Composition containing polyion complex particles

Abstract

To provide a composition including polyion complex particles whose sizes can be controlled without changing the molecular weight of cationic polymer.SOLUTION: Provided is a composition for a keratin substance, preferably cosmetic composition, more preferably cosmetic composition that contains (a) at least one kind of cationic polymer, (b) at least one kind of anionic polymer, (c) at least one kind of non-polymer acid or salt thereof and (d) water, where a ratio of the amount of cation of (a) cationic polymer for the amount of anion of (b) anionic polymer is more than 0.3 and less than 0.8, a ratio of the amount of cation of cationic polymer for the total of the amount of anion of (b) anionic polymer and the amount of anion of (c) non-polymer acid or salt thereof is more than 0.2 and less than 0.5, the charge concentration of cationic polymer is more than 0.71 mmol / g, the charge concentration of anionic polymer is more than 2.04 mmol / g and less than 10.64 mmol / g, and (a) cationic polymer, (b) anionic polymer and (c) non-polymer acid or salt thereof can form at least one polyion complex particle having a particle diameter of less than 1000 nm. A polyion complex particle diameter can be controlled without changing the molecular weight of cationic polymer or anionic polymer.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition, preferably a cosmetic composition, more preferably a cosmetic composition for keratin substances, containing polyion complex particles.

Background Art

[0002] Polyion complexes that can be formed from anionic polymers and cationic polymers are already known.

[0003] For example, WO2017 / 1'04221 discloses a composition containing at least one polyion complex particle useful for cosmetic treatment, comprising at least one cationic polymer, at least one anionic polymer, and at least one non-polymeric acid having two or more pKa values.

[0004] Also, WO2018 / 230673 discloses a composition containing such polyion complex particles and an oil, which may further contain an oil gelling agent. The oil gelling agent is used to enhance the stability of the composition.

[0005] Furthermore, JP-A-2014-114272 discloses controlling the particle size of polyion complex particles by changing the molecular weight of the cationic polymer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

[0007] [Non-Patent Document 1] CTFA Dictionary [Non-Patent Document 2] "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 [Non-Patent Document 3] Organic Synthetic Chemistry, Vol. 25, No. 2, pp. 167-179 (1967) [Overview of the project] [Problems that the invention aims to solve]

[0008] Therefore, an object of the present invention is to provide a composition containing polyion complex particles whose size can be controlled without changing the molecular weight of the cationic polymer. [Means for solving the problem]

[0009] The above objective of the present invention is, (a) at least one cationic polymer, (b) at least one anionic polymer, (c) at least one nonpolymeric acid or a salt thereof, (d) Water and A composition containing, preferably a cosmetic composition, more preferably a cosmetic composition for keratin substances, (a) The ratio of the amount of cations in the cationic polymer to (b) the amount of anions in the anionic polymer is greater than 0.3 and less than 0.8. (a) The ratio of the amount of cations in the cationic polymer to the sum of (b) the amount of anions in the anionic polymer and (c) the sum of the amount of anions in the nonpolymeric acid or its salt is greater than 0.2 and less than 0.5. (a) The charge concentration of the cationic polymer is greater than 0.71 mmol / g, (b) The charge concentration of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g, and (a) a cationic polymer, (b) an anionic polymer, and (c) a nonpolymeric acid or a salt thereof can form at least one polyion complex particle having a particle size of less than 1000 nm. This can be achieved through composition.

[0010] (a) The cationic polymer may be selected from (co)polyamines.

[0011] (a) The cationic polymer may be selected from the group consisting of polylysine, chitosan, and mixtures thereof.

[0012] The amount of (a) cationic polymer in the composition according to the present invention may be 0.001% to 2% by mass, preferably 0.005% to 1.5% by mass, and more preferably 0.01% to 1% by mass, based on the total mass of the composition.

[0013] (b) The anionic polymer may be selected from polysaccharides.

[0014] (b) The anionic polymer may be selected from the group consisting of hyaluronate, ι-carrageenan, Λ-carrageenan, algin, chondroitin sulfate, pectin, and mixtures thereof.

[0015] The amount of (b) anionic polymer in the composition according to the present invention may be 0.001% to 2% by mass, preferably 0.005% to 1.5% by mass, and more preferably 0.01% to 1% by mass, based on the total mass of the composition.

[0016] (c) The nonpolymer acid may have two or more pKa values.

[0017] (c) The nonpolymeric acid may be selected from the group consisting of phytic acid, citric acid, lactic acid, and mixtures thereof.

