JP2022093930A - Composition comprising polyion complex particle and filler - Google Patents

Abstract

To provide a composition that can provide an improved moisturizing texture, preferably a combination of an improved moisturizing texture and an improved mat feeling.SOLUTION: The present invention relates to a composition comprising: (a) at least one particle, comprising at least one cationic polymer and at least one anionic polymer, and at least one non-polymeric acid having two or more pKa values or salt(s) thereof; (b) at least one filler; and (c) water.SELECTED DRAWING: None

Description

The present invention relates to compositions containing polyion complex particles and fillers, and cosmetic methods using the compositions.

It is known that the shine or stickiness of the skin due to sebum can emphasize the roughness of the skin. In other words, shiny skin may make the roughness of the skin such as pores and wrinkles more noticeable. Therefore, the user of the cosmetics wants to realize a matte feeling on the appearance of the skin.

There are several oil absorbing powders. Such powders can be used in cosmetics to provide a matte effect on the skin by absorbing sebum with these powders.

However, oil-absorbing powders often result in undesired dryness or squeaky feel, even in cosmetics containing water. In other words, it is often difficult to use oil-absorbing powders in water-containing cosmetics to provide a good moisturizing texture.

The above problems are not limited to oil-absorbing powders. For example, the use of fillers in cosmetics may result in a squeaky texture, and even if the cosmetic contains water, it may not be possible to obtain a good moisturizing texture.

European Patent Application No. 0080976 French Patent No. 2077143 French Patent No. 2393573 French Patent No. 1492597 US Pat. No. 4,131,576 US Pat. No. 3,589,578 US Pat. No. 4,031,307 French Patent No. 2162025 French Patent No. 2280361 French Patent No. 2252840 French Patent No. 2368508 French Patent No. 1583363 US Pat. No. 3,227,615 US Pat. No. 2,961,347 French Patent No. 20080759 French Patent No. 2190406 French Patent No. 2320330 French Patent No. 2270846 French Patent No. 2316271 French Patent No. 2336434 French Patent No. 2413907 US Pat. No. 2,273,780 US Pat. No. 2,375,853 US Pat. No. 2,388,614 US Pat. No. 2,454,547 US Pat. No. 3,206,462 US Pat. No. 2,261,002 US Pat. No. 2,271,378 US Pat. No. 3,874,870 US Pat. No. 4,001,432 US Pat. No. 3,929,990 US Pat. No. 3,966,904 US Pat. No. 4,005,193 US Pat. No. 4,025,617 US Pat. No. 4,025,627 US Pat. No. 4,025,653 US Pat. No. 4,026,945 US Pat. No. 4,027,020 European Patent Application No. 0122324 EP-A-0750899 EP-A-1069172 EP-A-0173109 US Pat. No. 7,470,725 JP-A-2014-088307 JP-A-2014-218433 JP-A-2018-177620

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 "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715 D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998), pp. 2101-2127 Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990 The Journal of the American Chemical Society, Vol. 60, pp. 309, February 1938 Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957 Barrett, E. P .; Joyner, L. G .; Halenda, P. P., J. Am. Chem. Soc. 73, 373 (1951) Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics

Therefore, there is a need for a composition that contains a filler but can provide an improved moisturizing texture.

Therefore, it is an object of the present invention to provide a composition capable of providing an improved moisturizing texture, preferably both an improved moisturizing texture and a matte feel-imparting effect.

The above object of the present invention is
(a) Below:
At least one cationic polymer and at least one anionic polymer,
And at least one particle, including at least one non-polymeric acid or salt thereof having a pKa value of two or more.
(b) At least one filler and
(c) It can be achieved by a composition comprising water.

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

Cationic polymers include cyclopolymers of alkyl diallylamines and cyclopolymers of dialkyldiallylammoniums, such as (co) polydialyldialkylammonium chloride, (co) polyamines, such as (co) polylysine, cationic (co) polyamino acids, such as collagen. You can choose from the group consisting of cationic cellulose polymers, as well as salts thereof.

The amount of (a) the cationic polymer forming the particles in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably with respect to the total mass of the composition. Can be 0.1% by weight to 5% by weight.

The anionic polymer can be selected from hyaluronic acid and its derivatives.

The amount of the anionic polymer (a) forming the particles in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably with respect to the total mass of the composition. Can be 0.1% by weight to 5% by weight.

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

The amount of the non-polymeric acid or a salt thereof having two or more pKa values forming the particles (a) in the composition according to the present invention is 0.01% by mass to 15% by mass, based on the total mass of the composition. It may be preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass.

The amount of (a) particles in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5 with respect to the total mass of the composition. It may be% by mass.

(b) The filler can be selected from hydrophilic or hydrophobic oil absorbing powders. The hydrophobic oil-absorbing powder can be selected from hydrophobic silica, preferably hydrophobic silica airgel, more preferably a powder of hydrophobic aerogel of silica syllate.

The amount of the filler (b) in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5 with respect to the total mass of the composition. It may be% by mass.

The amount of (c) water in the composition according to the present invention is 50% by mass to 95% by mass, preferably 60% by mass to 90% by mass, and more preferably 70% by mass to 85% with respect to the total mass of the composition. It can be% by mass.

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

The present invention is also a cosmetic method for keratin substances such as skin.
The step of applying the composition according to the present invention to the keratin substance, and
It also relates to a method comprising drying the composition to form a cosmetic film on the keratin material.

As a result of diligent studies, the present inventors have discovered that it is possible to provide a composition capable of providing an improved moisturizing texture, preferably a combination of an improved moisturizing texture and a matte feeling-imparting effect.

Therefore, the composition according to the present invention is
(a) Below:
At least one cationic polymer and at least one anionic polymer,
And with at least one particle, including at least one non-polymeric acid having a pKa value of two or more or a salt thereof.
(b) At least one filler and
(c) Including water.

The compositions according to the invention can provide an improved or enhanced moisturizing texture, eg, a better moisturizing feel.

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

In addition, the composition according to the present invention can reduce or prevent the squeaky texture.

When the filler is oil-absorbent, the composition according to the invention can take up sebum. Therefore, the composition according to the present invention can reduce the shine on the keratin substance such as the skin, and can make the roughness of the skin such as pores and wrinkles inconspicuous. Accordingly, the composition according to the present invention can provide an optical matte feel-imparting effect while providing an improved moisturizing texture. Therefore, the composition according to the present invention can provide both an improved moisturizing texture and an optical matte feeling imparting effect. The effect of imparting an optical matte feeling is considered to be brought about immediately after the composition according to the present invention is applied, and / or is considered to last for a long time.

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

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

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

The amount of (a) particles in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more with respect to the total mass of the composition.

The amount of (a) particles in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the composition.

The amount of (a) particles in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5 with respect to the total mass of the composition. It may be% by mass.

When the composition according to the invention contains (d) at least one oil as described below, the plurality of (a) particles can be present at the interface between (c) water and (d) oil. .. Therefore, (a) particles can stabilize the emulsion. For example, if (c) water forms a continuous phase and (d) oil forms a dispersed phase, (a) the particles can form an O / W emulsion that can resemble a so-called pickering emulsion.

Alternatively, the plurality of (a) particles can form a capsule having a hollow. (d) At least one oil can be present in the hollow. In other words, (d) oil can be incorporated into capsules. The walls of the capsule may consist of (a) a continuous layer or coating formed from the particles. I'm not going to stick to theory, but (a) particles spontaneously reassemble at the interface between (c) water and (d) oil to form (d) hollow capsules to contain the oil. It is thought that it can be done. For example, a continuous phase composed of (c) water and a dispersed phase composed of (d) oil in a capsule can form an O / W emulsion that can be similar to a so-called pickering emulsion.

The above is considered to mean that (a) the particles themselves are amphipathic. (a) The particles themselves are insoluble in oil or water.

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

The types of cationic and anionic polymers are not limited. Two or more different types of cationic polymers may be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers can be used. Two or more different types of anionic polymers may be used in combination. Therefore, a single type of anionic polymer or a combination of different types of anionic polymers can be used.

The amount of cationic polymer / anionic polymer, for example the chemical equivalent ratio, may be 0.05-18, preferably 0.1-10, more preferably 0.5-5.0. Specifically, the number of cationic groups of the cationic polymer / the number of anionic groups of the anionic polymer may be preferably 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0. be.

The total amount of the cationic and anionic polymers in the composition according to the present invention may be 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more with respect to the total mass of the composition.

The total amount of the cationic and anionic polymers in the composition according to the present invention may be 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, based on the total mass of the composition.

The total amount of the cationic and anionic polymers in the composition according to the present invention is 0.1% by mass to 30% by mass, preferably 0.5% by mass to 25% by mass, more preferably 1% by mass with respect to the total mass of the composition. It may be 20% by mass.

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

The molecular weight of the cationic polymer may be preferably 500 or more, preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more.

Unless otherwise defined herein, "molecular weight" means number average molecular weight.

The cationic polymer is at least one positive selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group. It can have a charge and / or may have a portion having a positive charge. The term (primary) "amino group" herein means -NH ₂ groups.

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

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

(1) Derived from the ester and amide of acrylic acid or methacrylic acid, the following formula:

(During the ceremony,
R ₁ and R ₂ may be the same or different and may be selected from hydrogen and an alkyl group containing 1 to 6 carbon atoms, eg, a methyl group and an ethyl group.
R ₃ may be the same or different, selected from hydrogen and CH ₃
The symbol A may be the same or different, with a linear or branched alkyl group containing 1 to 6 carbon atoms, eg, 2 to 3 carbon atoms, and 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 and benzyl groups containing 1 to 18 carbon atoms, 1 to 6 in at least one embodiment. It is an alkyl group containing 10 carbon atoms.
X is a homopolymer and copolymer comprising at least one unit selected from the units of anions derived from inorganic or organic acids such as metosulfate anions and halide ions, eg chloride and bromide ions.

The copolymers of family (1) above may also contain at least one unit derived from a comonomer, which is an acrylamide, methacrylicamide, diacetoneacrylamide, a lower alkyl group with a nitrogen atom (C ₁ to C ₄ ). You can choose from substituted acrylamide and methacrylicamides, acrylic acids or groups derived from methacrylic acid and esters thereof, vinyl lactams such as vinylpyrrolidone and vinyl caprolactam, and vinyl esters.

Examples of copolymers of family (1) include, but are not limited to:
Copolymers of acrylamide with dimethylaminoethyl methacrylate, quaternized with dimethyl sulfate or dimethyl halide,
Copolymers of acrylamide with methacryloyloxyethyltrimethylammonium chloride, such as those described in European Patent Application No. 0080976,
Copolymer of acrylamide and methacryloyloxyethyltrimethylammonium metosulfate,
Quartized or non-quaternized vinylpyrrolidone / acrylic acid or dialkylaminoalkyl methacrylate copolymers, such as those described in French Patents 2077143 and 2393573,
Dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidonter polymer,
Vinylpyrrolidone / methacrylamide propyldimethylamine copolymer, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylate copolymer, and crosslinked methacryloyloxy (C ₁ to C ₄ ) alkyltri (C ₁ to C ₄ ) alkylammonium salt polymers such as chloride. Following the homopolymerization or copolymerization of dimethylaminoethyl methacrylate quaternized with methyl, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride. A polymer obtained by cross-linking with a compound containing olefinic unsaturated, for example methylenebisacrylamide.

