4'-methoxybenzalmalonate dineopentyl and polyorganosiloxanes containing benzalmalonate functional groups, such as polysilicone-15, sold under the trademark "Parsol SLX" by Hoffmann-LaRoche; .
- Benzimidazole compounds, especially phenylbenzimidazole derivatives.
- Imidazoline compound: dimethoxybenzylidene dioxoimidazoline ethylhexyl propionate.
- Bis-benzazolyl compounds: derivatives described in EP-669,323 and US Pat. No. 2,463,264.
- Para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid), ethyl PABA, ethyl dihydroxypropyl PABA, dimethyl PABA pentyl, dimethyl PABA ethylhexyl, especially marketed under the trademark "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA sold under the trademark "Uvinul P25" by BASF.
- methylenebis-(hydroxyphenylbenzotriazole) compounds, such as 2,2'-methylenebis[6-(2H-benzotriazol-2-yl), which is sold in solid form by Fairmount Chemical under the trademark "Mixxim BB/200" -4-Methyl-phenol], 2,2'-methylene bis, commercially available in micronized form in an aqueous dispersion under the trademark "Tinosorb M" by BASF or under the trademark "Mixxim BB/100" by Fairmount Chemical. [6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and U.S. Patent Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-19,726,184 and the derivatives described in EP-893,119, as well as the drometrizole trisiloxanes marketed under the trademark "Silatrizole" by the company Rhodia Chimie or under the trademark "Mexoryl XL" by the company L'Oreal, as shown below.

- Benzoxazole compound: 2,4-bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2- ethylhexyl)imino-1,3,5-triazine.
- Shielding polymers and shielding silicones: silicones as described in WO 93/04665.
- Dimers derived from α-alkylstyrenes: dimers described in DE-19855649.
- 4,4-diarylbutadiene compound: 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

(b) The organic UV filter is preferably selected from the group consisting of:
Butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, 1, 1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone, 4-methylbenzylidenecamphor, ethylhexyltriazone, bis-ethylhexyloxyphenol Methoxyphenyltriazine, diethylhexylbutamide triazone, 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4'-aminobenzalmalonate) nate)-s-triazine, 2,4-bis-(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyl oxy]disiloxanyl}propyl)amino]-s-triazine, 2,4,6-tris-(diphenyl)-triazine, 2,4,6-tris-(terphenyl)-triazine, methylenebis-benzotriazolyltetramethyl Butylphenol, Drometrizole trisiloxane, Polysilicone-15, Dineopentyl 4'-methoxybenzalmalonate, 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4- Bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, camphorbenzalkonium methosulfate and the like A mixture of.

The amount of (b) organic UV filter in the composition according to the invention can be at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, relative to the total weight of the composition. .

The amount of (b) organic UV filter in the composition according to the invention can be up to 60% by weight, preferably up to 50% by weight, more preferably up to 40% by weight, relative to the total weight of the composition. .

The amount of (b) organic UV filter in the composition according to the invention is from 10% to 60% by weight, preferably from 20% to 50% by weight, more preferably 30% by weight, relative to the total weight of the composition. to 40% by mass.

[SPF improver]
The composition according to the invention comprises (c) at least one SPF enhancer. When using two or more types of (c) SPF improvers, they may be the same or different.

The term "SPF enhancer" means a compound or composition that, when used in a formulation with a UV screening agent, increases the SPF value of the formulation without increasing the amount of UV screening agent in the formulation. do.

(c) The SPF improver is preferably in the form of particles, more preferably spherical particles.

(c) Preferred examples of SPF improvers are hollow particles, especially hollow latex particles.

Hollow latex particles according to the invention may have a particle size generally in the range from 100 to 380 nm, preferably from 150 to 375 nm, more preferably from 190 to 350 nm, more particularly from 251 to 325 nm, the particle size being similar to Brookhaven BI Volume average particle size measured by -90 photon correlation spectrometer.

For a given particle size, hollow latex particles according to the invention generally have a maximum hollowness fraction. The hollow latex particles preferably contain a hollowness of 0.1% to 50%, more preferably 5% to 50%. Hollowness is determined by comparing the volume occupied by latex particles after centrifugation from a diluted dispersion to the volume of void-free particles in the same composition.

Hollow latex particles according to the invention can be obtained from particles comprising at least one polymer for the core and at least one polymer for the shell. The core and shell polymers can be obtained from a single polymerization step or a series of polymerization steps.

Typically, hollow latex particles are provided as part of an aqueous dispersion, generally stabilized with at least one emulsifier.

Hollow latex particles according to the invention can be prepared by conventional emulsion polymerization techniques. Such methods are described, inter alia, in the patents US 4,427,836, US 4,469,825, US 4,594,363, US 4,677,003, US 4,920,160 and US 4,970,241, or in the following patents and patent applications: EP267726, EP331421, US 490,229 and US 5,157,084 by conventional polymerization techniques.

The monomers used in the shell of the latex particles are preferably composed of one or more unsaturated nonionic ethylene units. Optionally, one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group may be polymerized in the shell.

The monomers that make up the shell are selected to exhibit a glass transition temperature (Tg) high enough to withstand the voiding of the hollow latex particles. Preferably, the glass transition temperature is above 50°C, more preferably above 60°C, even more preferably above 70°C. This temperature Tg can be determined by DSC (differential scanning calorimetry).

The monomers used in the emulsion polymerization of the core polymer of the latex particles of the invention are preferably composed of one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the core comprises at least 5% by weight of monoethylenically unsaturated monomers containing at least one carboxylic acid group, relative to the total weight of the core monomers.

The core polymer can be prepared, for example, by emulsion homopolymerization of monoethylenically unsaturated monomers containing at least one acid group or by copolymerization of two or three monoethylenically unsaturated monomers containing at least one acid group. It can be obtained by Preferably, the monoethylenically unsaturated monomer containing at least one acid group is copolymerized with one or more ethylenically unsaturated nonionic monomers.

The core or shell polymer comprises from 0.1% to 20% by weight, preferably from 0.1% to 3% by weight, relative to the total weight of the core monomers, of polyethylenically unsaturated monomers, such as ethylene glycol di(meth)acrylate. , allyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or divinylbenzene. Alternatively, the core or shell polymer may optionally contain from 0.1% to 60% by weight of butadiene, based on the total weight of the core monomers.