[0018] The amount of (c) nonpolymeric acid or salt thereof in the composition according to the present invention may be 0.001% to 1% by mass, preferably 0.005% to 0.5% by mass, and more preferably 0.01% to 0.1% by mass, based on the total mass of the composition.

[0019] The amount of (d) water in the composition according to the present invention may be 60% to 97% by mass, preferably 70% to 96% by mass, and more preferably 80% to 95% by mass, based on the total mass of the composition.

[0020] The pH of the composition according to the present invention may be 3 to 9, preferably 3.5 to 8.5, and more preferably 4 to 8.

[0021] The present invention also relates to a cosmetic method for keratinous materials, comprising the steps of applying a composition according to the present invention to a keratinous material and drying the composition to form a cosmetic film on the keratinous material.

[0022] The present invention also, (d) In a composition containing water, (a) at least one cationic polymer, (b) at least one anionic polymer, and (c) at least one nonpolymeric acid or a salt thereof of, (a) a cationic polymer, (b) an anionic polymer, and (c) a nonpolymeric acid or a salt thereof, for use in forming at least one polyion complex particle having a particle size of less than 1000 nm, (a) The ratio of the amount of cations in the cationic polymer to (b) the amount of anions in the anionic polymer is greater than 0.3 and less than 0.8. (a) The ratio of the amount of cations in the cationic polymer to the sum of (b) the amount of anions in the anionic polymer and (c) the sum of the amount of anions in the nonpolymeric acid or its salt is greater than 0.2 and less than 0.5. (a) The charge concentration of the cationic polymer is greater than 0.71 mmol / g, and (b) The charge concentration of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g. Regarding use. [Modes for carrying out the invention]

[0023] As a result of diligent research, the present inventors have discovered that it is possible to provide a composition containing polyion complex particles whose size can be controlled without changing the molecular weight of the cationic polymer.

[0024] Therefore, the composition according to the present invention is (a) at least one cationic polymer, (b) at least one anionic polymer, (c) at least one nonpolymeric acid or a salt thereof, (d) Water and A composition containing, preferably a cosmetic composition, more preferably a cosmetic composition for keratin substances, (a) The ratio of the amount of cations in the cationic polymer to (b) the amount of anions in the anionic polymer is greater than 0.3 and less than 0.8. (a) The ratio of the amount of cations in the cationic polymer to the sum of (b) the amount of anions in the anionic polymer and (c) the sum of the amount of anions in the nonpolymeric acid or its salt is greater than 0.2 and less than 0.5. (a) The charge concentration of the cationic polymer is greater than 0.71 mmol / g, (b) The charge concentration of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g, and (a) a cationic polymer, (b) an anionic polymer, and (c) a nonpolymeric acid or a salt thereof can form at least one polyion complex particle having a particle size of less than 1000 nm. It is a composition.

[0025] The present invention can be characterized by satisfying specific conditions regarding the charge of the cationic polymer, the anionic polymer, and the nonpolymer acid or its salt, for controlling the particle size of polyion complex particles formed from a cationic polymer, anionic polymer, and a nonpolymer acid or its salt.

[0026] According to the present invention, it is possible to control the particle size of a polyion complex without changing the molecular weight of the cationic polymer or anionic polymer.

[0027] The particle size of the polyion complex particles can be controlled to less than 1000 nm by this invention.

[0028] Since the polyion complex particles can be controlled to be "nano" sized, the compositions according to the present invention can be transparent or translucent, preferably transparent.

[0029] The compositions and other related materials according to the present invention will be described in more detail from here on.

[0030] [Charge Conditions] According to the present invention, (a) the charge concentration of the cationic polymer is greater than 0.71 mmol / g, and (b) the charge concentration of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g.

[0031] Here, "charge concentration" refers to the concentration of charged (ionized) or charge-capable (ionizable) functional groups in molecules, such as cationic polymers and anionic polymers. Charge concentration can be considered as "charge density" or "charge equivalent." Here, "charge concentration" is an absolute value.

[0032] Charge concentration reflects the density of functional groups that can act as cations or anions in an aqueous medium such as water. Examples of functional groups that can act as cations in water include amino groups and ammonium groups. Examples of functional groups that can act as anions in water include sulfonic acid groups and phosphate groups.