(2) Cationic cellulose polymers such as cellulose ether derivatives containing one or more quaternary ammonium groups described in French Patent No. 1492597, eg, named "JR" (JR) by Union Carbide Corporation. Polymers sold in 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as quaternary ammonium of hydroxyethyl cellulose reacted with epoxides substituted with trimethylammonium groups.

The cationic cellulose polymer preferably has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.

The quaternary ammonium group has the following chemical formula (I):

(During the ceremony,
Each of R ₁ and R ₂ represents a C ₁ to C ₃ alkyl group, preferably a methyl or ethyl group, more preferably a methyl group.
R ₃ represents a C ₁ to C ₂₄ alkyl group, preferably a methyl or ethyl group, more preferably a methyl group.
X- represents an anion, preferably a halide ion, more preferably a chloride ion,
n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0.
R ₄ indicates a C ₁ to C ₄ alkylene group, preferably an ethylene group or a propylene group)
It may be present in a quaternary ammonium group-containing group that may be represented by.

The leftmost ether bond (-O-) in the above chemical formula (I) can be bonded to the sugar ring of the polysaccharide.

The quaternary ammonium group-containing group is preferably -O-CH ₂ -CH (OH) -CH ₂ -N ⁺ (CH ₃ ) ₃ .

(3) For example, cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with a water-soluble monomer of quaternary ammonium described in US Pat. No. 4,131,576, for example, methacryloylethyltrimethylammonium, methacrylamidopropyltrimethyl. Hydroxyalkyl cellulose grafted with salts selected from ammonium and dimethyldiallylammonium salts, such as hydroxymethyl-, hydroxyethyl- and hydroxypropyl cellulose.

Examples of commercial products corresponding to these polymers include products sold by National Starch under the names "Celquat® L 200" and "Celquat® H 100".

(4) Non-cellulosic cationic polysaccharides described in US Pat. Nos. 3,589,578 and 4,031,307, such as guar gum containing a cationic trialkylammonium group, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride. Salt-modified guar gum, such as a salt of 2,3-epoxypropyltrimethylammonium, for example chloride-modified guar gum (guar hydroxypropyltrimonium chloride) can also be used.

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

(5) A divalent alkylene group or hydroxy containing a linear or branched chain optionally interrupted by a piperazinyl unit and at least one element selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings. Polymers containing alkylene groups, as well as oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patents 2162025 and 2280361.

(6) For example, water-soluble polyaminoamides prepared by polycondensing an acidic compound with a polyamine, and these polyaminoamides are epihalohydrin; diepoxide; dianhydride; unsaturated dianhydride; bis-unsaturated derivative; bishalohydrin. Bisazetidinium; bishaloacyldiamine; bisalkylhalide; bifunctional that is reactive with elements selected from bishalohydrin, bishaloacidinium, bishaloacyldiamine, bisalkylhalide, epihalohydrin, diepoxide and bisunsaturated derivatives. It may be crosslinked with an element selected from the oligomers obtained from the reaction of the sex compound; the crosslinker is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides. Are optionally alkylated, or if they contain at least one tertiary amine functional group, they may be quaternized. Such polymers are described, for example, in French Patents Nos. 2252840 and 2368508.

(7) A polyaminoamide derivative obtained by condensing a polyalkylene polyamine with a polycarboxylic acid and then alkylating it with a bifunctional agent, for example, one alkyl group such as methyl, ethyl and propyl groups. Adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymer containing up to 4 carbon atoms and 1 to 4 carbon atoms having an alkylene group such as an ethylene group. Such polymers are described, for example, in French Patent No. 1583363. In at least one embodiment, these derivatives can be selected from adipate / dimethylaminohydroxypropyldiethylenetriamine polymers.

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

(9) Alkyl diallylamine cyclopolymers and dialkyl diallyl-ammonium cyclopolymers, for example homos containing at least one unit selected from the units of the following formulas (Ia) and (Ib): as the main constituents of the chain. Polymers and copolymers.

(During the ceremony,
k and t may be the same or different and are equal to 0 or 1, and 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, with an alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group containing, for example, 1 to 5 carbon atoms, and a lower group (the alkyl group contains, for example, 1 to 5 carbon atoms). C ₁ to C ₄ ) Selected from amidoalkyl groups, or R ₁₀ and R ₁₁ may be combined with the nitrogen atom to which they are attached to form heterocyclic groups such as piperidinyl and morpholinyl. ,
Y'is an anion such as bromide ion, chloride ion, acetate ion, borate ion, citrate ion, tartrate ion, hydrogen sulfate ion, hydrogen sulfite ion, sulfate ion and phosphate ion). These polymers are described, for example, in French Patent No. 2080759 and its additional patent No. 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) polydialyldialkylammonium chlorides, eg, dimethyldiallylammonium chloride homopolymers sold by CALGON under the name "MERQUAT® 100" (and low mass average molecular weight). Examples thereof include, but are not limited to, copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".

Quaternary diammonium polymer containing at least one repeating unit of formula (II):

{In the ceremony,
R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different, with aliphatic, alicyclic and aryl aliphatic groups containing 1 to 20 carbon atoms, and lower hydroxy. Selected from alkyl aliphatic groups, or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ optionally have a second heteroatom other than nitrogen, either together or separately with the nitrogen atom to which they are attached. The complex rings contained in the selection may be formed, or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different, and may be a nitrile group, an ester group, an acyl group, an amide group, and the like. At least one group selected from -CO-OR ₁₇ -E group and -CO-NH-R ₁₇ -E group [in the formula, R ₁₇ is an alkylene group and E is a quaternary ammonium group]. Selected from linear or branched C ₁ to C ₆ alkyl groups substituted with,
A ₁ and B ₁ may be the same or different and are selected from polymethylene groups containing 2-20 carbon atoms, which are linear or branched, saturated or unsaturated. Often, it is selected from an aromatic ring, oxygen, sulfur, sulfoxide group, sulfone group, disulfide group, amino group, alkylamino group, hydroxyl group, quaternary ammonium group, ureido group, amide group and ester group. At least one element may be concatenated or inserted into the main chain and included.
X ^- is an anion derived from an inorganic or organic acid and
A ₁ , R ₁₃ and R ₁₅ may combine with the two nitrogen atoms to which they are attached to form a piperazine ring.
If A ₁ is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B ₁ can be selected from:
-(CH ₂ ) _n -CO-E'-OC- (CH ₂ ) _n-
[In the formula, E'is as follows:
a) Formula -OZO- (In the formula, 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 )-
(In the formula, x and y may be the same or different, an integer in the range 1 to 4 representing the defined unique degree of polymerization, and a number in the range 1 to 4 representing the average degree of polymerization. Glycol residue, selected from (selected from) groups,
b) Bis-secondary diamine residues, eg piperazine derivatives,
c) Formula-NH-Y-NH-(In the formula, Y is selected from linear or branched hydrocarbon groups and divalent groups -CH ₂ -CH ₂ -SS-CH ₂ -CH _2- ) Bis-primary diamine residues, as well as
d) Selected from the ureylene groups of equation-NH-CO-NH-]}.

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

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

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

(In the formula, 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. Can be the same or different, and is an integer in the range 2-20, where X ^- is an anion derived from an inorganic or organic acid).

(11) Polyquaternary ammonium polymer containing the unit of formula (IV):

(During the ceremony,
R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ may be the same or different, hydrogen, methyl group, ethyl group, propyl group, β-hydroxyethyl group, β-hydroxypropyl group, -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH groups (in the formula, p is chosen from an integer in the range 0-6), provided that R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are hydrogen at the same time. Never
r and s may be the same or different and are chosen from integers in the range 1-6.
q is chosen from integers in the range 0-34,
X ^- is an anion, eg a halide ion,
A is selected from the dihalide group and the -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -group).

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

(12) A quaternary polymer of vinylpyrrolidone and vinylimidazole.
Other examples of suitable cationic polymers include cationic proteins and cationic protein hydrolysates, polymers containing polyalkyleneimines such as polyethyleneimine, units selected from vinylpyridine units and vinylpyridinium units, polyamines and epichloros. Examples 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 quaternary ammonium group-containing cellulose ether derivative, eg, a product sold by UNION CARBIDE CORPORATION under the name "JR 400", cationic. Cyclopolymers, for example homopolymers and copolymers of dimethyldiallylammonium chloride sold by CALGON under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S, 2,3-epoxy It is selected from guar gum modified with a propyltrimethylammonium salt, as well as a quaternary polymer of vinylpyrrolidone and vinylimidazole.

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

Examples of (co) polyamines include chitosan, (co) polyallylamine, (co) polyvinylamine, (co) polyaniline, (co) polyvinylimidazole, (co) polydimethylaminoethylene methacrylate, (co) polyvinylpyridine, for example (co) Co) Poly-1-methyl-2-vinylpyridine, (co) polyimine, eg (co) polyethyleneimine, (co) polypyridine, eg (co) poly (quaternary pyridine), (co) polybiguanide, eg (co) Examples include polyaminopropylbiguanide, (co) polylysine, (co) polyornitine, (co) polyarginine, (co) polyhistidine, aminodextran, aminocellulose, amino (co) polyvinyl acetal, and salts thereof. can.

As the (co) polyamine, it is preferable to use (co) polylysine. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine can be 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, propylene glycol and glycerol. Polylysine is commercially available in various forms such as poly D-lysine and poly L-lysine. Polylysine can be in the form of salts and / or solutions.

(14) Cationic polyamino acid As the cationic polymer, it is possible to use a cationic polyamino acid having a plurality of amino groups and carboxyl groups, which may be a cationic homopolymer or a copolymer. The amino group can be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in the polymer backbone of the cationic polyamino acid, or in the pendant group if present. The carboxyl group, if present, may be present in the pendant group of the cationic polyamino acid.

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

The following description relates to preferred embodiments of cationic polymers.

It may be preferable that the cationic polymer be selected from cationic starch.

Examples of cationic starches are starches modified with 2,3-epoxypropyltrimethylammonium salts (eg, chlorides), such as SENSOMER Cl-50 from Ondeo or Pencare ™ DP 1015 from Ingredion. There is a product on the market known as starch hydroxypropyltrimonium chloride according to the INCI name.

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

The gum may be selected from the group consisting, for example, cassia gum, karaya gum, konjac gum, tragacanto gum, tara gum, acacia gum. And gum arabic.

Examples of cationic gums include cationic polygalactomannan derivatives such as guar gum derivatives and cassia gum derivatives such as CTFA: guar hydroxypropyltrimonium chloride, hydroxypropylguarhydroxypropyltrimonium chloride, and cassia hydroxypropyltrimonium chloride. Can be mentioned. Guar hydroxypropyltrimonium chloride is commercially available from Rhodia Inc. under the Jaguar ™ brand name series and from Ashland Inc. under the N-Hance brand name series. Cassia hydroxypropyltrimonium chloride is commercially available from Lubrizol Advanced Materials, Inc. under the Trademark ClearHance ™ from Sensorer ™ CT-250 and Sensorer ™ CT-400 or Ashland Inc.