Monoethylenically unsaturated monomers containing at least one carboxylic acid group include, for example, acrylic acid, methacrylic acid, acryloyloxypropionic acid, (meth)acryloyloxypropionic acid, itaconic acid, aconitic acid, maleic acid or maleic anhydride. Acids include fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate.

In one embodiment, the monomer is selected from acrylic acid and methacrylic acid.

Monoethylenically unsaturated nonionic monomers include, for example, styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, C ₁ -C ₂₀ alkyl esters of (meth)acrylic acid, and (C ₃ -C ₂₀ ) alkenyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Includes benzyl acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate. According to the invention, the term (meth)acrylic denotes a general expression encompassing both methacrylic or acrylic. The term (meth)acrylate refers to a general expression encompassing both methacrylates or acrylates.

The void portion of the core of the latex particle is preferably created by swelling the core with a swelling agent comprising one or more volatile compounds. The swelling agent permeates the shell to swell the core. The volatile components of the swelling agent can then be removed by drying the latex particles, thus creating voids within the particles. The swelling agent is preferably an aqueous system. Mention may be made, for example, of ammonia, ammonium hydroxide, alkali metal hydroxides such as sodium hydroxide, and volatile amines such as trimethylamine or triethylamine.

Hollow latex particles may be incorporated into the compositions of the invention along with swelling agents. In that case, volatile compounds are removed when drying the composition. Hollow latex particles may also be added to the composition after the volatile compounds of the swelling agent have been removed.

Hollow latex particles that can be used according to the invention are those described in patent US 5,663,213 and patent application EP 1092421.

According to one particular embodiment of the invention, the hollow latex particles used are under the INCI name styrene/acrylate copolymer, a copolymer of styrene and (meth)acrylic acid or one of its C ₁ -C ₂₀ alkyl esters. such as the product sold under the trade name Sunspheres(TM) Powder by Rohm & Haas, which consists of 11% PEG-8 laurate, 2.5% water, and 0.5% dodecyl. It is an aqueous dispersion containing 86% styrene/acrylate copolymer in a mixture of sodium benzenesulfonate.

Another example of an SPF enhancer that can typically reflect UV light is glass microspheres. Typically, the glass microspheres used in the compositions of the present invention are essentially homogeneous, with essentially uniform sphericity, between about 5 μm and 70 μm, such as between about 10 μm and 20 μm. It has an average particle size of Glass microspheres useful in the present invention include hollow calcium aluminum borosilicate microspheres (commercially available from Presperse Inc. under the trade name LUXSIL®), sodium borosilicate microspheres (available from PQ Corporation under the trade name Q-CEL 570), as well as calcium/sodium borosilicate hollow microspheres (commercially available from 3M under the trade names ES 22 and 1K), calcium/sodium borosilicate microspheres (commercially available from 3M under the trade names ES 22 and 1K), Scotchlite™ K ₂₀ products).

(c) Another preferred example of an SPF improver is porous silica in the form of microparticles, especially spherical microparticles. The spherical microparticles of porous silica according to the invention preferably have an average particle size in the range from 0.5 to 20 μm, more particularly from 3 to 15 μm.

They preferably have a specific surface area ranging from 50 to 1000 m ² /g, more particularly from 150 to 800 m ² /g.

They preferably have a specific pore volume in the range from 0.5 to 5 ml/g, more particularly from 1 to 2 ml/g.

As examples of porous silica microbeads, the following commercial products can be used:
Silica Beads SB 150 manufactured by Miyoshi Kasei Co., Ltd.
Sunsphere H-51 manufactured by Asahi Glass Co., Ltd.
Sunsil 130 manufactured by Sunjin,
Spherica P-1500 manufactured by Ikeda Bussan Co., Ltd. and Sylosphere manufactured by Fuji Silicia Chemical Co., Ltd.

(c) Another preferred example of an SPF improver is silica particles containing metal oxides, such as titanium dioxide and zinc oxide (silica particles containing metal oxides). Silica particles may be porous or non-porous. The silica particles may be surface-treated to become hydrophobic. For example, silica particles may be surface-treated with an alkylsilane. The metal oxide may be in the form of nanoparticles and may have an average particle size ranging from 10 to 70 nm, preferably from 10 to 50 nm, more preferably from 10 to 30 nm. The silica particles comprising metal oxides may have an average particle size ranging from 0.1 to 30 μm, preferably from 0.5 to 20 μm, more preferably from 1 to 10 μm. Examples of silica particles containing metal oxides include Sunsil Tin40, Sunsil Tin40-AS, Sunsil Tin50, Sunsil-Tin50-As, and Sunsil-TZin50-As (manufactured by Sunjin).

(c) Another preferred example of the SPF improver is multilayer spherical composite particles.

Multilayer spherical composite particles are
i) a core comprising at least one material A having a refractive index in the range from 1.3 to 1.8;
ii) at least one layer covering said core comprising at least one material B having a refractive index in the range from 1.9 to 3.1;
iii) optionally at least one second layer covering material B comprising at least one material C having a refractive index in the range of 1.3 to 1.8.

Multilayer spherical composite particles are
i) a core comprising at least one material A having a refractive index in the range from 1.3 to 1.8;
ii) at least one layer covering said core comprising at least one material B having a refractive index in the range from 1.9 to 3.1;
iii) at least one second layer covering material B comprising at least one material C having a refractive index in the range from 1.3 to 1.8.

The various layers of the multilayer spherical composite particle may be approximately concentric.

The multilayer spherical composite particles may preferably be characterized by an average diameter in the range from 0.05 to 45 μm, more preferentially in the range from 0.05 to 10 μm, even more preferably in the range from 0.05 to 1 μm.

Materials A, B and C may consist of organic and/or inorganic substances.

Organic materials A and C with a refractive index of 1.3 to 1.8 are poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylene, polypropylene, polystyrene, polycaprolactam, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters and polyethers. , as well as mixtures thereof.