[0033] The charge concentration can be calculated as follows:

[0034] Charge concentration = (Number of sites on the molecule that have or can have a charge) / (Molecular weight of the molecule with counterions, if present) (In the formula, if the molecule is in the form of a polymer, the molecule means the repeating unit of the polymer.)

[0035] According to the present invention, the ratio of (a) the amount of cations in the cationic polymer to (b) the amount of anions in the anionic polymer is greater than 0.3 and less than 0.8.

[0036] (a) The amount of cations in a cationic polymer can be calculated by multiplying the charge concentration of the cationic polymer by the amount of the cationic polymer.

[0037] (b) The amount of anions in the anionic polymer can be calculated by multiplying the charge concentration of the anionic polymer by the amount of the anionic polymer.

[0038] (a) The ratio of the amount of cations in a cationic polymer to (b) the amount of anions in an anionic polymer can be calculated by dividing the amount of cations in (a) the cationic polymer by the amount of anions in (b) the anionic polymer.

[0039] The above ratio may reflect the ratio of (a) the number of moles of cationic functional groups in the cationic polymer to (b) the number of moles of anionic functional groups in the anionic polymer.

[0040] According to the present invention, the ratio of (a) the amount of cations in the cationic polymer to the sum of (b) the amount of anions in the anionic polymer and (c) the amount of anions in the nonpolymer acid or its salt is greater than 0.2 and less than 0.5.

[0041] (c) The amount of anions in the nonpolymer acid or its salt can be calculated by multiplying the charge concentration of component (c) by the amount of component (c).

[0042] The ratio of the amount of cations in (a) a cationic polymer to the sum of (b) the amount of anions in anionic polymers and (c) the sum of the anions in nonpolymeric acids or their salts can be calculated by dividing the amount of cations in (a) a cationic polymer by the sum of (b) the amount of anions in anionic polymers and (c) the sum of the anions in nonpolymeric anionic acids or their salts.

[0043] The above ratios may reflect the ratio of (a) the number of moles of cationic functional groups in the cationic polymer to (b) the number of moles of anionic functional groups in the anionic polymer and (c) the nonpolymeric acid or its salt.

[0044] [Polyion complex] According to the present invention, (a) a cationic polymer, (b) an anionic polymer, and (c) a nonpolymeric acid or a salt thereof can form at least one polyion complex particle having a particle size of less than 1000 nm.

[0045] The particle size of the polyion complex particles in the composition according to the present invention is less than 1000 nm, preferably less than 800 nm, more preferably less than 600 nm, even more preferably less than 400 nm, and particularly preferably 200 nm.

[0046] The particle size of the polyion complex particles in the composition according to the present invention may be 2 nm or larger, preferably 4 nm or larger, more preferably 6 nm or larger, even more preferably 8 nm or larger, and particularly 10 nm or larger.

[0047] This particle size can be measured by dynamic light scattering. The particle size may be based on the volume-average diameter.

[0048] Therefore, the composition according to the present invention may contain at least one type of polyion complex particle. Two or more different types of polyion complex particles may be used in combination. Therefore, a single type of polyion complex particle or a combination of different types of polyion complex particles may be used.

[0049] The amount of polyion complex particles in the composition according to the present invention may be 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, based on the total mass of the composition.

[0050] The amount of polyion complex 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.

[0051] The amount of polyion complex particles in the composition according to the present invention may be 0.001% to 15% by mass, preferably 0.005% to 10% by mass, and more preferably 0.01% to 5% by mass, relative to the total mass of the composition.

[0052] (cationic polymer) The composition according to the present invention comprises (a) at least one cationic polymer. Two or more cationic polymers may be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers may be used.

[0053] (a) The cationic polymer has or may have one or more positive charges.

[0054] (a) The charge concentration or charge density of the cationic polymer is greater than 0.71 mmol / g, preferably greater than 1 mmol / g, more preferably greater than 2 mmol / g, more preferably greater than 3 mmol / g, more preferably greater than 4 mmol / g, more preferably greater than 5 mmol / g, more preferably greater than 6 mmol / g, and even more preferably greater than 7 mmol / g.

[0055] The molecular weight of the cationic polymer may be 1,000 or more, preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 1,000,000 or more.

[0056] Unless otherwise defined herein, "molecular weight" means number-average molecular weight.

[0057] Cationic polymers may have and / or have positively charged moieties selected from the group consisting of primary, secondary, or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. Here, the term (primary) "amino group" means an -NH2 group.

[0058] Cationic polymers may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two monomers and terpolymers obtained from more than two monomers, for example, three monomers.