Cationic polymers include cyclopolymers of alkyl diallylamines and cyclopolymers of dialkyldialylammoniums, such as (co) polydialyldialkylammonium chloride, (co) polyamines, such as (co) polylysine, cationic (co) polyamino acids, such as cations. It may be preferred to be selected from the group consisting of polylysine, cationic cellulose polymers, and salts thereof.

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

The cationic polymer is selected from the group consisting of polylysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan, and mixtures thereof. May be more preferred.

The amount of the cationic polymer in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of the cationic polymer in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

The amount of the cationic polymer in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass with respect to the total mass of the composition. Can be%.

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

The molecular weight of the anionic polymer is 300 or more, preferably 1,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, still more preferably 1,000,000 or more. May be preferable.

Unless otherwise defined in the description, "molecular weight" can mean a number average molecular weight.

The anionic polymer is at least one negative 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. It may have a portion that can have a charge and / or have a negative charge.

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

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

The anionic polymer may contain at least one hydrophobic chain.

Anionic polymers that may contain at least one hydrophobic chain are selected from carboxylic acids containing α, β-ethylenic unsaturated (monomer a') and 2-acrylamide-2-methylpropanesulfonic acid (monomer a''). The monomer (a) is a non-surface active monomer (b) containing ethylenically unsaturated other than (a), and / or an acrylic monomer containing α, β-monoethylene unsaturated or monoethylene unsaturated. Obtaining by copolymerizing an isocyanate monomer with a monovalent nonionic amphoteric component or a monomer (c) containing ethylenically unsaturated obtained by reacting with a primary or secondary fatty amine. Can be done.

Therefore, anionic polymers with at least one hydrophobic chain can be obtained by one of two synthetic pathways:
--Monomeres (a') and (c), or (a') and (b) and (c), or (a'') and (c), or (a'') and (b) and (c) By copolymerization with
-Or the monomer (a'), or the copolymer formed from the monomers (a') and (b), or (a'') and (b), is a monovalent nonionic amphipathic compound or the first. By modification (specifically, esterification or amidation) with a secondary or secondary fatty amine.

2-acrylamide-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering --Macromolecules , 2000, Vol. 33, No. 10-3694-3704 ”and the ones disclosed in Applications EP-A-0750899 and EP-A-1069172.

The carboxylic acid containing α, β-monoethylene unsaturated substance constituting the monomer (a') is selected from a large number of acids, specifically acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. Can be done. This is preferably acrylic acid or methacrylic acid.

The copolymer can include a monomer (b) containing a monoethylenically unsaturated without surfactant properties. Preferred monomers are those that give a water-insoluble polymer when homopolymerized. These can be selected from, for example, acrylic acid and alkyl methacrylate (C ₁ to C ₄ ), such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylate. 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, where a single ethylenic group is the only group that is reactive under polymerization conditions. However, monomers containing groups that react under the action of heat, such as hydroxyethyl acrylate, can optionally be used.

The monomer (c) is an acrylic monomer containing an α, β-monoethyl unsaturated, for example (a), or an isocyanate monomer containing a monoethyl unsaturated, which is a monovalent nonionic amphoteric compound or a first. Obtained by reacting with a tertiary or secondary fatty amine.

Monovalent nonionic amphipathic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. Monovalent nonionic amphipathic compounds are generally alkoxylated hydrophobic compounds containing alkylene oxides that form the hydrophilic moieties of the molecule. Hydrophobic compounds are generally composed of aliphatic alcohols or alkylphenols, in which carbonic chains containing at least 6 carbon atoms constitute the hydrophobic portion of the amphipathic compound.

A preferred monovalent nonionic amphipathic compound is a compound having the following formula (V):
R- (OCH ₂ CHR') _m- (OCH ₂ CH ₂ ) _n -OH (V)
(In the formula, R is selected from an alkyl or alkylene group containing 6 to 30 carbon atoms and an alkylaryl group having an alkyl group containing 8 to 30 carbon atoms, and R'is 1 to 4 Selected from alkyl groups containing carbon atoms of, n is an average number in the range of approximately 1 to 150, m is an average number in the range of approximately 0 to 50, where n is at least the same as m. The size).

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

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

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

The monomer (c) is, in particular, an acrylate, methacrylate or itaconate of an oxyethyleneated (1-50EO) C ₆ -C ₃₀ fatty alcohol, such as steareth-20 methacrylate, oxyethyleneated (25EO) behenyl methacrylate, oxyethyleneylated ( 20EO) monocetyl itaconate, oxyethylenated (20EO) monostearyl itaconate or polyoxyethylenated (25EO) from acrylates modified with C ₁₂ to C ₂₄ alcohols, and oxyethylenated (1 to 50 EO) C ₆ to You can choose from dimethyl-m-isopropenylbenzyl isocyanate of C ₃₀ fatty alcohols, for example dimethyl-m-isopropenylbenzyl isocyanate of oxyethylated behenyl alcohols in particular.

According to a particular embodiment of the invention, the anionic polymer is (a) a carboxylic acid containing an α, β-ethylenically unsaturated, and (b) a non-surface active monomer containing an ethylenically unsaturated other than (a). , And (c) an acrylic terpolymer obtained from a nonionic urethane monomer which is a reaction product of a monovalent nonionic amphoteric compound and an isocyanate containing a monoethylenically unsaturated.

Anionic polymers containing at least one hydrophobic chain include, in particular, acrylic acid / ethyl acrylate / alkyl acrylate terpolymers, eg, as a 30% aqueous dispersion sold under the name Acusol 823 by Rohm & Haas. Products; Acrylic / Steareth Methacrylate-20 Polymers, eg Products sold under the name Aculyn 22 by Rohm &Haas; (Meta) Acrylic Acid / Ethyl Acrylate / Oxyethyleneated (25EO) Behenyl Methaster Polymers, eg Rohm Product as an aqueous emulsion sold by & Haas under the name Aculyn 28; Acrylic acid / oxyethylenated (20EO) monocetyl itaconate polymer, eg 30% aqueous dispersion sold under the name Structure 3001 by National Starch. Product as a body; Acrylic acid / Oxyethyleneated (20EO) monostearyl itaconate polymer, for example a product as a 30% aqueous dispersion sold under the name Structure 2001 by National Starch; Acrylic / Polyoxyethylated (25EO) ) C ₁₂ -C ₂₄ Alcohol-modified acrylate copolymers, eg 30-32% copolymer latex sold under the name Synthalen W2000 by 3V SA; or dimethyl-meth of methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol. -Isopropenylbenzyl isocyanate tarpolymers, such as products as 24% aqueous dispersions containing 40 ethylene oxide groups disclosed in Document EP-A-0173109 can be mentioned.

The anionic polymer may also be a polyester-5, eg, a product sold by EASTMAN CHEMICAL under the name Eastman AQ ™ 55S Polymer, having the following chemical formula:

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

Anionic polymers include polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (eg carboxymethyl cellulose), anionic (co) polyamino acids such as (co) polyglutamic acid, (co) poly (meth) acrylic acid, (co) polyamine. A group consisting of acid, (co) polystyrene sulfonate, (co) poly (vinyl sulfate), dextran sulfate, chondroitin sulfate, (co) polymaleic acid, (co) polyfumolic acid, maleic acid (co) polymer, and salts thereof. It may be preferable to be selected from.

The maleic acid copolymer comprises one or more maleic acid comonomer and one or more comonomer selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, an olefin containing 2 to 20 carbon atoms, and styrene. good.

Therefore, a "maleic acid copolymer" is one or more maleic acid comonomer and vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing 2 to 20 carbon atoms such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene. , And any polymer obtained by copolymerization with one or more comonomer selected from styrene, the maleic acid comonomer is optionally partially or completely hydrolyzed. Preferably, a hydrophilic polymer, that is, a polymer having a water solubility of 2 g / l or more is used.

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

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

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

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

For example, the styrene / maleic acid (50/50) copolymer in the form of ammonium salts in 30% water, sold by Cray Valley under the reference name SMA1000H®, or the reference name SMA1000HNa® by Cray Valley. ), A styrene / maleic acid (50/50) copolymer in the form of sodium salts in 40% water can be used.

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.

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

Hyaluronic acid can be represented by the following chemical formula.

In the context of the present invention, the term "hyaluronic acid" specifically includes the basic unit of hyaluronic acid of the following equation:

This is the smallest portion of the disaccharide dimer, hyaluronic acid containing D-glucuronic acid and N-acetylglucosamine.

The term "hyaluronic acid and its derivatives" also, in the context of the present invention, alternate β (1,4) and β (1,3) glucosides having a molecular weight (MW) that can range from 380 to 13,000,000 daltons. Also included are linear polymers containing the above polymer units that are bonded together within the chain via a bond. This molecular weight largely depends on the source from which hyaluronic acid is obtained and / or the method of preparation.

The term "hyaluronan and its derivatives" also includes hyaluronate in the context of the present invention. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as magnesium salt, ammonium salts, and mixtures thereof.

In its natural state, hyaluronic acid is found in percellular gels in the connective tissue substrates of connective tissues of vertebrate organs such as the dermis and epithelial tissues, especially in the epidermis, synovial fluid of joints, vitreous humor, human umbilical cord, and chicken crown. Present in the protrusion.

As such, the term "hyaluronic acid and its derivatives" includes all fractions or subunits of hyaluronic acid having a molecular weight within the molecular weight range specifically recalled above.

In the context of the present invention, it is preferred to use a hyaluronic acid fraction that does not have inflammatory activity.

As an example of various hyaluronic acid decompositions, the listed biological activities of hyaluronic acid are reviewed according to their molecular weights, such as "Hyaluronan fragments: an information-rich system", R. Stern, etc., European Journal of Cell Biology 58. (2006) You may refer to pages 699 to 715.

According to a preferred embodiment of the invention, the suitable hyaluronic acid fractions contained in the invention have a molecular weight between 50,000 and 5,000,000, particularly between 100,000 and 5,000,000, particularly between 400,000 and 5,000,000 Da. In this case, the term used is high molecular weight hyaluronic acid.

Alternatively, the hyaluronic acid fraction which may also be suitable for use in the present invention has a molecular weight between 50,000 and 400,000 Da. In this case, the term used is medium molecular weight hyaluronic acid.

Alternatively, the hyaluronic acid fraction that may be suitable for use in the present invention has a molecular weight of less than 50,000 Da. In this case, the term used is low molecular weight hyaluronic acid.

Finally, the term "hyaluronic acid and its derivatives" is also one in which all or part of the carboxylic acid groups of the hyaluronic acid ester, in particular the acid functional group, are esterified with an alkyloxyethylated or alcohol, 1 Includes those containing up to 20 carbon atoms, especially those in which the degree of substitution of D-glucuronic acid levels in hyaluronic acid is in the range of 0.5-50%.

In particular, methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid can be mentioned. Such esters are specifically described in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998), pp. 2101-2127.