Inorganic materials A and C with a refractive index of 1.3 to 1.8 can be selected from the group formed by glass, silica, calcium carbonate and aluminum oxide, and mixtures thereof.

More specifically, silica is used for materials A and C.

The inorganic material B with a refractive index of 1.9 to 3.1 can be selected from metal oxides.

The metal oxide is preferably selected from oxides of titanium, zinc, iron and zirconium, or mixtures thereof, more particularly titanium dioxide and zinc oxide, and mixtures thereof.

Particularly preferably titanium dioxide (TiO ₂ ) is used. In particular, titanium dioxide (TiO ₂ ) may be in rutile and/or anatase form and/or in amorphous form.

These metal oxides may be in the form of particles, generally having an average elementary particle size of between 0.01 and 0.20 μm. Advantageously, the metal oxide particles used have an average particle size of less than 0.10 μm, even better between 0.01 and 0.1 μm, more particularly between 0.015 and 0.05 μm.

According to one particular form of the invention, the multilayer spherical composite particles are
i) a core made of silica;
ii) at least one layer of titanium dioxide covering said core;
iii) at least one second layer of silica covering the titanium dioxide layer.

Preferentially, the core based on material A represents from 1% to 99% by weight, more preferentially from 10% to 95% by weight, relative to the total weight of the spherical composite particles.

Preferentially, the layer based on material B represents from 0.5% to 50% by weight, more preferentially from 1% to 40% by weight, relative to the total weight of the spherical composite particles.

Preferentially, the layer based on material C represents from 0.5% to 50% by weight, more preferentially from 1% to 40% by weight, relative to the total weight of the spherical composite particles.

Among the multilayer spherical composite particles that can be used according to the invention, more particularly a silica core of 82% by weight, a first layer of titanium dioxide of 5% by weight and a second layer of 13% by weight of silica. Multilayer spherical composite particles having an average diameter of 0.6 μm are used, such as the product supplied by JGC Catalysts & Chemicals Co., Ltd. and sold under the trade name STM ACS-0050510.

Multilayer spherical composite particles that can be used according to the invention are known per se. Its definition and the method for its preparation are described in patent JP 3605118.

They can be obtained according to a method of preparation comprising the following steps. In the first step, hydrolysis of alkoxysilane (ie monomethyltriethoxysilane) in ethanol solution is carried out in the presence of aqueous ammonia with stirring, followed by calcination to obtain spherical silica particles. A metal hydrolyzate (i.e., titanium hydrolyzate) is prepared using an alcoholic solution of a metal oxide alkoxide (i.e., a solution of titanium isopropoxide in isopropanol) under stirring in a nitrogen medium, and then After filtration and rinsing, the resulting powder is heated at 300° C. for 4 hours and allowed to cool to room temperature. The resulting hydrolyzate is adhered to the surface of spherical silica particles in the presence of alcohol to obtain the first layer of metal oxide inner coating of the composite particles. After filtration and rinsing, the resulting powder is heated at 300° C. for 4 hours and allowed to cool to room temperature. The powder thus coated is then contacted with an ethanolic solution of an alkoxysilane (ie tetraethoxysilane) in the presence of hydrochloric acid with stirring for 24 hours. A second outer layer of silica is thus formed and then optionally subsequently calcined.

(c) SPF improvers consist of (co)polymers of (meth)acrylic acid, (meth)acrylates and/or styrene; glass; silica; metal oxides such as titanium dioxide and zinc oxide; and mixtures thereof. Preferably, it is made from at least one material selected from the group. As (co)polymers of (meth)acrylic acid, (meth)acrylates and/or styrene, poly(meth)acrylates such as PMMA, copolymers of (meth)acrylic acid and (meth)acrylates, and (meth)acrylic acid , (meth)acrylates, and copolymers of styrene. However, (c) SPF improvers are preferably made from inorganic materials such as silica and metal oxides (eg titanium dioxide and zinc oxide).

(c) The SPF improver is more preferably selected from the group consisting of hollow particles, silica particles containing metal oxides, multilayer spherical composite particles, and mixtures thereof.

(c) The SPF enhancer comprises a multilayer spherical composite particle, in particular a silica core particle, at least one first layer comprising titanium dioxide covering said core particle, and at least one second layer comprising silica covering said first layer. It is more preferable that the layer is selected from the group consisting of the following layers.

The amount of (c) SPF improver in the composition according to the invention can be at least 0.1% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight, relative to the total weight of the composition. .

The amount of (c) SPF improver in the composition according to the invention can be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, relative to the total weight of the composition. .

The amount of (c) SPF improver in the composition according to the invention is from 0.1% to 15% by weight, preferably from 0.5% to 10% by weight, more preferably 1% by weight, relative to the total weight of the composition. to 5% by mass.

In the compositions of the present invention, (c) the SPF improver can be used in an amount equal to or less than the amount of (b) organic UV filter present in the composition.

Typically, the ratio of (c) SPF enhancer to (b) organic UV filter is within the range of about 1: about 1 to about 1: about 20, such as about 1: about 1 to about 1: about 10. It is.

[water]
The composition according to the invention comprises (d) water.

(d) Water can form the discontinuous or dispersed (internal) phase of the W/O composition according to the invention.

(d) The amount of water can be 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the composition.

(d) The amount of water can be 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, based on the total weight of the composition.

(d) The amount of water can be from 1% to 50% by weight, preferably from 10% to 40% by weight, more preferably from 20% to 30% by weight, relative to the total weight of the composition. .

[Additional oil]
The composition according to the invention may comprise (e) at least one additional oil. If two or more (e) additional oils are used, they may be the same or different. (e) Additional oil is different from (b) organic UV filter.

As used herein, "oil" means a fatty compound or substance that is in liquid or paste (non-solid) form at room temperature (25° C.) under atmospheric pressure (760 mmHg). As the oil, those commonly used in cosmetics can be used alone or in combination. These oils may be volatile or non-volatile.

The oil can be a non-polar oil, such as a hydrocarbon oil, a silicone oil, etc.; a polar oil, such as vegetable or animal oils and ester or ether oils; or mixtures thereof.

The oil can be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

Examples of vegetable oils include, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, Mention may be made of sesame oil, soybean oil, peanut oil, and mixtures thereof.