[0059] Cationic polymers can be selected from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are as follows:

[0060] (1) Derived from esters and amides of acrylic acid or methacrylic acid, and the following formula:

[0061] [ka]

[0062] (In the formula, R1 and R2 may be the same or different, and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups. R3 may be the same or different, and is selected from hydrogen and CH3. Symbol A may be the same or different, and is selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, for example, 2 to 3 carbon atoms, and hydroxyalkyl groups containing 1 to 4 carbon atoms. R4, R5, and R6 may be the same or different, and are selected from alkyl groups containing 1 to 18 carbon atoms, benzyl groups, and, in at least one embodiment, alkyl groups containing 1 to 6 carbon atoms. X is an anion derived from an inorganic or organic acid, such as the methosulfate anion, and a halide ion, such as the chloride ion and the bromide ion. Homopolymers and copolymers comprising at least one unit selected from the units of .

[0063] The copolymers of Family (1) may also include at least one unit derived from a comonomer, which may be selected from acrylamide, methacrylamide, diacetoneacrylamide, acrylamide and methacrylamide in which the nitrogen atom is substituted with a (C1-C4) lower alkyl group, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams, such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

[0064] Examples of copolymers in Family (1) include, but are not limited to, the following: A copolymer of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide. For example, the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride described in European Patent Application No. 0080976, A copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate. For example, as described in French Patent No. 2077143 and No. 2393573, quaternized or non-quaternized vinylpyrrolidone / acrylic acid or dialkylaminoalkyl methacrylate copolymer, Dimethylaminoethyl methacrylate / vinyl caprolactam / vinyl pyrrolidon polymer, Vinylpyrrolidone / methacrylamidopropyldimethylamine copolymer, quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamido copolymer, and A crosslinked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salt polymer, for example, a homopolymer of dimethylaminoethyl methacrylate quaternized with methyl chloride, or a copolymer of acrylamide and dimethylaminoethyl methacrylate quaternized with methyl chloride, or a polymer obtained by crosslinking the homopolymer or copolymer thereof with a compound containing olefinic unsaturation, for example, methylenebisacrylamide.

[0065] (2) Cationic cellulose derivatives, such as cellulose ether derivatives containing quaternary ammonium groups, are polymers described, for example, in French Patent No. 1492597, and sold by Union Carbide Corporation under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as quaternary ammonium of hydroxyethylcellulose reacted with an epoxide substituted with a trimethylammonium group.

[0066] (3) Cationic cellulose derivatives, such as cellulose copolymers and cellulose derivatives, such as those described in U.S. Patent No. 4,131,576, such as methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium and dimethyldiallylammonium salts, grafted with hydroxyalkyl cellulose, such as hydroxymethyl-, hydroxyethyl- and hydroxypropylcellulose.

[0067] Examples of commercially available products equivalent to these polymers include those sold by National Starch under the names "Celquat® L 200" and "Celquat® H 100".

[0068] (4) Non-cellulose cationic polysaccharides as described in U.S. Patent Nos. 3,589,578 and 4,031,307, such as guar gum containing a cationic trialkylammonium group, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride. Guar gum modified with salts, such as 2,3-epoxypropyltrimethylammonium chloride (guar hydroxypropyltrimonium chloride), may also be used.

[0069] Such products are sold by MEYHALL, for example, under the product names JAGUAR®C13 S, JAGUAR®C15, JAGUAR®C17, and JAGUAR®C162.

[0070] (5) Polymers comprising divalent alkylene or hydroxyalkylene groups including piperazinyl units and linear or branched chains optionally interposed by at least one element selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, as well as oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patent Nos. 2162025 and 2280361.

[0071] (6) For example, water-soluble polyaminoamides prepared by polycondensation of an acidic compound with a polyamine; these polyaminoamides may be crosslinked with elements selected from elements selected from bishalohydrins, bisazetidinium, bishaloacyidiamine, bisalkyl halides, and oligomers obtained from the reaction of a difunctional compound that is reactive with an element selected from bishalohydrins, bisazetidinium, bishaloacyidiamine, bisalkyl halides, epihalohydrins, diexides, and bisunsaturated derivatives; the crosslinking agent is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may optionally be alkylated, or if they contain at least one tertiary amine functional group, they may be quaternized. Such polymers are described, for example, in French Patent Nos. 2252840 and 2368508.