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

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

Specifically, hyaluronic acid is traded by Hyactive under the trade name CPN (MW: 10-150 kDa), by Solidance under the trade name Cristalhyal (MW: 1.1 × 10 ⁶ ), and by Bioland under the trade name Nutra HA (MW: 820000 Da). ), Supplied by Bioland under the name Nutra AF (MW: 69000Da), Bioland under the name Oligo HA (MW: 6100Da), or otherwise by Vam Farmacos Metica under the name D Factor (MW: 380Da). Can be hyaluronic acid.

The amount of the anionic polymer in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of the anionic polymer in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

The amount of the anionic polymer in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass with respect to the total mass of the composition. Can be%.

(Non-polymeric acid with two or more acid dissociation constants)
The compositions according to the invention may comprise at least one non-polymeric acid having two or more pKa values or a salt thereof, i.e., at least one non-polymeric acid having two or more acid dissociation constants or a salt thereof. .. The pKa value (acid dissociation constant) is well known to those of skill in the art and should be determined at a constant temperature, eg 25 ° C.

Non-polymeric acids or salts thereof with two or more pKa values can be incorporated into (a) particles. Non-polymeric acids with two or more pKa values can function as cross-linking agents for anionic and / or amphoteric polymers.

The term "non-polymer" is used herein to mean that an acid is not obtained by polymerizing two or more monomers. Therefore, the non-polymeric acid does not correspond to the acid obtained by polymerizing two or more kinds of monomers such as polycarboxylic acid.

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

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

As used herein, the term "salt" means a salt formed by adding a suitable base to a non-polymeric acid having a pKa value of two or more, which is according to methods known to those of skill in the art. It can be obtained from the reaction of a non-polymeric acid having two or more pKa values with a base. Examples of the salt include a metal salt, for example, a salt with an alkali metal such as Na and K, a salt with an alkaline earth metal such as Mg and Ca, and an ammonium salt.

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

The non-polymeric acid having a pKa value of 2 or more is selected from the group consisting of a carboxylic acid group, a sulfate group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a phenolic hydroxyl group, and a mixture thereof, at least 2 It may have one acid group.

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

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

Non-polymeric acids or salts thereof having two or more pKa values are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, apple. Acids, citric acid, aconitic acid, oxaloacetate, tartaric acid, and salts thereof; asparagic acid, glutamate, and salts thereof; terephthalylidenedicampharsulfonic acid, or a salt thereof (Mexoryl SX), benzophenone-9; phytic acid. And its salts; Red No. 2 (Amaranth), Red No. 102 (New Coccin), Yellow No. 5 (Tartrazine), Yellow No. 6 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue No. 1 (Blue No. 1 (Fast Green FCF) Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Red No. 201 (Resole Rubin B), Red No. 202 (Resole Rubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Resole Red CA), Red No. 207 (Resole Red BA), Red No. 208 (Resole Red SR), Red No. 219 (Brilliant Treki Red R), Red No. 220 (Deep Maroon), Red No. 227 (Fast Acid Magenta), Yellow No. 203 (Kinoline Yellow WS) , Green No. 201 (Alizanin Cyanin Green F), Green No. 204 (Pyranin Conch), Green No. 205 (Light Green SF Yellow), Blue No. 203 (Patent Blue CA), Blue No. 205 (Alphazulin FG), Red No. 401 (Violamin R), Red No. 405 (Permanent Red F5R), Red No. 502 (Ponso 3R), Red No. 503 (Ponso R), Red No. 504 (Ponso SX), Green No. 401 (Naftor Green B), Green From No. 402 (Guinea Green B) and Black No. 401 (Naftor 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. You can choose from a group of

Non-polymeric acids or salts thereof having two or more pKa values are terephthalylidenedicampharsulfonic acid and its salts (Megizolyl SX), Yellow No. 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and their salts. , And may preferably be selected from the group consisting of mixtures thereof.

The amount of the non-polymeric acid or a salt thereof having two or more pKa values in the composition according to the present invention is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1 with respect to the total mass of the composition. It may be mass% or more.

The amount of the non-polymeric acid or a salt thereof having two or more pKa values in the composition according to the present invention is 15% by mass or less, preferably 10% by mass or less, more preferably 5 with respect to the total mass of the composition. It can be less than or equal to mass%.

The amount of the non-polymeric acid or salt thereof having two or more pKa values in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, based on the total mass of the composition. %, More preferably 0.1% by mass to 5% by mass.

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

The term "filler" is meant to mean colorless or white, inorganic or synthetic particles that are insoluble in the liquid components that may be present in the compositions according to the invention, regardless of the temperature at which the composition is produced. Should be understood.

(b) The filler may be inorganic or organic, and may have a spherical or oval shape regardless of the crystal form (for example, thin plate, cubic system, hexagonal system, orthorhombic system, etc.). May be good. Not limited to talc, mica, silica, silica syrylate, kaolin, sericite, calcined talc, calcined mica, calcined sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium carbonate, carbonic acid. Formed of magnesium hydrogen and hydroxyapatite, polyamide [Nylon®], powder formed of poly-β-alanine and polyethylene, powder formed of polyurethane, tetrafluoroethylene polymer [Teflon®] Powder, lauryl lysine, starch, polymer hollow microspheres, eg poly (vinylidene chloride) / acrylonitrile hollow microspheres, eg Expancel® (Nobel Industrie), or acrylic acid copolymer hollow microspheres, silicone resin micros. Beads [eg, Tospearls® from Toshiba], particles formed of polyorganosiloxane elastomers, precipitated calcium carbonate, magnesium carbonate, basic magnesium carbonate, hollow silica microspheres, glass or ceramic microcapsules, or 8 to Metallic soaps derived from organic carboxylic acids having 22 carbon atoms, such as 12-18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate can be mentioned. can.

In the present invention, examples of the filler include metal oxides, preferably titanium oxide, zinc oxide and mixtures thereof.

The filler suitable for the present invention may be, for example, a filler having an average particle size of less than 100 μm, particularly between 1 and 50 μm, for example, between 4 and 20 μm.

(b) The filler can be selected from hydrophilic or hydrophobic oil absorbing powders.

Hydrophilic or hydrophobic oil-absorbing powders are capable of absorbing (and / or adsorbing) oils or liquid fatty substances, such as sebum (from the skin).

The hydrophilic or hydrophobic oil absorbing powder may contain porous or hollow particles, particularly porous or hollow spherical particles.

[Hydrophilic oil absorbing powder]
For the purposes of the present invention, the term "hydrophilic" oil-absorbing powder means that the powder (or particles) is individually dispersed in water so that aggregates are not formed.

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

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

The amount of oil absorbed (and / or adsorbed) can be measured according to the method described in NF Standard T 30-022 for determining the amount of oil absorbed by a powder. This corresponds to the amount of oil absorbed / adsorbed on the available surface of the powder as measured by the wet spot.

A powder in an amount of m = 2 g is placed on a glass plate, and then oil (ester oil, silicone oil, etc.) is added dropwise. After adding 4-5 drops of oil to the powder, mix using a spatula and continue adding the oil until an aggregate of oil and powder is formed. At this point, add the oil drop by drop, then grind the mixture with a spatula. When a firm and smooth paste is obtained, stop adding the oil. The paste must be able to spread on a glass plate without cracking or forming lumps. Then the volume Vs (represented in ml) of the oil used is noted. The oil absorption amount corresponds to the Vs / m ratio.

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

The hydrophilic oil absorbing powder may be organic or inorganic.

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

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

The term "cellulose ester", in the above and in the text below, means a polymer consisting of the α (1-4) sequence of partially or completely esterified anhydrous glucose rings, which esterification is said above. With all or part of the free hydroxyl functional groups of the anhydrous glucose ring and linear or branched carboxylic acids or carboxylic acid derivatives (acidides or acid anhydrides) containing 1 to 4 carbon atoms. Obtained by the reaction of. Preferably, the cellulose ester is obtained by reacting a part of the free hydroxyl functional group of the ring with a carboxylic acid containing 1 to 4 carbon atoms. Advantageously, the cellulose ester is selected from cellulose acetate, cellulose propionate, cellulose butyrate, cellulose isobutyrate, cellulose acetobutyrate and cellulose acetopropionate, and mixtures thereof.

The term "cellulose ether" means a polymer consisting of the α (1-4) sequence of a partially etherified anhydrous glucose ring, with some of the free hydroxyl functional groups in the ring substituted with -OR groups. R is preferably a linear or branched alkyl group containing 1 to 4 carbon atoms. Therefore, the cellulose ether is preferably selected from cellulose alkyl ethers having an alkyl group containing 1 to 4 carbon atoms, such as cellulose methyl, propyl, isopropyl, butyl and isobutyl ethers.

Examples of cellulose and its derivatives include the following spherical cellulose particles marketed by Daito Kasei Kogyo Co., Ltd. in Japan: Cellulobeads USF with a particle size of 4 μm (oil absorption is 250 ml / 100 g) (porous cellulose). ) Is included.

The silica powders mentioned include porous silica microspheres, in particular Sunsphere® H31 and Sunsphere® H51 (oil absorption equal to 150 ml / 100 g) by Asahi Glass Co., Ltd., MSS-500- by Kobo. Sold under the name 3H; Amorphous hollow silica particles, especially those sold by Kobo under the name Silica Shells (oil absorption equal to 550 ml / 100 g); Silysia 350 by Fuji Silysia Chemical Ltd. Porous silica microspheres sold under the name of (oil absorption equal to 310 ml / 100 g); and silica powder sold by Oriental Silycas under the name Finesil X35 (oil absorption equal to 380 ml / 100 g). included.

A particularly mentioned silicate is aluminum silicate (oil absorption equal to 195 ml / 100 g) sold by Kyowa Chemical Industry Co., Ltd. under the name of Kyowaad® 700PEL.

The pearlite powders specifically mentioned are products sold by World Minerals under the names Optimat® 1430 OR and Optimat® 2550 OR (oil absorption equal to 240 ml / 100 g).

Magnesium carbonate powder, in particular, is a product sold by Buschle & Lepper under the name Tipo Carbomagel® (oil absorption equal to 214 ml / 100 g).

Magnesium carbonate / magnesium hydroxide powder, which is particularly mentioned, is a product of mMgCO ₃ -Mg (OH) ₂ -nH ₂ O sold by Nittetsu Mining Co., Ltd. under the name of Mg Tube (oil absorption is 250 to 310 ml / 100 g). Is equal to).

The hydrophilic oil absorbing powder preferably contains at least one selected from the group consisting of cellulose, silica, pearlite, and mixtures thereof.

(Hydrophobic oil absorbing powder)
For the purposes of the present invention, the term "hydrophobic" oil-absorbing powder means that the powder (or particles) is individually dispersed in the oil so that aggregates are not formed.

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

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

The hydrophobic oil absorbing powder may be organic or inorganic.

Organic hydrophobic oil absorbing powder:
Organic hydrophobic oil-absorbing powders are polyamide (especially nylon-6) powders, acrylic polymers, especially polymethyl methacrylate, polymethyl methacrylate / ethylene glycol dimethacrylate, polyallyl methacrylate / ethylene glycol dimethacrylate, or ethylene glycol dimethacrylate / lauryl methacrylate. You can choose from the group consisting of copolymer powders and mixtures thereof. The material may be crosslinked.