As examples of animal oils, mention may be made, for example, of squalene and squalane.

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

The ester oil preferably contains a saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono- or polyacid and a saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyacid. It is a liquid ester with _{a 1} to C ₂₆ aliphatic monoalcohol or polyalcohol, and the total number of carbon atoms in the ester is 10 or more.

Preferably, for esters of monoalcohols, 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, ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates, such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate. , isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C ₄ -C ₂₂ dicarboxylic acids or tricarboxylic acids with C ₁ -C ₂₂ alcohols, and monocarboxylic acids, dicarboxylic acids or tricarboxylic acids with non-sugar C ₄ -C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols Esters with can also be used.

Among others, the following may be mentioned: diethyl sebacate, lauroylsarcosine isopropyl, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate. 2-ethylhexyl), diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, citric acid Trioleyl acid, neopentyl glycol diheptanoate, diethylene glycol diisononanoate.

As ester oils it is possible to use sugar esters and diesters of C ₆ to C ₃₀ , preferably C ₁₂ to C ₂₂ fatty acids. The term "sugar" may mean an oxygen-bearing hydrocarbon-based compound containing at least 4 carbon atoms, with or without aldehyde or ketone functionality, and containing some alcohol functionality. be recalled. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives. , such as methylglucose.

Sugar esters of fatty acids are in particular esters or mixtures of esters of the sugars mentioned above with linear or branched, saturated or unsaturated C ₆ -C ₃₀ , preferably C ₁₂ -C ₂₂ fatty acids. Can be selected from the group including. If they are unsaturated, these compounds may have 1 to 3 conjugated or nonconjugated carbon-carbon double bonds.

Esters according to this variant can also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters are, for example, oleates, laurates, palmitates, myristates, behenates, coconut fatty acid esters, stearates, linoleates, linolenates, caprates and arachidonic esters. , or mixtures thereof, such as mixed esters of oleopalmitic acid, oleostearic acid and palmitostearic acid, and pentaerythrityl tetraethylhexanoate, among others.

More particularly, monoesters and diesters, especially mono- or dioleates of sucrose, glucose or methylglucose, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates. Esters are used.

An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is methylglucose dioleate.

Examples of preferred ester oils include, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octoate, octyldodecyl octoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexanoate. -Ethylhexyl, 2-ethylhexyl octoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroylsarcosine, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, laurine Hexyl acid, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate , and mixtures thereof.

Examples of artificial triglycerides include, for example, caprylic caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, tri(capric/caprylic)glyceride, and Mention may be made of tri(capric/caprylic/linolenic) glyceryl.

Examples of silicone oils include, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc.; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethyl Mention may be made of cyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.; and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes containing at least one aryl group.

These silicone oils may also be organically modified. Organomodified silicones that can be used according to the invention are silicone oils as defined above and contain in their structure one or more organic functional groups bonded via hydrocarbon groups.

Organopolysiloxanes are defined in more detail in Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile.

If they are volatile, the silicones are more particularly selected from those having a boiling point between 60°C and 260°C, more particularly:
(i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5 silicon atoms. These are, for example, the octamethylcyclotetrasiloxane sold under the name Volatile Silicone® 7207 by the company Union Carbide or under the name Silbione® 70045 V2 by the company Rhodia, the name Volatile Silicone (by Union Carbide) 7158, sold under the name Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane, sold under the name Silsoft 1217 by Momentive Performance Materials; It is a mixture of The following formula:

Mention may also be made of cyclocopolymers of the type dimethylsiloxane/methylalkylsiloxane, for example Silicone Volatile® FZ 3109 sold by Union Carbide. Mixtures of cyclic polydialkylsiloxanes and organosilicon compounds, such as mixtures of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and octamethylcyclotetrasiloxane and oxy-1,1'-bis(2, Mention may also be made of mixtures with 2,2',2',3,3'-hexatrimethylsilyloxy)neopentane; and
(ii) Linear volatile polydialkylsiloxanes containing from 2 to 9 silicon atoms and having a viscosity at 25°C of less than or equal to 5×10 ^-6 m ² /s. An example is, inter alia, decamethyltetrasiloxane sold under the name SH 200 by the company Toray Silicone. Silicones belonging to this class are also described in articles published in Cosmetics and Toiletries, Volume 91, January 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. Silicone viscosity is measured at 25°C according to ASTM Standard 445, Appendix C.

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

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products:
- Silbione® oil or Mirasil® oil of the 47 and 70047 series sold by Rhodia, for example oil 70047 V 500000,
- Mirasil® series oils sold by Rhodia,
- 200 series oils from Dow Corning, e.g. DC200 with a viscosity of 60000 mm ² /s, as well as
- Viscasil® oil from General Electric and certain oils of 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 oils from Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes, such as phenylsilicone oils.

Phenyl silicone oil has the following formula:

(In the formula,
R ₁ to R ₁₀ are each independently a saturated or unsaturated, linear, cyclic or branched C ₁ to C ₃₀ hydrocarbon group, preferably a C ₁ to C ₁₂ hydrocarbon group; More preferably C ₁ -C ₆ hydrocarbon groups, especially methyl, ethyl, propyl or butyl groups,
m, n, p and q are each independently an integer of 0 or more and 900 or less, preferably 0 or more and 500 or less, more preferably 0 or more and 100 or less,
However, the sum n+m+q is other than 0)
phenyl silicone.

Examples that may be mentioned include products sold under the following names:
- Silbione® oil from the 70641 series manufactured by Rhodia,
- Rhodorsil® 70633 and 763 series oils manufactured by Rhodia;
- Dow Corning 556 Cosmetic Grade Fluid,
- Silicones of the PK series manufactured by Bayer, for example product PK20,
- Certain oils of the SF series manufactured by General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (in the above formula, R ₁ to R ₁₀ are methyl, p, q, and n=0, and m=1) is preferred.

The organically modified liquid silicone may contain, inter alia, polyethyleneoxy and/or polypropyleneoxy groups. Mention may therefore be made of the silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd. and the oils Silwet® L722 and L77 from Union Carbide.