[0072] (7) Polyaminoamide derivatives obtained by condensing a polyalkylene polyamine with a polycarboxylic acid and subsequently alkylating it with a bifunctional agent, such as adipic acid / dialkylaminohydroxyalkyldialkylentriamine polymers, in which the alkyl group contains 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, and the alkylene group contains 1 to 4 carbon atoms, such as an ethylene group. Such polymers are described, for example, in French Patent No. 1583363. In at least one embodiment, these derivatives may be selected from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.

[0073] (8) A polymer obtained by the reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with diglycolic acid and a dicarboxylic acid selected from saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid may be in the range of 0.8:1 to 1.4:1, and the resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine groups of the polyaminoamide in the range of 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Patent Nos. 3,227,615 and 2,961,347.

[0074] (9) Cyclopolymers of alkyldiallylamines and cyclopolymers of dialkyldiallylammonium, for example, the following formulas (Ia) and (Ib) as the main components of the chain:

[0075] [ka]

[0076] (In the formula, k and t may be the same or different, and are equal to 0 or 1, and their sum k+t is equal to 1. R 12 It is selected from hydrogen and methyl groups, R 10and R 11 may be the same or different and are selected from an alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group contains, for example, 1 to 5 carbon atoms, and a lower (C1 - C4) amidoalkyl group, or R 10 and R 11 may together with the nitrogen atom to which they are attached form a heterocyclic group such as piperidinyl and morpholinyl, Y' is an anion such as bromide ion, chloride ion, acetate ion, borate ion, citrate ion, tartrate ion, hydrogen sulfate ion, hydrogen sulfite ion, sulfate ion and phosphate ion) homopolymers and copolymers containing at least one unit selected from the units of ). These polymers are described, for example, in French Patent No. 2080759 and its additional patent No. 2190406.

[0077] In one embodiment, R 10 and R 11 may be the same or different and are selected from an alkyl group containing 1 to 4 carbon atoms.

[0078] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chloride, such as the dimethyldiallylammonium chloride homopolymer (and its homologs of low average molecular weight) sold by CALGON under the name "MERQUAT® 100", and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550".

[0079] (10) Formula (II):

[0080]

Chemical formula

[0081] {In the formula, R 13 、R 14 、R15 and R 16 These may be the same or different, and are selected from aliphatic, alicyclic and aryl aliphatic groups containing 1 to 20 carbon atoms, and lower hydroxyalkyl aliphatic groups, or R 13 , R 14 , R 15 and R 16 They may form a heterocycle containing a second heteroatom other than nitrogen, either together with or separately from the nitrogen atom to which they are bonded, or R 13 , R 14 , R 15 and R 16 These may be the same or different, and include nitrile groups, ester groups, acyl groups, amide groups, and -CO-OR groups. 17 -E group and -CO-NH-R 17 -E group (in the formula, R 17 (where is an alkylene group and E is a quaternary ammonium group) is selected from linear or branched C1-C6 alkyl groups which are substituted with at least one group selected from the above, A1 and B1 may be the same or different, selected from a polymethylene group containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked to or inserted into the main chain, at least one element 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. X - These are anions derived from inorganic or organic acids, A1, R 13 and R 15 These may also form a piperazine ring together with the two nitrogen atoms to which they are bonded. If A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, then B1 is as follows: -(CH2) n -CO-E'-OC-(CH2) n - [In the formula, E' is as follows: a) Formula -OZO-(wherein Z is a linear or branched hydrocarbon-based group, and the following formula: -(CH2-CH2-O) x -CH2-CH2- -[CH2-CH(CH3)-O] y -CH2-CH(CH3)- (In the formula, x and y may be the same or different, and are selected from integers in the range of 1 to 4 representing a defined unique degree of polymerization, and numbers in the range of 1 to 4 representing the average degree of polymerization.) (Selected from the base) The glycol residue, b) Bis-secondary diamine residues, e.g., piperazine derivatives, c) Bis-primary diamine residues of the formula -NH-Y-NH- (wherein Y is selected from a linear or branched hydrocarbon-based group and a divalent group -CH2-CH2-SS-CH2-CH2-), and d) Urylene group of formula -NH-CO-NH- [Selected from] Can be selected from} A quaternary diammonium polymer comprising at least one repeating unit.

[0082] In at least one embodiment, X - These are anions, such as chloride ions or bromide ions.