The organic hydrophobic oil absorbing powder may be preferably selected from acrylic polymers, especially those of ethylene glycol dimethacrylate / lauryl methacrylate copolymers.

Examples of organic hydrophobic oil absorbing powders include the fillers described below.

Acrylic polymer powders such as porous polymethylmethacrylate (INCI name methylmethacrylate cross-polymer), for example, a sphere sold under the name Covabead LH85 by Sensorient, sold under the name Microsponge 5640 by Cardinal Health Technologies. Porous polymethylmethacrylate / ethylene glycol dimethacrylate sphere (oil absorption equal to 155 ml / 100 g), ethylene glycol dimethacrylate / lauryl methacrylate crosslinked copolymer powder, especially the name of Polytrap® 6603 manufactured by Amcol Health & Beauty Solutions. Acrylonitrile / methylmethacrylate / vinylidene chloride copolymer (oil absorption equal to 1,040 ml / 100 g) sold by Akzo Novel under the name Expancel 551DE40D42. included.

The polyamide powders mentioned include nylon-6 powders, especially products sold by Ube Kosan Co., Ltd. under the name Pomp610 (oil absorption equal to 202 ml / 100 g).

Inorganic hydrophobic oil absorbing powder:
The inorganic hydrophobic oil absorbing powder may have at least one inorganic core and at least one hydrophobic coating.

The inorganic hydrophobic oil-absorbing powder is preferably selected from hydrophobic silica, preferably hydrophobic silica airgel, more preferably hydrophobic aerogel of silica syllate, and mixtures thereof.

The term "hydrophobic silica" is understood to mean any silica that has been treated so that its surface is hydrophobic.

Hydrophobic silica, in particular silica silylate, may be based on silica airgel, a porous material obtained by replacing the liquid component of silica gel with air (by drying).

They are generally synthesized in a liquid medium by the sol-gel method and then dried, usually by extraction with a supercritical fluid, the most commonly used supercritical fluid is supercritical CO ₂ . This type of drying makes it possible to avoid shrinkage of pores and materials. The sol-gel process and various drying operations are described in detail in Brinker CJ and Scherer GW, Sol-Gel Science, New York, Academic Press, 1990.

Airgel is a material with high porosity. In the present specification, silica airgel generally refers to solid silica having a porous structure obtained by replacing the medium contained in the wet silica gel with air by drying the wet silica gel while maintaining the solid network structure of silica. Point to. Porosity is the amount of air contained in the apparent volume of a material expressed as a volume percentage. The hydrophobic silica airgel of the present invention may have a porosity of 60% or more, preferably 70% or more, more preferably 80% or more.

Hydrophobic silica airgel particles have a specific surface area (SW) per mass unit in the range of 500 to 1,500 m ² / g, preferably 600 to 1,200 m ² / g, more preferably 600 to 800 m ² / g, and / or.
Volume in the range of 1 to 1,500 μm, preferably 1 to 1,000 μm, more preferably 1 to 100 μm, particularly 1 to 30 μm, more preferably 5 to 25 μm, more preferably 5 to 20 μm, even more preferably 5 to 15 μm. It can indicate a size expressed in average diameter (D [0.5]).

The specific surface area per unit of mass can be determined by the nitrogen absorption method known as the BET (Brunauer-Emmett-Teller) method, which is described in The Journal of the American Chemical Society, Vol. 60, p. 309, Described in February 1938, it corresponds to the international standard ISO 5794/1 (Annex D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

The size of hydrophobic silica airgel particles can be measured by static light scattering using a commercially available particle size analyzer, MasterSizer 2000 from Malvern. The data is processed based on the Mie scattering theory. This theory, which is rigorous with respect to isotropic particles, allows the determination of "effective" particle sizes in the case of non-spherical particles. This theory is described in detail in Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

Hydrophobic silica airgel particles can advantageously exhibit a packing density (r) in the range 0.04 g / cm ³ to 0.10 g / cm ³ , preferably 0.05 g / cm ³ to 0.08 g / cm ³ . can.

In the context of the present invention, this density, known as the packing density, can be evaluated according to the following protocol:
Pour 40 g of powder into a graduated cylinder;
Then place the graduated cylinder on a Stampf Volumeter Stav 2003 device;
Subsequently, the graduated cylinder is subjected to a series of 2500 filling operations (this operation is repeated until the volume difference between the two consecutive tests is less than 2%);
The final volume Vf of the filled powder is then measured directly in a graduated cylinder. The packing density is determined by the m / Vf ratio (Vf is cm ³ and w is represented by g), which in this case is 40 / Vf.

US Pat. No. 7,470,725 may be referred to for the preparation of hydrophobic silica airgel particles surface-modified by silylation.

In particular, hydrophobic silica airgel particles surface-modified with a trimethylsilyl group are used.

Examples of inorganic hydrophobic oil-absorbing powders include polydimethylsiloxane-coated amorphous silica microspheres, especially those sold under the names of Sunsphere (registered trademark) H33 and Sunsphere (registered trademark) H53 (oil absorption amount is 400 ml / 100 g). (Equal to), precipitated silica powder surface-treated with inorganic wax, for example, precipitated silica treated with polyethylene wax, especially those sold by Evonik-Degussa under the name Acematt OR 412 (oil absorption 398 ml / 100 g). (Equal to), and silica acylate (oil absorption equal to 1,040 ml / 100 g) sold by Dow under the name VM-2270.

As the inorganic hydrophobic oil absorbing powder, it is preferable to use silica silylate sold by Dow under the name VM-2270, the particles having an average size in the range of 5 to 15 μm and 600 to 800 m ² / g. The specific surface area per mass unit in the range of is shown.

Hydrophobic silica airgel particles can be characterized by the spherical shape of each particle. Due to this spherical shape, the hydrophobic silica airgel particles can provide good smoothness to the cosmetic composition. The sphericality of the hydrophobic silica airgel can be determined by the average roundness.

Spherical hydrophobic silica airgel particles can have an average roundness of 0.8 or higher, preferably 0.82 or higher. The spherical hydrophobic silica airgel can have an average roundness of less than 1, preferably 0.99 or less, more preferably 0.98 or less, even more preferably 0.97 or less, even more preferably 0.96 or less, most preferably 0.95 or less. ..

The "average roundness" can be determined by an image analysis method. In particular, "average roundness" is obtained by image analysis of scanning electron microscope (SEM) images of more than 2,000 aerogel particles observed at a magnification of 1,000 by secondary electron detection using a scanning electron microscope (SEM). It can be an arithmetic average of the roundness to be obtained.

The "roundness" of each airgel particle is a value determined by the following equation:
C = 4πS / L ²
[In the formula, C represents the roundness, S represents the area (projected area) of the airgel particles in the image, and L represents the length of the circumference (outer circumference) of the airgel particles in the image].
As the average roundness approaches 1, the shape of each particle becomes more spherical.

Hydrophobic silica airgel particles that can be used in accordance with the present invention are preferably of the type of silylated silica (INCI name: silica silicate). Preferably, the hydrophobic silica airgel particles may be those described in JP-A-2014-088307, JP-A-2014-218433, or JP-A-2018-177620.

It is preferable to use a hydrophobic airgel of silica syllate as the inorganic hydrophobic oil absorbing powder.

Hydrophobicity of Silica Sililate The hydrophobicity of airgel is that the hydrophobizing agent is present on the surface of silica by the following formula:
≡ Si-OH
(In the formula, the symbol "≡" represents the valence of the remaining 3 Si atoms)
The silanol group is reacted with the silanol group represented by the following formula:
(≡Si-O-) _(4-n) SiR _n
(In the equation, n is an integer from 1 to 3, each R is an independent hydrocarbyl group, and two or more Rs may be the same or different from each other, where n is 2 or more).
It can be obtained by converting to the group represented by.

The hydrophobizing agent may be a silylating agent. Therefore, according to one preferred embodiment, in the hydrophobic airgel of silica silicate, the silica particles can be surface modified by silylation. Examples of the silylating agent include treatment agents having one of the following formulas (1) to (3).

Equation (1):
R _n SiX _(4-n)
[In the formula, n represents an integer of 1 to 3, R represents a hydrocarbyl group, and X is desorbed from the molecule by breaking the bond with the Si atom during reaction with a compound having a hydroxyl group. Represents a group that can (ie, a leaving group), where each R can be different, where n is greater than or equal to 2, and each X can be different, where n is less than or equal to 2.]

Equation (2):

[In the formula, R ¹ represents an alkylene group, R ² and R ³ independently represent a hydrocarbyl group, and R ⁴ and R ⁵ independently represent a hydrogen atom or a hydrocarbyl group].

Equation (3):

[In the equation, R ⁶ and R ⁷ independently represent hydrocarbyl groups, m represents an integer from 3 to 6, and if there are two or more R ⁶ , each R ⁶ may be different, R ⁷ Each R ⁷ may be different if there are more than one.]

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

Examples of the leaving group represented by X include halogen atoms such as chlorine and bromine, alkoxy groups such as methoxy and ethoxy groups, and groups represented by -NH-SiR ₃ (in the formula, the definition of R is: It is the same as the definition of R in Eq. (1)).

Specific examples of the hydrophobic agent represented by the above formula (1) include chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, and hexamethyldisilazane.

Most preferably, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, and / or hexamethyldisilazane may be used from the viewpoint of favorable reactivity.

The number of bonds between the Si atom and the silanol group on the silica skeleton varies depending on the number of leaving groups X (4-n). For example, if n is 2, the following join occurs:
(≡Si-O-) ₂ SiR ₂

If n is 3, the following joins occur:
≡ Si-O-SiR ₃

In this way, silanol groups can be silylated, thereby hydrophobizing.

In the above formula (2), R ¹ may be an alkylene group, preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms.

In the above formula (2), R ² and R ³ are independently hydrocarbyl groups, and the same preferable group as the group of R in the formula (1) can be mentioned. R ⁴ represents a hydrogen atom or a hydrocarbyl group, and when it is a hydrocarbyl group, the same preferable group as R in the formula (1) can be mentioned. Treatment of silica gel with the compound of formula (2) (cyclic silazane) results in cleavage of the Si-N bond by reaction with the silanol group, thus resulting in the following bonds on the surface of the silica skeleton in the gel:
(≡Si-O-) ₂ SiR ² R ³

In this way, the silanol group can also be silylated by the cyclic silazan of the above formula (2), whereby hydrophobization can be carried out.

Specific examples of the cyclic silazane represented by the above equation (3) include hexamethylcyclotrisilazane and octamethylcyclotetrasilazane.

In the above formula (3), R ⁶ and R ⁷ are independently hydrocarbyl groups, and the same preferable groups as R in the formula (2) can be mentioned. m represents an integer from 3 to 6. Treatment of silica gel with the compound of formula (3) (cyclic siloxane) results in the following bonds on the surface of the silica skeleton in the gel:
(≡Si-O-) ₂ SiR ⁶ R ⁷

In this way, the silanol group can also be silylated by the cyclic siloxane of the above formula (3), whereby hydrophobization can be carried out.

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

Hydrophobic aerogels of silica silicate produce silica sol, turn the sol into a gel, age the gel, wash the aged gel, replace the water in the washing gel with a solvent, and treat the gel with a hydrophobizing agent. , Can be prepared by drying the hydrophobized silica.