Hydrocarbon oils can be selected from:
- straight-chain or branched, optionally cyclic C ₆ -C ₁₆ lower alkanes. Examples that may be mentioned include 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 petrolatum, polydecene and hydrogenated polyisobutenes, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g. liquid paraffin), paraffin, vaseline or petrolatum, naphthalene, etc.; hydrogenated polyisobutene, Mention may be made of isoeicosane, and decene/butene copolymers; and mixtures thereof.

The term "fat" in fatty alcohols is meant to contain a relatively large number of carbon atoms. Therefore, alcohols having 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 12 or more carbon atoms are included within the scope of fatty alcohols. Fatty alcohols can be saturated or unsaturated. Fatty alcohols may be linear or branched.

Fatty alcohols have the structure R-OH (where R is a saturated and unsaturated alcohol containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, more preferably from 12 to 20 carbon atoms). (selected from linear and branched groups). In at least one embodiment, R can 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 hydroxyl group.

Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, Mention may be made of erucil alcohol, and mixtures thereof.

Preferably, the fatty alcohol is a saturated fatty alcohol.

Thus, fatty alcohols are straight-chain or branched, saturated or unsaturated C ₆ -C ₃₀ alcohols, preferably straight-chain or branched, saturated C ₆ -C ₃₀ alcohols, more preferably straight-chain or It can be selected from branched, saturated C ₁₂ -C ₂₀ alcohols.

The term "saturated fatty alcohol" as used herein refers to alcohols with long aliphatic saturated carbon chains. Preferably, the saturated fatty alcohol is selected from any linear or branched, saturated C ₆ to C ₃₀ fatty alcohol. Among the straight-chain or branched, saturated C ₆ -C ₃₀ fatty alcohols, preferably the straight-chain or branched saturated C ₁₂ -C ₂₀ fatty alcohols can be used. More preferably, any linear or branched, saturated C ₁₆ -C ₂₀ fatty alcohol can be used. More preferably, branched C ₁₆ -C ₂₀ fatty alcohols can be used.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (eg, cetearyl alcohol) as well as behenyl alcohol can 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 selected from octyldodecanol, hexyldecanol and mixtures thereof.

(e) The additional oil is preferably selected from polar oils, more preferably from ester oils, artificial triglycerides and mixtures thereof, even more preferably from ester oils, artificial triglycerides and mixtures thereof.

The amount of (e) additional oil in the composition according to the invention can be at least 0.01% by weight, preferably at least 0.1% by weight, more preferably at least 1% by weight, relative to the total weight of the composition. .

The amount of (e) additional oil in the composition according to the invention can be up to 40% by weight, preferably up to 35% by weight, more preferably up to 30% by weight, relative to the total weight of the composition. .

The amount of (e) additional oil in the composition according to the invention is from 0.01% to 40% by weight, preferably from 0.1% to 35% by weight, more preferably 1% by weight, relative to the total weight of the composition. to 30% by mass.

[Beauty active ingredients]
The composition according to the invention may comprise (b) at least one (additional) cosmetically active ingredient in addition to the organic UV filter. Additional cosmetic active ingredients are not limited to (b) organic UV filters; Two or more additional cosmetically active ingredients may be used in combination. Thus, a single type of additional cosmetic active ingredient or a combination of different types of additional cosmetic active ingredients can be used.

Among the additional cosmetic active ingredients used are antioxidants, cleansing agents, free radical scavengers, humectants, skin whitening agents, liporegulators, anti-acne agents, anti-dandruff agents, anti-aging agents, softening agents. Mention may be made of anti-wrinkle agents, keratolytic agents, fresheners, antibacterial agents, antifungal agents, antiperspirants, deodorants, skin conditioners, anesthetics, nutritional agents, and sebum or moisture absorbers.

The composition according to the invention comprises from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.5% to 10% by weight, relative to the total weight of the composition. %, more preferably 1% to 5% by weight.

[Optional additives]
In addition to the aforementioned ingredients, the compositions according to the invention contain ingredients typically used in cosmetics, in particular surfactants or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents. (e) Additional silicone and silicone derivatives other than oil, natural extracts derived from animals or plants, wax, etc. may be included within the range that does not impair the effects of the present invention.

The composition according to the invention comprises from 0.001% to 30% by weight, preferably from 0.01% to 20% by weight, more preferably from 0.1% by weight, relative to the total weight of the composition. It may be included in an amount of 10% by mass.

[Composition]
Since the composition according to the invention comprises at least one (b) organic UV filter which may be fatty or oily, the composition according to the invention may comprise at least one fatty or oily phase.

On the other hand, since the composition according to the invention comprises (d) water, the composition according to the invention can comprise at least one aqueous phase.

The aqueous phase may contain at least one C ₂ to C ₆ monohydric alcohol. Two or more C ₂ to C ₆ monohydric alcohols may be used in combination.

C ₂ -C ₆ monohydric alcohols suitable for the invention may contain 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, for example ethanol, isopropanol, propanol or butanol.

Ethanol and isopropanol, preferably ethanol, are very particularly suitable for the present invention.

The amount of C ₂ -C ₆ monohydric alcohol in the composition according to the invention is not more than 20% by weight, preferably not more than 15% by weight, more preferably not more than 10% by weight, relative to the total weight of the composition. Can be done. On the other hand, the amount of C ₂ -C ₆ monohydric alcohol in the composition according to the invention is at least 1% by weight, preferably at least 2% by weight, more preferably at least 3% by weight, based on the total weight of the composition. be. For example, the amount of C ₂ -C ₆ monohydric alcohol may be from 5% to 20% by weight, preferably from 6% to 15% by weight, more preferably from 7% to 10% by weight relative to the total weight of the composition. %.

The composition according to the invention is of the W/O (water-in-oil) type. The W/O composition according to the invention comprises a continuous, oily or fatty (outer) phase and a dispersed or aqueous (inner) phase.

The composition according to the invention can be in the form of a W/O emulsion. Compositions according to the invention in the form of W/O emulsions may typically contain at least one surfactant or emulsifier.