[0083] This type of polymer is, for example, represented by French Patent Nos. 2320330; 2270846; 2316271; 2336434; and 2413907, and U.S. Patents Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; and 2,261,0 It is listed in No. 02; No. 2,271,378; No. 3,874,870; No. 4,001,432; No. 3,929,990; No. 3,966,904; No. 4,005,193; No. 4,025,617; No. 4,025,627; No. 4,025,653; No. 4,026,945; and No. 4,027,020.

[0084] A non-limiting example of such a polymer is equation (III):

[0085] [ka]

[0086] (In the formula, R 13 , R 14 , R 15 and R 16 n and p may be the same or different, selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p may be the same or different, integers in the range of 2 to 20, X - (These are anions derived from inorganic or organic acids.) Examples include those containing at least one repeating unit.

[0087] (11) Formula (IV):

[0088] [ka]

[0089] (In the formula, R 18 , R 19 , R 20 and R 21 These may be the same or different, and include hydrogen, methyl group, ethyl group, propyl group, β-hydroxyethyl group, β-hydroxypropyl group, and -CH2CH2(OCH2CH2). p Selected from OH groups (wherein p is selected from integers in the range of 0 to 6), however, R 18 , R 19 , R 20 and R 21 They cannot be hydrogen at the same time. r and s may be the same or different, and are selected from integers in the range of 1 to 6. q is selected from integers in the range of 0 to 34. X- These are anions, such as halide ions. A is selected from dihalide and -CH2-CH2-O-CH2-CH2- groups. A polyquaternary ammonium polymer containing units.

[0090] Such compounds are described, for example, in European Patent Application No. 0122324.

[0091] (12) Quaternary polymer of vinylpyrrolidone and vinylimidazole.

[0092] Other suitable examples of cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines such as polyethyleneimine, polymers containing units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines and epichlorohydrins, quaternary polyurenes, and chitin derivatives.

[0093] According to one embodiment of the present invention, at least one cationic polymer is selected from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold by UNION CARBIDE CORPORATION under the name "JR 400", cationic cyclopolymers, such as homopolymers and copolymers of dimethyldiallylammonium chloride sold by CALGON under the names MERQUAT® 100, MERQUAT® 550, and MERQUAT® S, guar gum modified with 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0094] (13) Polyamines As the cationic polymer, it is also possible to use a (co)polyamine, which may be a homopolymer or copolymer having multiple amino groups. The amino groups may be primary, secondary, tertiary, or quaternary amino groups. The amino groups may be present in the polymer backbone of the (co)polyamine, or in the pendant groups, if present.

[0095] Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridine, e.g., (co)poly-1-methyl-2-vinylpyridine, (co)polyimines, e.g., (co)polyethyleneimine, (co)polypyridine, e.g., (co)poly(quaternary pyridine), (co)polybiguanides, e.g., (co)polyaminopropylbiguanides, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinylacetal, and salts thereof.

[0096] As the (co)polyamine, (co)polylysine is preferred. Polylysine is well known. Polylysine may be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine may be ε-poly-L-lysine, which is typically used as a natural preservative in food. Polylysine is a polymer electrolyte 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 may also be in the form of a salt and / or a solution.

[0097] (14) Cationic polyamino acids As the cationic polymer, it is also possible to use a cationic polyamino acid, which may be a cationic homopolymer or copolymer having multiple amino groups and carboxyl groups. The amino groups may be primary, secondary, tertiary, or quaternary amino groups. The amino groups may be present in the polymer backbone of the cationic polyamino acid, or in the pendant groups, if present. The carboxyl groups may be present in the pendant groups of the cationic polyamino acid, if present.

[0098] 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 hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, and cocodimonium hydroxypropyl hydrolyzed soy protein.

[0099] (a) The cationic polymer may preferably be selected from (co)polyamines.

[0100] (a) The cationic polymer may be more preferably selected from the group consisting of polylysine, chitosan, and mixtures thereof.

[0101] The amount of (a) cationic polymer in the composition according to the present invention may be 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, based on the total mass of the composition.

[0102] The amount of (a) cationic polymer in the composition according to the present invention may be 2% by mass or less, preferably 1.5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the composition.

[0103] The amount of (a) cationic polymer in the composition according to the present invention may be 0.001% to 2% by mass, preferably 0.005% to 1.5% by mass, and more preferably 0.01% to 1% by mass, based on the total mass of the composition.

[0104] (Anionic polymer) The composition according to the present invention comprises (b) at least one anionic polymer. Two or more anionic polymers may be used in combination. Therefore, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

[0105] (b) The anionic polymer has or may have one or more negative charges.