The specific surface area of the hydrophobic airgel of silica syllate determined by the BET method is 200 m ² / g or more, preferably 400 m ² / g or more, more preferably 500 m ² / g or more, and 1200 m ² / g or less. It can be preferably 1000 m ² / g or less, more preferably 800 m ² / g or less.

The pore volume of the hydrophobic airgel of silica syllate determined by the BJH method is 1 ml / g or more, preferably 2 ml / g or more, more preferably 3 ml / g or more, and 10 ml / g or less, preferably 10 ml / g or less. It can be 8 ml / g or less, more preferably 7 ml / g or less. The peak pore radius of the hydrophobic silica airgel of silica syllate determined by the BJH method is 5 nm or more, preferably 10 nm or more, more preferably 12 nm or more, 50 nm or less, preferably 40 nm or less, more preferably. It can be 30 nm or less.

The "pore volume determined by the BJH method" is described above by the BJH method (Barrett, E.P .; Joyner, LG .; Halenda, P.P., J. Am. Chem. Soc. 73, 373 (1951)). It refers to the pore volume derived from pores with a pore radius of 1 nm to 100 nm, which is obtained by analyzing the adsorption isotherm on the nitrogen adsorption side obtained by the same method as "specific surface area determined by the BET method". The "peak pore radius determined by the BJT method" is the cumulative pore volume based on the log of the pore radius obtained by analyzing the adsorption isotherm on the nitrogen adsorption side obtained by the same method as above by the BJH method. It refers to the value of the pore radius that produces the peak in the pore distribution curve (volume distribution curve) plotted with the differentiation on the vertical axis and the pore radius on the horizontal axis.

The average particle size of the hydrophobic airgel of silica syllate can be 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and an average of 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less by an image analysis method. It may have a particle size.

The "average particle size" here can be measured by an image analysis method. In particular, the "average particle size" value is, for example, a scanning electron microscope (SEM) image of more than 2,000 aerogel particles observed at a magnification of 1,000 by secondary electron detection using a scanning electron microscope (SEM). It is an arithmetic average of the equivalent circle diameter that can be obtained by image analysis. The "equivalent circle diameter" of each airgel particle is the diameter of a circle having an area equal to the area (projected area) of the airgel particles in the image.

Preferably, the hydrophobic airgel of silica syllate has an oil absorption capacity that can be measured at the wet point of 2 ml / g or more, preferably 3 ml / g or more, more preferably 4 ml / g or more, as described above. , Most preferably 5 ml / g or more, preferably 12 ml / g or less, preferably 10 ml / g or less, more preferably 8 ml / g or less, and most preferably 7 ml / g or less.

The amount of the filler (b) in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more with respect to the total mass of the composition.

The amount of the filler (b) in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

The amount of the filler (b) in the composition according to the present invention is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5 with respect to the total mass of the composition. It may be% by mass.

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

(c) The amount of water may be 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the composition.

(c) The amount of water may be 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, based on the total mass of the composition.

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

[pH]
The pH of the composition according to the invention can be 3-9, preferably 3.3-8.5, more preferably 3.5-8.

At a pH of 3-9, (a) the particles can be very stable.

The pH of the composition according to the invention is adjusted by adding at least one alkaline agent and / or at least one acid other than a non-polymeric acid having a pKa value of two or more or a salt thereof, and (a) in the particles. It can be adjusted by incorporating it. The pH of the composition according to the invention can also be adjusted by adding at least one buffer.

(Alkaline agent)
The composition according to the present invention may contain at least one alkaline agent. Two or more kinds of alkaline agents may be used in combination. Therefore, a single type of alkaline agent or a combination of different types of alkaline agents can be used.

The alkaline agent may be an inorganic alkaline agent. The inorganic alkaline agent is selected from the group consisting of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates and monohydrogen phosphates such as sodium phosphate or sodium monohydrogen phosphate. Is preferable.

Examples of the inorganic alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Sodium hydroxide is preferable as the inorganic alkaline agent.

The alkaline agent may be an organic alkaline agent. Organic alkaline agents include monoamines and their derivatives, diamines and their derivatives, polyamines and their derivatives, basic amino acids and their derivatives, basic amino acid oligomers and their derivatives, basic amino acid polymers and their derivatives, urea and its derivatives, It is preferably selected from the group consisting of guanidine and its derivatives.

Examples of organic alkaline agents include alkanolamines such as mono-, di- and tri-ethanolamines, and isopropanolamines; ureas, guanidines and derivatives thereof; basic amino acids such as lysine, ornithine or arginine; and diamines such as: Structure:

(In the formula, R represents an alkylene such as propylene optionally substituted with a hydroxyl or C ₁ to C ₄ alkyl group, and R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, Alkyl groups (indicating C ₁ to C ₄ hydroxyalkyl groups) can be mentioned, which can be exemplified by 1,3-propanediamine and its derivatives. Arginine, urea and monoethanolamine are preferred.

The alkaline agent has a total amount of 0.01% by mass to 15% by mass, preferably 0.02% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass, based on the total mass of the composition, depending on its solubility. Can be used.

(acid)
The composition according to the invention may contain at least one acid. Two or more acids may be used in combination. Therefore, a single type of acid or a combination of different types of acids can be used.

The acid may be any inorganic or organic acid commonly used in cosmetics, preferably an inorganic acid. Monovalent acids and / or polyvalent acids can be used. Monovalent acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) can be used. HCl is preferred.

The acid is used in a total amount of 0.01% by mass to 15% by mass, preferably 0.02% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass, based on the total mass of the composition, depending on its solubility. can do.

(Buffer)
The composition according to the invention may contain at least one buffer. Two or more buffers may be used in combination. Therefore, a single type of buffer or a combination of different types of buffer can be used.

The buffers include acetate buffer (eg acetic acid + sodium acetate), phosphate buffer (eg sodium dihydrogen phosphate + disodium hydrogen phosphate), citrate buffer (eg citrate + sodium citrate). ), Borate buffer (eg, borate + sodium borate), tartrate buffer (eg, tartrate + sodium tartrate dihydrate), Tris buffer (eg, Tris (hydroxymethyl) aminomethane), and Hepes. A buffer solution (4- (2-hydroxyethyl) -1-piperazine ethanesulfonic acid) can be mentioned.

[oil]
The composition according to the invention may contain at least one oil. If more than one (d) oil is used, they may be the same or different.

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

The oil may be a hydrocarbon oil, a non-polar oil such as silicone oil, a vegetable oil or an animal oil, a polar oil such as an ester oil or an ether oil, or a mixture thereof.

The oil may be selected from the group consisting of plant or animal derived oils, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

Examples of vegetable oils are, for example, apricot oil, flaxseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, southern ka oil, sunflower oil, benivana oil, jojoba oil, sunflower oil, almond oil, rapeseed oil. , Sesame oil, soybean oil, peanut oil, and mixtures thereof.

Examples of animal oils include squalene and squalene, for example.

Examples of synthetic oils include alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

Ester oils are preferably saturated or unsaturated linear or branched C ₁ to C ₂₆ aliphatic monoacids or polyacids and saturated or unsaturated linear or branched C ₁ to C ₂₆ . It is a liquid ester with an aliphatic monovalent alcohol or a polyhydric alcohol, and the total number of carbon atoms of these esters is 10 or more.

Preferably, in the case of an ester of a monohydric alcohol, at least one of the alcohols and acids from which the ester of the present invention is derived is branched.

Among the monoesters of monoacids and monohydric alcohols, ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristate, such as isopropyl myristate or ethyl myristate, isosetyl stearate, 2-ethylhexyl isononanoate, Examples thereof include isononyl isononanoate, isodecyl neopentate and isostearyl neopentate.

C ₄ to C ₂₂ Dicarboxylic acid or tricarboxylic acid and ester of C ₁ to C ₂₂ alcohol, as well as monocarboxylic acid, dicarboxylic acid or tricarboxylic acid and non-sugar C ₄ to C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy Esters with alcohol can also be used.

Specific examples include: diethyl sevacinate, isopropyl lauroyl sarcosin isopropyl, diisopropyl sevacinate, bis sevacinate (2-ethylhexyl), diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis adipate ( 2-Ethylhexyl), diisostearyl adipate, bis maleate (2-ethylhexyl), triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactic acid, glyceryl trioctanoate, trioctyldodecyl citrate, citrate Trioleyl acid, neopentyl glycol diheptate, and diethylene glycol diisononanonate.

As the ester oil, sugar esters and diesters of C ₆ to C ₃₀ , preferably C ₁₂ to C ₂₂ fatty acids can be used. The term "sugar" means an oxygenated hydrocarbon compound containing or without an aldehyde or ketone functional group, containing some alcohol functional groups and containing at least 4 carbon atoms. Is recalled. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

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

The sugar ester of the fatty acid is, in particular, a group containing an ester or a mixture of the above-mentioned sugar and a linear or branched saturated or unsaturated C ₆ to C ₃₀ , preferably C ₁₂ to C ₂₂ fatty acid. You can choose from. These compounds, if unsaturated, can have 1 to 3 conjugated or unconjugated carbon-carbon double bonds.

The ester due to this modification can also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters include, for example, oleic acid ester, lauric acid ester, palmitic acid ester, myristic acid ester, behenic acid ester, coconut fatty acid ester, stearic acid ester, linoleic acid ester, linolenic acid ester, capric acid ester and arachidonic acid ester. , Or a mixture thereof, for example a mixed ester of oleopalmitic acid, oleostearic acid, and palmitostearic acid, and pentaerythrityl tetraethylhexanoate.

More specifically, monoesters and diesters, especially monooleic acid or dioleic acid esters of sucrose, glucose or methyl glucose, stearic acid esters, behenic acid esters, oleopalmitic acid esters, linoleic acid esters, linolenic acid esters and oleosteer. Acid esters are used.

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

Examples of preferred ester oils include, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanate, octyldodecyl octanate, isodecyl neopentate, myristyl propionate, 2-ethylhexanoic acid 2. -Ethylhexyl, 2-ethylhexyl octanate, 2-ethylhexyl caprylate / 2-ethylhexyl caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylic carbonate, isopropyl lauroyl sarcosate, isononyl isononanoate, ethylhexyl palmitate, laurin Isohexyl acid, hexyl laurate, isosetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, tri (2-ethylhexanoic acid) glyceryl, tetra (2-ethylhexanoic acid) pentaerythrityl, 2-ethylhexyl succinate , Diethyl sebacate, and mixtures thereof.

Examples of artificial triglycerides include, for example, capryl caprylic acid glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, tri (capric acid / caprylic acid) glyceryl and Tri (caprylic acid / caprylic acid / linolenic acid) glyceryl can be mentioned.

Examples of silicone oils include linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc., cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, etc. Examples thereof include decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and mixtures thereof.

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

These silicone oils may also be organically modified. Organically modified silicones that can be used in accordance with the present invention are silicone oils that contain one or more organic functional groups as defined above and in their structure that are attached via hydrocarbon-based groups.

Organopolysiloxane is defined in more detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. The organopolysiloxane may be volatile or non-volatile.