The composition according to the invention can be a cosmetic composition. The cosmetic composition according to the invention can therefore be intended for application to keratinous materials. The term keratin material as used herein refers to a material containing keratin as a main constituent, examples of which include skin, scalp, nails, lips, hair, and the like. The cosmetic composition according to the invention is therefore preferably used in cosmetic methods for keratin materials, especially the skin.

The cosmetic composition according to the invention can therefore be a dermocosmetic composition, preferably a skin care composition or a skin make-up composition, in particular a composition for protecting the skin from ultraviolet radiation.

Compositions according to the invention can be prepared by mixing the above-mentioned essential and optional ingredients according to any of the methods well known to those skilled in the art.

[Film]
The composition according to the invention can be used to prepare coatings. (a) Polyion complexes can aggregate and coalesce into a continuous film.

The invention therefore also provides a method for preparing a coating, preferably a decorative coating, with a thickness of preferably greater than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, comprising:
applying a composition according to the invention to a substrate, preferably a keratin substrate, more preferably skin;
and drying the composition.

There is no upper limit to the thickness of the coating prepared by the composition according to the invention. Thus, for example, the thickness of the coating prepared by the composition according to the invention can be 1 mm or less, preferably 500 μm or less, more preferably 300 μm or less, even more preferably 100 μm or less.

The method according to the invention comprises the steps of: applying a composition according to the invention to a substrate, preferably a keratin substrate, more preferably skin; and drying the composition. does not require spin-coating or spraying, so even relatively thick coatings can be easily prepared. Therefore, the method for preparing the coating allows relatively thick coatings to be prepared without using any special equipment such as spin coaters and spray machines.

Even if the films prepared by the compositions according to the invention are relatively thick, they can still be thin and transparent and therefore may not be easy to perceive. The films prepared by the compositions according to the invention can therefore preferably be used as cosmetic films.

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

If the substrate is not a keratin substrate, it is preferably water-soluble, since it is possible to leave behind the film prepared by the composition according to the invention by washing the substrate with water. Because there is. Examples of water-soluble materials include poly(meth)acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, and the like. PVA is preferred.

If the non-keratinous substrate is in the form of a sheet, it may have a thickness that exceeds the thickness of the coating prepared by the composition according to the invention, in order to facilitate handling of the coating adhered to the substrate sheet. You may. The thickness of the non-keratin substrate sheet is not limited, but can be from 1 μm to 5 mm, preferably from 10 μm to 1 mm, more preferably from 50 to 500 μm.

More preferably, the film prepared by the composition according to the invention is removable from a non-keratinous substrate. The removal method is not limited. The film prepared by the composition according to the invention may therefore be peeled off from a non-keratinous substrate or removed by dissolving the substrate sheet in a solvent such as water.

The present invention also provides
(1) applying the composition according to the invention to a substrate, preferably a keratin substrate, more preferably skin;
a coating, preferably a decorative coating, preferably with a thickness of more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, prepared by a method comprising the step of drying the composition,
and
(2)(i) at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(ii) at least one anionic polymer and at least one non-polymeric base or salt thereof having a pKb value of two or more; or
(iii) at least one amphoteric polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more and/or at least one non-polymeric base or salt thereof having a pKb value of two or more; It may relate to a coating, preferably a decorative coating, comprising at least one organic UV filter, preferably having a thickness of more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more.

The above discussion regarding cationic, anionic and amphoteric polymers, as well as the organic UV filters described above, non-polymeric acids with pKa values of 2 or more, and non-polymeric bases with pKb values of 2 or more, are applicable to the coatings ( Can be applied to those in 1) and (2).

The coating thus obtained by the method described above can be self-supporting. The term "self-supporting" as used herein means that the coating can be in the form of a sheet and can be handled as an independent sheet without the aid of a substrate or support. Accordingly, the term "autonomy" can have the same meaning as "self-supporting."

Preferably, the coating prepared by the composition according to the invention is hydrophobic.

The term "hydrophobic" as used herein means that the solubility of the polymer in water (preferably in a volume of 1 liter) at 20 to 40°C, preferably 25 to 40°C, more preferably 30 to 40°C This means less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, based on the total weight. Most preferably, the polymer is not soluble in water.

If the film prepared by the composition according to the invention is hydrophobic, the film can have water-resistant properties, thus even if the surface of the keratin substrate is wet, for example due to sweat or rain. It can remain on keratin substrates such as skin. Therefore, if the film prepared by the composition according to the invention provides any cosmetic effect, that cosmetic effect can last for a long time.

On the other hand, the film prepared by the composition according to the invention can be easily removed from keratin substrates such as skin under alkaline conditions such as pH 8 to 12, preferably 9 to 11. The film prepared by the composition according to the invention is therefore difficult to remove with water, but can be easily removed with soap capable of providing such alkaline conditions.

The coating prepared by the composition according to the invention may comprise a layer of at least one biocompatible and/or biodegradable polymer. Combinations of two or more biocompatible and/or biodegradable polymers may be used. Thus, a single type of biocompatible and/or biodegradable polymer or a combination of different types of biocompatible and/or biodegradable polymers can be used.

The term "biocompatible" polymer as used herein indicates that the polymer does not have excessive interaction between the polymer and cells within the body, including the skin, and that the polymer is not recognized as foreign by the body. means.

The term "biodegradable" polymer as used herein means that the polymer can be degraded or broken down in an organism, for example by the organism's own metabolism or by the metabolism of microorganisms that may be present in the organism. Biodegradable polymers can also be degraded by hydrolysis.

If the film prepared by the composition according to the invention comprises biocompatible and/or biodegradable polymers, it is less or non-irritating to the skin and does not cause rashes. In addition, the use of biocompatible and/or biodegradable polymers allows the film to adhere well to the skin as a cosmetic film.

The films prepared by the compositions according to the invention can be used in the cosmetic treatment of keratin materials, preferably the skin, especially the face. The coating prepared by the composition according to the invention may be of any shape or form. For example, it can be used as a full face mask sheet or as a patch for parts of the face such as the cheeks, nose, and around the eyes.

Since the coating prepared by the composition according to the invention comprises at least one organic UV filter, it can provide the UV blocking effect derived from the organic UV filter. Typically, organic UV filters can be removed from the surface of keratin substrates such as skin by sebum and the like. However, since the organic UV filter is contained in a film, it is difficult for the organic UV filter to be removed by sebum or the like, thereby producing a UV blocking effect that lasts for a long time.