[0106] (b) The charge concentration or charge density of the anionic polymer is greater than 2.04 mmol / g, preferably greater than 2.20 mmol / g, and more preferably greater than 2.40 mmol / g.

[0107] (b) The charge concentration or charge density of the anionic polymer is less than 10.64 mmol / g, preferably less than 8.00 mmol / g, and more preferably less than 6.00 mmol / g.

[0108] (b) The charge concentration or charge density of the anionic polymer is preferably less than 5.00 mmol / g, more preferably less than 4.70 mmol / g, and even more preferably less than 4.40 mmol / g.

[0109] (b) The charge concentration or charge density of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g, preferably greater than 2.20 mmol / g and less than 8.00 mmol / g, and more preferably greater than 2.40 mmol / g and less than 6.00 mmol / g.

[0110] (b) The charge concentration or charge density of the anionic polymer is preferably greater than 2.04 mmol / g and less than 5.00 mmol / g, more preferably greater than 2.20 mmol / g and less than 4.70 mmol / g, and even more preferably greater than 2.40 mmol / g and less than 4.40 mmol / g.

[0111] The molecular weight of the anionic polymer may be 1,000 or more, preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more.

[0112] Anionic polymers may have at least one negative charge selected from the group consisting of sulfate groups, sulfate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups, phosphate groups, phosphonic acid groups, phosphonate groups, carboxylic acid groups, and carboxylate groups, and / or may have a negatively charged moiety.

[0113] Anionic polymers may be homopolymers or copolymers. The term "copolymer" is understood to mean both copolymers obtained from two monomers and terpolymers obtained from more than two monomers, for example, three monomers.

[0114] Anionic polymers can be selected from natural and synthetic anionic polymers.

[0115] The anionic polymer may contain at least one hydrophobic chain.

[0116] An anionic polymer, which may contain at least one hydrophobic chain, can be obtained by copolymerizing a monomer (a) selected from a carboxylic acid containing α,β-ethylenically unsaturated compounds (monomer a') and 2-acrylamido-2-methylpropanesulfonic acid (monomer a'') with a monomer (c) containing ethylenically unsaturated compounds obtained from the reaction of an acrylic monomer containing α,β-monoethylenically unsaturated compounds or an isocyanate monomer containing monoethylenically unsaturated compounds with a monovalent nonionic amphiphilic component or a primary or secondary fatty amine.

[0117] Therefore, anionic polymers having at least one hydrophobic chain can be obtained by one of the following two synthetic routes: - Copolymerization of monomer (a') and (c), or (a') and (b) and (c), or (a'') and (c), or (a'') and (b) and (c), - Modification (especially esterification or amidation) of a copolymer formed from monomer (a'), or from monomer (a') and (b), or from (a'') and (b), with a monovalent nonionic amphiphilic compound or primary or secondary fatty amine.

[0118] Examples of 2-acrylamido-2-methylpropanesulfonate copolymers include those disclosed in the paper "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering" - Macromolecules, 2000, Vol. 33, No. 10, pp. 3694-3704, and applications EP-A-0750899 and EP-A-1069172.

[0119] The carboxylic acid containing α,β-monoethylenically unsaturated compounds that constitute monomer (a') can be selected from a number of acids, particularly acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid. Preferably, this is acrylic acid or methacrylic acid.

[0120] The copolymer may contain monomer (b) which is monoethylenically unsaturated and does not possess surfactant properties. Preferred monomers are those which yield a water-insoluble polymer when homopolymerized. These can be selected from, for example, C1-C4 alkyl acrylates and methacrylates, 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, in which a single ethylenic group is the only group that is reactive under polymerization conditions. However, monomers containing a group that reacts under the action of heat, such as hydroxyethyl acrylate, can be optionally used.

[0121] Monomer (c) is obtained by the reaction of an acrylic monomer containing α,β-monoethylene unsaturated compounds, such as (a), or an isocyanate monomer containing monoethylene unsaturated compounds, with a monovalent nonionic amphiphilic compound or a primary or secondary fatty amine.

[0122] Monovalent nonionic amphiphilic compounds or primary or secondary fatty amines used to produce nonionic monomers (c) are well known. Monovalent nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds containing alkylene oxides that form the hydrophilic portion of the molecule. Hydrophobic compounds are generally composed of aliphatic alcohols or alkylphenols, in which a carbon chain containing at least six carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.