If they are volatile, silicones are more specifically selected from those having a boiling point between 60 ° C and 260 ° C, and even more specifically:
(i) Cyclic polydialkylsiloxane containing 3-7, preferably 4-5 silicon atoms. These are, for example, octamethylcyclotetrasiloxanes sold under the name Volatile Silicone® 7207 by Union Carbide or under the name Silbione® 70045 V2 by Rhodia, Union Carbide. Sold by Rhodia under the name Volatile Silicone® 7158, Decamethyl Cyclopentasiloxane sold by Rhodia under the name Silbione® 70045 V5, and Momentive Performance Materials under the name Silsoft 1217. Dodecamethylcyclopentasiloxane, as well as mixtures thereof. Cyclocopolymers of the type such as dimethylsiloxane / methylalkylsiloxane of the following formula, for example, Silicone Volatile® FZ 3109 sold by Union Carbide can also be mentioned.

Mixtures of cyclic polydialkylsiloxanes and organosilicon compounds, such as mixtures of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50), and octamethylcyclotetrasiloxane and oxy-1,1'-bis (2). , 2,2', 2', 3,3'-hexatrimethylsilyloxy) A mixture with neopentane can also be mentioned.
(ii) A linear volatile polydialkylsiloxane containing 2-9 silicon atoms and having a viscosity of 5 × 10 ^-6 m ² / s or less at 25 ° C. An example is the decamethyltetrasiloxane sold under the name SH 200, in particular by Toray Silicone. Silicones in this category are also described in the papers published in Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. Silicone viscosities are measured at 25 ° C. according to ASTM Standard 445 Annex C.

Non-volatile polydialkylsiloxane may be used. These non-volatile silicones are selected from polydialkylsiloxanes in more detail, and among them, polydimethylsiloxanes mainly containing a trimethylsilyl terminal group can be mentioned.

Among these polydialkylsiloxanes, the following commercial products can be mentioned without limitation:
--Silbione® 47 and 70 047 series of Silbione® oils or Mirasil® oils sold by Rhodia, eg 70 047 V 500 000 oils;
--Mirasil® series oil sold by Rhodia;
--200 series oils from Dow Corning, eg DC200 with a viscosity of 60,000 mm ² / s; and
--General Electric's Viscasil® oil and General Electric's SF series specific oils (SF 96, SF 18).

Polydimethylsiloxane containing a dimethylsilanol end group, known by the name Dimethiconol (CTFA), such as Rhodia's 48 Series oils can also be mentioned.

Among the silicones containing an aryl group, polydiarylsiloxane, particularly polydiphenylsiloxane and polyalkylarylsiloxane, for example, phenylsilicone oil can be mentioned.

Phenylsilicone oil can be selected from the following phenylsilicone:

(During the ceremony,
R ₁ to R ₁₀ are independent of each other, saturated or unsaturated, linear, cyclic or branched C ₁ to C ₃₀ hydrocarbon groups, preferably C ₁ to C ₁₂ hydrocarbon groups, and more. It is preferably a C ₁ to C ₆ hydrocarbon group, specifically a methyl, ethyl, propyl or butyl group.
m, n, p, and q are integers of 0 to 900 including both ends, preferably 0 to 500 including both ends, and more preferably 0 to 100 including both ends, independently of each other.
However, the sum n + m + q is other than 0).

Examples that can be given are products sold under the following names:
--70 641 series of Silbione® oils from Rhodia;
--Rhodia Rhodorsil® 70 633 and 763 series oils;
--Dow Corning 556 Cosmetic Grade Fluid;
--Bayer PK series silicone, for example product PK20;
--Specific oils in the SF series from General Electric, such as SF 1023, SF 1154, SF 1250, and SF 1265.

As the phenylsilicone oil, phenyltrimethicone (in the above formula, R ₁ to R ₁₀ are methyl, p, q, and n = 0, and m = 1) is preferable.

The organically modified liquid silicone may contain polyethylene oxy and / or polypropylene oxy groups in particular. Therefore, silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd. and Silwet® L722 and L77, which are oils manufactured by Union Carbide, can be mentioned.

Hydrocarbon oils can be selected from:
—— Linear or branched, optionally cyclic C ₆ to C ₁₆ lower alkanes (examples such as hexane, undecane, dodecane, tridecane, and isoparaffin, eg isohexadecane, isododecane and isodecane. There is), and
—— Linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petrolatum, polydecene and hydrogenated polyisobutene, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (eg liquid paraffin), paraffin, petrolatum or petrolatum, naphthalene and the like; hydropolyisobutene. , Isoeicosan, and decene / butene copolymers; and mixtures thereof.

The term "fat" in fatty alcohols means to include a relatively large number of carbon atoms. Therefore, alcohols having 4 or more, preferably 6 or more, more preferably 12 or more carbon atoms are included in the range of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

Fatal alcohols are saturated and unsaturated, containing structural R-OH (where R is 4-40 carbon atoms, preferably 6-30 carbon atoms, more preferably 12-20 carbon atoms. Saturated, can have (chosen from linear and branched groups). In at least one embodiment, R can be selected from C ₁₂ to C ₂₀ alkyl groups and C ₁₂ to 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, linoleil alcohol, palmitrail alcohol, arachidnyl alcohol, Elsyl alcohol and mixtures thereof can be mentioned.

The fatty alcohol is preferably saturated fatty alcohol.

Thus, the fatty alcohols are linear or branched, saturated or unsaturated C ₆ to C ₃₀ alcohols, preferably linear or branched, saturated C ₆ to C ₃₀ alcohols, more preferably straight. You can choose from chained or branched, saturated C ₁₂ to C ₂₀ alcohols.

The term "saturated fatty alcohol" here means an alcohol having a long aliphatic saturated carbon chain. It is preferred that the saturated fatty alcohol be selected from any linear or branched saturated C ₆ -C ₃₀ fatty alcohol. Among the linear or branched saturated C ₆ to C ₃₀ fatty alcohols, the linear or branched saturated C ₁₂ to C ₂₀ fatty alcohols may be preferably used. Any linear or branched saturated C ₁₆ -C ₂₀ fatty alcohol may be more preferably used. Branched C ₁₆ -C ₂₀ fatty alcohols may be used even more preferably.

Examples of saturated fatty alcohols include 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), and behenyl alcohol can be used as saturated fatty alcohols.

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.

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

(A) Oils that are (a) surrounded by particles or (a) present in the hollow of capsules formed by particles cannot come into direct contact with keratinous substances such as skin. Therefore, it is considered that the composition according to the present invention does not give a sticky or oily feeling even when (d) the oil has a sticky or oily feeling.

The amount of (d) oil in the composition according to the present invention may be 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more with respect to the total mass of the composition.

The amount of (d) oil in the composition according to the present invention may be 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less with respect to the total mass of the composition.

The amount of (d) oil in the composition according to the present invention is 0.1% by mass to 50% by mass, preferably 0.5% by mass to 40% by mass, and more preferably 1% by mass to 30% by mass with respect to the total mass of the composition. It may be% by mass.

[Optional additive]
In addition to the above-mentioned components, the composition according to the present invention contains components typically used in cosmetics, specifically, surfactants (particularly nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickening. Agents, organic volatile or non-volatile solvents, hydrophilic or hydrophobic UV shielding agents, (d) silicones and silicone derivatives other than oils, natural extracts derived from animals or plants, waxes, etc., impair the effects of the present invention. It may be included within the range not included.

In the composition according to the present invention, the above optional additives are added to the total mass of the composition in an amount of 0.01% by mass to 50% by mass, preferably 0.05% by mass to 30% by mass, and more preferably 0.1% by mass or more. It may be contained in an amount of 10% by mass.

[Composition]
The compositions according to the invention may be intended to be used as cosmetic compositions. Therefore, the cosmetic composition according to the present invention may be intended to be applied to a keratin substance. The keratin substance in the present specification means a substance containing keratin as a main component, and examples thereof include skin, scalp, nails, lips, hair and the like. Therefore, the cosmetic composition according to the invention is preferably used for keratin substances, especially cosmetic methods for the skin.

Therefore, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin make-up composition, and more preferably a skin care composition.

The composition according to the present invention can be prepared by mixing the above essential components with optional components according to any of the methods well known to those skilled in the art.

If necessary, the above-mentioned essential components or optional components may be heated. Therefore, heating can be performed when the above essential components and optional components are mixed.

The composition according to the invention may be in the form of an emulsion, an O / W emulsion or a W / O emulsion, if it contains (d) oil. The composition according to the invention is preferably in the form of an O / W emulsion, because it can impart a refreshing sensation due to (c) water forming its outer phase.

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

Therefore, the present invention is also a method for preparing a film having a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more, still more preferably 2 μm or more, preferably a decorative film.
A step of applying the composition according to the present invention to a substrate, preferably a keratin substance, more preferably to the skin.
It also relates to a method comprising a step of drying the composition.

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

Since the method for preparing a film which may be related to the present invention includes a step of applying the composition according to the present invention to a base material, preferably a keratin substance, more preferably to the skin, and a step of drying the composition. The method does not require any spin coating or spraying, and therefore even relatively thick films can be easily prepared. Therefore, the method for preparing a film that may be related to the present invention can prepare a relatively thick film without using any special equipment such as a spin coater and a spray machine.

Even if the film prepared by the above method is relatively thick, it can still be thin and transparent and therefore may not be easy to perceive. Therefore, the film can preferably be used as a decorative film.

When the base material is not a keratin substance such as skin, the composition according to the present invention can be applied to a base material made from any material other than keratin. The material of the non-keratin substrate is not limited. Two or more materials may be used in combination. Therefore, 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.

When the substrate is not a keratin substance, the substrate is preferably water soluble, because it is possible to leave a film by washing the substrate with water. Examples of the water-soluble material include poly (meth) acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate and the like. PVA is preferred.

When the non-keratin substrate is in the form of a sheet, it has a thickness that exceeds the thickness of the film prepared by the above method to facilitate the handling of the film attached to the substrate sheet. May be good. The thickness of the non-keratin substrate sheet is not limited, but may be 1 μm to 5 mm, preferably 10 μm to 1 mm, and more preferably 50 to 500 μm.

It is more preferable that the film prepared by the above method can be peeled off from the non-keratin substrate. The peeling method is not limited. Therefore, the film prepared by the above method may be peeled off from the non-keratin base material, or may be peeled off by dissolving the base material sheet in a solvent such as water.

Therefore, the present invention also
(1) A film having a thickness of more than 0.1 μm, more preferably 1.5 μm or more, still more preferably 2 μm or more, preferably a decorative film.
A step of applying the composition according to the present invention to a substrate, preferably a keratin substance, more preferably to the skin.
A film prepared by a method comprising a step of drying the composition,
and
(2) A film having a thickness of more than 0.1 μm, more preferably 1.5 μm or more, still more preferably 2 μm or more, preferably a decorative film.
A coating containing at least one cationic polymer and at least one anionic polymer, and at least one non-polymeric acid or salt thereof having two or more pKa values, and optionally at least one oil. Also related to.

The above description of cationic and anionic polymers, as well as non-polymeric acids or salts thereof having two or more pKa values and the above oils can be applied to those in the above coatings (1) and (2).