[Beauty method]
The present invention also provides
The present invention relates to a cosmetic method for keratin substrates, such as skin, which method comprises applying a composition according to the invention to the keratin substrate.

Preferably, the cosmetic method according to the present invention further includes the step of drying the composition to form a cosmetic film on the keratin substrate.

Cosmetic methods herein refer to non-therapeutic cosmetic methods for caring for and/or making up keratin-based surfaces such as skin.

In the above method, the cosmetic film is resistant to water with a pH of 7 or less and is removable with water with a pH of more than 7, preferably 8 or more, more preferably 9 or more.

In other words, the cosmetic film described above may be water resistant under neutral or acidic conditions, such as at a pH of 7 or less, preferably in a range of 6 or more and 7 or less, more preferably in a range of 5 or more and 7 or less; The cosmetic film can be removed under alkaline conditions, such as at a pH above 7, preferably above 8, more preferably above 9. The upper limit of pH is preferably 13, more preferably 12, even more preferably 11.

Therefore, the cosmetic film described above can be water-resistant and therefore cannot remain on the keratin substrate, such as the skin, even when the surface of the keratin substrate is wet, for example due to sweat or rain. can. On the other hand, the above cosmetic film can be easily removed from a keratin substrate such as skin under alkaline conditions. The film prepared by the composition according to the invention is therefore difficult to remove with water, but can be easily removed with soap capable of providing alkaline conditions.

Since the above cosmetic film contains an organic UV filter, the above cosmetic film protects the keratin base material such as the skin from ultraviolet rays, thereby suppressing skin darkening and improving skin color and uniformity. , and/or to treat skin aging.

Furthermore, even if the cosmetic film does not contain any other cosmetically active ingredients, the cosmetic film absorbs or adsorbs bad odors due to the properties of the polyion complex in the cosmetic film, and is effective against keratin base materials such as skin. It may have a cosmetic effect, such as changing the appearance, changing the feel of the keratin substrate, and/or protecting the keratin substrate from dirt or contaminants, for example.

In addition, the cosmetic film described above can instantly change or modify the appearance of the skin by changing light reflection on the skin, etc., even if the cosmetic film does not contain any cosmetically active ingredients. . Thus, the cosmetic film described above may be able to hide skin imperfections such as pores or wrinkles. Furthermore, the cosmetic film described above can instantly change or modify the feel of the skin by changing the surface roughness, etc. on the skin. Furthermore, the cosmetic film described above can immediately protect the skin by covering the surface of the skin as a barrier and protecting the skin from environmental stresses such as pollutants, contaminants, etc.

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

If the above cosmetic film comprises (b) at least one additional cosmetically active ingredient other than an organic UV filter, the cosmetic film may have the cosmetic effect provided by the additional cosmetically active ingredient. For example, if the cosmetic film contains at least one cosmetically active ingredient selected from anti-aging agents, sebum suppressants, deodorants, antiperspirants, skin whitening agents and mixtures thereof, the cosmetic film may prevent skin aging. The skin can be treated to absorb sebum on the skin, control odor on the skin, control sweating on the skin, and/or whiten the skin.

It is also possible to apply a make-up or skin care cosmetic composition to the film prepared by the composition according to the invention after it has been applied to the skin.

[use]
The present invention also provides
(b) at least one organic UV filter;
(c) at least one SPF enhancer;
(d) for increasing the UV absorbance of the composition in a W/O type composition, preferably a cosmetic composition, more preferably a dermocosmetic composition, comprising water;
(a)
(i) at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(ii) at least one anionic polymer and at least one non-polymeric base or salt thereof having a pKb value of two or more; or
(iii) at least one amphoteric polymer and at least one non-polymeric acid or salt thereof having more than one pKa value and/or at least one non-polymer base having more than one pKb value; or a salt thereof.

The above description regarding cationic, anionic and amphoteric polymers, as well as organic UV filters as described above, non-polymeric acids with pKa values of two or more, and non-polymeric bases with pKb values of two or more, are in accordance with the present invention. can be applied to the use of

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

(Examples 1 and 2 and Comparative Examples 1 and 2)
[Preparation]
Each of the compositions according to Example 1 and Example 2 (Example 1 and Example 2) and the composition according to Comparative Example 1 and Comparative Example 2 (Comparative Example 1 and Comparative Example 2) was mixed with the components shown in Table 1. It was prepared by All amounts of ingredients are based on "wt %" as active ingredient.

[evaluation]
(W/O type)
The appearance of each of the compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 was observed by microscopy to determine whether the compositions were of W/O type. The results are shown in Table 1. The meanings of “applicable” and “not applicable” in Table 1 are as follows.
Applicable: W/O type Not applicable: O/W type

(UV absorbance)
Each of the compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 was homogenized by shaking 10 times in a capped container. Each of the homogeneous compositions was transferred onto a plate (Helio plate HD 6, PMMA, roughness: 6 μm) with an adjustable pipette in an amount of 20 mg per cm ² of the plate and then spread evenly with the fingers. The coated plates were air dried for 15 minutes at room temperature. The resulting sample plate was placed in a Labsphere Ultraviolet Transmittance Analyzer (Model UV-2000, manufactured by Solar Light Company, Philadelphia, Pennsylvania). Ultraviolet irradiation was performed at 12 points on the sample plate. The UV absorbance by the sample plate at wavelengths from 250 to 450 nm was recorded.

The results are shown in Figures 1 and 2.

From FIG. 1 it is clear that the composition according to Example 1 has a higher UV absorbance than the composition according to Comparative Example 1, especially from 290 nm to 380 nm. Higher UV absorbance can be attributed to polyion complexes.

From FIG. 2 it is clear that the composition according to Example 2 has a higher UV absorbance than the composition according to Comparative Example 2, especially from 290 nm to 380 nm. Higher UV absorbance can be attributed to polyion complexes.

Figures 1 and 2 demonstrate that polyion complexes can enhance the UV absorbance of W/O type compositions. The UV absorbance of a composition comprising an organic UV filter and an SPF improver is already higher than the UV absorbance of a composition comprising an organic UV filter and no SPF improver. The UV absorbance of a composition according to the invention comprising a polyion complex, an organic UV filter and an SPF improver can further increase the UV absorbance of a composition comprising an organic UV filter and an SPF improver.

(Comparative Examples 3 and 4)
[Preparation]
Each of the compositions according to Comparative Example 3 and Comparative Example 4 (Comparative Example 3 and Comparative Example 4) was prepared by mixing the components shown in Table 2. All amounts of ingredients are based on "wt %" as active ingredient.

[evaluation]
(W/O type)
The appearance of each of the compositions according to Comparative Examples 3 and 4 was observed by microscopy to determine whether the compositions were W/O type. The results are shown in Table 2. The meanings of “applicable” and “not applicable” in Table 2 are as follows.
Applicable: W/O type Not applicable: O/W type

(UV absorbance)
Each of the compositions according to Comparative Examples 3 and 4 was homogenized by shaking 10 times in a capped container. Each of the homogeneous compositions was transferred onto a plate (Helio plate HD 6, PMMA, roughness: 6 μm) with an adjustable pipette in an amount of 20 mg per cm ² of the plate and then spread evenly with the fingers. The coated plates were air dried for 15 minutes at room temperature. The resulting sample plate was placed in a Labsphere Ultraviolet Transmittance Analyzer (Model UV-2000, manufactured by Solar Light Company, Philadelphia, Pennsylvania). Ultraviolet irradiation was performed at 12 points on the sample plate. The UV absorbance by the sample plate was recorded in the wavelength range from 250 to 450 nm.

The results are shown in Figure 3.

From FIG. 3 it is clear that the composition according to Comparative Example 3 has a lower UV absorbance than the composition according to Comparative Example 4, especially from 290 nm to 380 nm. Lower UV absorbance can be attributed to polyion complexes.

Figure 3 demonstrates that polyion complexes are unable to enhance the UV absorbance of O/W compositions.

Claims (13)

(a)(i) at least one polyionic complex comprising at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more;
(b) at least one organic UV filter;
(c) at least one SPF enhancer;
(d) containing water;
the cationic polymer has at least one quaternary ammonium group containing at least one C ₈ -C ₃₀ hydrocarbon group;
The at least one non-polymeric acid or salt thereof having two or more pKa values is terephthalylidene dicamphorsulfonic acid and its salt, Sunset Yellow FCF, ascorbic acid, phytic acid and its salt, and mixtures thereof. selected from the group consisting of
the SPF improver is selected from hollow particles of styrene/acrylate copolymer, multilayer spherical composite particles comprising a silica core particle and a first layer comprising titanium dioxide and a second layer comprising silica, and mixtures thereof;
The amount of the cationic polymer is from 0.001% to 25% by weight based on the total weight of the composition,
The amount of the at least one non-polymeric acid or its salt having two or more pKa values is from 0.001% by weight to 10% by weight based on the total weight of the composition,
The amount of the organic UV filter (b) is 10% by mass to 60% by mass based on the total mass of the composition,
A W/O type composition, wherein the amount of the SPF improver (c) is from 0.1% by mass to 15% by mass based on the total mass of the composition . The cationic polymer has at least one selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. 2. The composition according to claim 1, wherein the composition can have two positive charges and/or has a positively charged moiety. 3. A composition according to claim 1 or 2 , wherein the cationic polymer is selected from the group consisting of polyquaternium-24, polyquaternium-67 and mixtures thereof . 4. A composition according to claim 1, wherein the amount of cationic polymer in the composition is from 0.01% to 20% by weight , relative to the total weight of the composition. 5. A composition according to any one of claims 1 to 4 , wherein the non-polymeric acid having a pKa value of two or more is selected from the group consisting of phytic acid and its salts, and mixtures thereof. 6. The method according to claim 1, wherein the amount of the non-polymeric acid or its salt having two or more pKa values in the composition is from 0.01% to 5 % by weight , based on the total weight of the composition. The composition described in Section. 7. The composition according to claim 1, wherein the amount of (b) organic UV filter in the composition is from 20% to 50% by weight, relative to the total weight of the composition. 8. A composition according to any one of claims 1 to 7 , wherein the amount of (c) SPF improver in the composition is from 0.5% to 10% by weight , relative to the total weight of the composition. 9. A composition according to any one of claims 1 to 8 , wherein the amount of (d) water in the composition is from 1% to 50% by weight, relative to the total weight of the composition. 10. A composition according to any one of claims 1 to 9 , further comprising (e) at least one additional oil. 11. A composition according to any one of claims 1 to 10, which is a cosmetic composition. A beauty method for keratin substrates, the method comprising:
12. A method comprising applying a composition according to any one of claims 1 to 11 to a keratin substrate. (b) at least one organic UV filter;
(c) at least one SPF enhancer;
(d) for increasing the UV absorbance of the composition in a W/O type composition containing water;
(a)(i) the use of at least one polyionic complex comprising at least one cationic polymer and at least one non-polymeric acid or salt thereof having a pKa value of two or more ;
the cationic polymer has at least one quaternary ammonium group containing at least one C ₈ -C ₃₀ hydrocarbon group;
The at least one non-polymeric acid or salt thereof having two or more pKa values is terephthalylidene dicamphorsulfonic acid and its salt, Sunset Yellow FCF, ascorbic acid, phytic acid and its salt, and mixtures thereof. selected from the group consisting of
the SPF improver is selected from hollow particles of styrene/acrylate copolymer, multilayer spherical composite particles comprising a core comprising silica, a first layer comprising titanium dioxide and a second layer comprising silica, and mixtures thereof;
The amount of the cationic polymer is from 0.001% to 25% by weight based on the total weight of the composition,
The amount of the at least one non-polymeric acid or its salt having two or more pKa values is from 0.001% by mass to 10% by mass, based on the total mass of the composition,
The amount of the organic UV filter (b) is from 10% by mass to 60% by mass based on the total mass of the composition,
The use in which the amount of the SPF improver (c) is from 0.1% to 15% by weight, based on the total weight of the composition.

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