The film thus obtained as 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 treated as an independent sheet without the assistance of a substrate or support. Therefore, the term "independence" can have the same meaning as "self-supporting".

The above film is preferably hydrophobic.

The term "hydrophobic" as used herein refers to the solubility of a polymer in water (preferably 1 liter volume) at 20-40 ° C, preferably 25-40 ° C, more preferably 30-40 ° C. It means that it is less than 10% by mass, preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1% by mass with respect to the total mass. Most preferably, the polymer is not soluble in water.

If the above film is hydrophobic, the film can have water resistance properties and therefore remain on the keratinous material such as skin even if the surface of the keratinous material is wet, for example by sweat and rain. can do. Therefore, when the film imparts some cosmetic effect, the cosmetic effect can be sustained for a long time.

On the other hand, the above-mentioned film can be easily removed from a keratin substance such as skin under alkaline conditions such as pH 8 to 12, preferably 9 to 11. Therefore, the above film is difficult to remove with water, but can be easily removed with soap that can provide such alkaline conditions.

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

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

The term "biodegradable" polymer herein means that a polymer can be degraded or divided in vivo, for example by metabolism of the organism itself or of microorganisms that may be present in the organism. Also, biodegradable polymers can be degraded by hydrolysis.

If the above coating contains a biocompatible and / or biodegradable polymer, it is mild or non-irritating to the skin and does not cause any rash. In addition, the use of biocompatible and / or biodegradable polymers allows the above coatings to adhere well to the skin.

The above coatings can be used for keratin substances, preferably for cosmetic treatments of the skin, especially the face. The above film may have 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.

When the above film contains at least one hydrophilic or water-soluble UV shielding agent, the film can provide the UV shielding effect derived from the hydrophilic or water-soluble UV shielding agent. Generally, hydrophilic or water-soluble UV shielding agents can be removed from the surface of keratin substrates such as skin by water such as sweat and rain. However, since the hydrophilic or water-soluble UV shielding agent is contained in the above-mentioned film, it is difficult to remove the hydrophilic or water-soluble UV shielding agent with water, whereby the UV shielding agent lasts for a long time. The effect is brought about.

[Cosmetology method and use]
The present invention also
A beauty method for keratin substances such as skin
The step of applying the composition according to the present invention to the keratin substance, and
A method comprising the steps of drying the composition to form a cosmetic film on the keratin substance,
It also relates to the use of the composition according to the present invention for preparing a cosmetic film on a keratin substance such as skin.

The cosmetological method as used herein means a non-therapeutic cosmetological method for caring for and / or making up the surface of a keratin substance such as skin.

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

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

Accordingly, the above-mentioned cosmetic film can be made water resistant, and therefore, even when the surface of the keratin substance is wet with sweat and rain, for example, it remains on the keratin substance such as skin. Can be done. On the other hand, the above-mentioned cosmetic film can be easily removed from a keratin substance such as skin under alkaline conditions. Therefore, the above-mentioned cosmetic film is difficult to remove with water, but can be easily removed with soap that can bring about alkaline conditions.

When the above-mentioned cosmetic film contains a UV blocking agent that may be present in the composition according to the present invention, the above-mentioned cosmetic film protects keratin substances such as skin from ultraviolet rays, thereby suppressing darkening of the skin and skin. It can improve the color and uniformity of the skin and / or treat the aging of the skin.

Further, the above-mentioned cosmetic film absorbs or adsorbs a bad odor due to the characteristics of the polyion complex particles in the cosmetic film even when the cosmetic film does not contain any cosmetic active ingredient, and / or, for example, a stain or a contaminant. May have cosmetic effects such as protecting keratin substances from.

In addition, the above-mentioned cosmetic film can immediately change or modify the appearance of the skin by changing the light reflection or the like on the skin even when the cosmetic film does not contain any cosmetic active ingredient. .. Therefore, the above-mentioned cosmetic film may be able to hide skin defects such as pores or wrinkles. Further, the above-mentioned cosmetic film can immediately change or modify the tactile sensation of the skin by changing the surface roughness on the skin and the like. Further, the above-mentioned cosmetic film can immediately protect the skin by covering the surface of the skin as a barrier and shielding the skin from environmental stresses such as pollutants and impurities.

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

If the above cosmetic film contains at least one additional cosmetological active ingredient other than (d) oil, the cosmetological film can have the cosmetological effect provided by the additional cosmetological active ingredient. For example, if the cosmetic film contains at least one cosmetic active ingredient selected from anti-aging agents, sebum inhibitors, deodorants, anti-sweating agents, whitening agents and mixtures thereof, the cosmetic film will cause skin aging. It can be treated, absorb sebum on the skin, control odors on the skin, control sweating on the skin, and / or whiten the skin.

It is also possible to apply the make-up cosmetic composition to the above-mentioned cosmetic film or sheet after applying to the skin.

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

(Examples 1 to 11 and Comparative Examples 1 to 13)
[Preparation]
Each of the compositions according to Examples 1 to 11 and Comparative Examples 1 to 13 was prepared by mixing the components shown in Tables 1 to 5 according to the following steps 1 to 7.

1. The components of Phase A were mixed and homogenized at 75 ° C +/- 5 ° C to give a mixture of Phase A.
2. The components of Phase B were added to the mixture of Phase A and homogenized at 75 ° C +/- 5 ° C to give a mixture of Phases A and B.
3. The components of Phase C were added to the mixture of Phases A and B obtained in Step 2 and homogenized at 75 ° C +/- 5 ° C to obtain a mixture of Phases A, B and C.
4. The components of Phase D are added to the mixture of Phases A, B and C obtained in Step 3 and homogenized at 75 ° C +/- 5 ° C to give the mixture of Phases A, B, C and D. Obtained.
5. The components of Phase E were mixed and homogenized at 75 ° C +/- 5 ° C to give a mixture of Phase E.
6. The mixture of phase E obtained in step 5 is added to the mixture of phases A, B, C and D obtained in step 4 and homogenized at 75 ° C. +/- 5 ° C. to phase A, A mixture of B, C, D and E was obtained.
7. The components of Phase F were added to the mixture of Phases A, B, C, D and E obtained in Step 6, homogenized at 75 ° C +/- 5 ° C, and then cooled to room temperature.

All figures for the amounts of ingredients in Tables 1-5 are based on the "% by weight" of the active material.

[evaluation]
(Moisturizing texture)
Three panelists evaluated the texture from the viewpoint of the moisturizing feeling of each of the compositions according to Examples 1 to 11 and Comparative Examples 1 to 13 during and after the application of the composition. Specifically, each panelist applied each composition on his or her hands, stretched it to evaluate the moisturizing texture, and rated it from 1 (low) to 5 (high). It was then categorized into three categories based on the average grade:
Good: 4-5
Normal: More than 2 and less than 4 Defective: 1-2

The results are shown in Table 6.

Table 6 shows that the compositions according to the invention can provide an improved moisturizing texture.

On the other hand, Table 6 also shows that a composition lacking any of the essential components in the composition according to the invention can only provide a limited or relatively low quality moisturizing effect.

(Effect of giving an optical matte feeling)
The matte feeling-imparting effect of the compositions according to Examples 3, 5 and 9 to 11 and Comparative Example 1 was evaluated by an in vitro matte feeling imparting test. Specifically, each composition was spread over the entire contrast sheet by an automatic film coater to form a layer of 100 μm, and left at 37 ° C. for 24 hours to dry. An artificial sebum / sweat composition having the formulations shown in Table 7 below was then sprayed onto the layer on the contrast card at room temperature. The amount of artificial sebum / sweat composition sprayed onto each of the above layers was the same for each other.

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

The matte index was determined by the following formula:
Matte index =
{(Reflectance of the above layer 6 minutes after spraying)-(Reflectance of negative control)} / {(Reflectance of positive control 6 minutes after spraying)-(Reflectance of negative control)} * 100

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

The determined matte index (%) was classified according to the following evaluation criteria:
Excellent: 70 or more Good: 50 or more and less than 70 Bad: Less than 50

The results are shown in Table 8.

Table 8 shows that the composition according to the present invention can bring about a good or good matte feeling imparting effect. In order to obtain a good matte feeling-imparting effect, it is preferable to use (b) silica syllate as a filler.

On the other hand, Table 8 also shows that (b) a composition lacking an oil-absorbing powder as a filler cannot provide a matte feel-imparting effect.

Claims (15)

(a) Below:
At least one cationic polymer and at least one anionic polymer,
And at least one particle, including at least one non-polymeric acid or salt thereof having a pKa value of two or more.
(b) At least one filler and
(c) A composition comprising water. The cationic polymer is at least one selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group, and a pyridyl group. The composition according to claim 1, wherein the composition can have one positive charge and / or has a portion having a positive charge. The cationic polymer is a cyclopolymer of alkyl diallylamine and a cyclopolymer of dialkyl diallyl ammonium, for example, (co) polydialyldialkylammonium chloride, (co) polyamine, for example (co) polylysine, cationic (co) polyamino acid, for example collagen. The composition according to claim 1 or 2, selected from the group consisting of cationic cellulose polymers, and salts thereof. The amount of the cationic polymer forming the particles (a) in the composition is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably to the total mass of the composition. The composition according to any one of claims 1 to 3, which is 0.1% by mass to 5% by mass. The composition according to any one of claims 1 to 4, wherein the anionic polymer is selected from hyaluronic acid and its derivatives. The amount of (a) the anionic polymer forming the particles in the composition is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, more preferably to the total mass of the composition. The composition according to any one of claims 1 to 5, which is 0.1% by mass to 5% by mass. Claim 1 The non-polymeric acid or salt thereof having two or more pKa values is an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof, and more preferably phytic acid or a salt thereof. The composition according to any one of 6 to 6. The amount of the non-polymeric acid or salt thereof having two or more pKa values forming the particles (a) in the composition is 0.01% by mass to 15% by mass, preferably 15% by mass, based on the total mass of the composition. The composition according to any one of claims 1 to 7, wherein the composition is 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass. The amount of the particles (a) in the composition is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5 with respect to the total mass of the composition. The composition according to any one of claims 1 to 8, which is by mass%. The composition according to any one of claims 1 to 9, wherein the filler (b) is selected from a hydrophilic or hydrophobic oil-absorbing powder. The composition according to claim 10, wherein the hydrophobic oil-absorbing powder is selected from hydrophobic silica, preferably hydrophobic silica airgel, more preferably a powder of hydrophobic aerogel of silica syllate. The amount of the filler (b) in the composition is 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5 with respect to the total mass of the composition. The composition according to any one of claims 1 to 11, which is by mass%. The amount of the water (c) in the composition is 50% by mass to 95% by mass, preferably 60% by mass to 90% by mass, and more preferably 70% by mass to 85% by mass with respect to the total mass of the composition. The composition according to any one of claims 1 to 12, which is by mass%. The composition according to any one of claims 1 to 13, which is a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care cosmetic composition. A beauty method for keratin substances such as skin
A step of applying the composition according to any one of claims 1 to 14 to a keratin substance, and
A method comprising the steps of drying the composition to form a cosmetic film on a keratin substance.