[0123] A preferred monovalent nonionic amphiphilic compound is given by the following formula (V): R-(OCH2CHR') m -(OCH2CH2) n -OH (V) (In the formula, R is selected from alkyl or alkylene groups containing 6 to 30 carbon atoms, and alkylaryl groups having alkyl groups containing 8 to 30 carbon atoms; R' is selected from alkyl groups containing 1 to 4 carbon atoms; 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, provided that n is at least the same magnitude as m.) It is a compound that has [a certain characteristic].

[0124] Preferably, in the compound of formula (V), the R group is an alkyl group containing 12 to 26 carbon atoms and the alkyl group is C8-C 13 The alkylphenyl group is selected from the R' group, the R' group is a methyl group, m=0, and n=1 to 25.

[0125] Preferred primary and secondary fatty amines consist of one or two alkyl chains containing 6 to 30 carbon atoms.

[0126] The monomer used to form the nonionic urethane monomer (c) can be selected from a wide variety of compounds. Any compound may be used, including copolymerizable unsaturated compounds, such as acrylic, methacrylic, or allyl unsaturated compounds. Monomer (c) can be obtained, in particular, from isocyanates containing monoethylene unsaturated compounds, such as α,α-dimethyl-m-isopropenylbenzyl isocyanate.

[0127] Monomer (c) is particularly oxyethylene (1-50EO) C6-C 30 Acrylates, methacrylates, or itaconates of fatty alcohols, such as steareth-20 methacrylate, oxyethylene-(25EO)behenyl methacrylate, oxyethylene-(20EO)monocetyl itaconate, oxyethylene-(20EO)monostealyl itaconate, or polyoxyethylene-(25EO)C12 ~C 24 From alcohol-modified acrylates, and oxyethylene (1-50EO)C6-C 30 Dimethyl-m-isopropenylbenzyl isocyanates of fatty alcohols can be selected, for example, particularly dimethyl-m-isopropenylbenzyl isocyanates of oxyethylene-behenyl alcohols.

[0128] According to a particular embodiment of the present invention, the anionic polymer is selected from (a) a carboxylic acid containing α,β-ethylenically unsaturated compounds, (b) a non-surface-active monomer containing ethylenically unsaturated compounds other than those in (a), and (c) an acrylic polymer obtained from a nonionic urethane monomer which is a reaction product of a monovalent nonionic amphiphilic compound and an isocyanate containing monoethylenically unsaturated compounds.

[0129] Anionic polymers containing at least one hydrophobic chain include, in particular, acrylic acid / ethyl acrylate / alkyl acrylate terpolymer, e.g., a product sold by Rohm & Haas under the name Acusol 823 as a 30% aqueous dispersion; acrylate / steareth-20 methacrylate copolymer, e.g., a product sold by Rohm & Haas under the name Aculyn 22; (meth)acrylic acid / ethyl acrylate / oxyethylene-(25EO) behenyl methacrylate terpolymer, e.g., a product sold by Rohm & Haas under the name Aculyn 28 as an aqueous emulsion; acrylic acid / oxyethylene-(20EO) monocetyl itaconate copolymer, e.g., a product sold by National Starch under the name Structure 3001 as a 30% aqueous dispersion; acrylic acid / oxyethylene-(20EO) monostearyl itaconate copolymer, e.g., a product sold by National Starch under the name Structure Product sold in 2001 as a 30% aqueous dispersion; acrylate / polyoxyethylene (25EO)C 12 ~C 24Examples include copolymers of alcohol-modified acrylates, such as the 30-32% copolymer latex sold by 3V SA under the name Synthalen W2000; or terpolymers of dimethyl-meth-isopropenylbenzyl isocyanate of methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol, such as the product as a 24% aqueous dispersion containing 40 ethylene oxide groups disclosed in reference EP-A-0173109.

[0130] Anionic polymers may also be polyester-5, for example, a product sold by Eastman Chemical under the name Eastman AQ(trademark) 55S Polymer, having the following chemical formula.

[0131] [ka]

[0132] A: Dicarboxylic acid portion G: Glycol portion SO3 - Na + : Sodium sulfo group OH: Hydroxyl group

[0133] It is preferable that the anionic polymer is selected from the group consisting of polysaccharides, such as carrageenan (e.g., ι-carrageenan and Λ-carrageenan), pectin, alginic acid (algin), hyaluronic acid and cellulose polymers (e.g., carboxymethylcellulose), anionic (co)polyamino acids, such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyamine acid, (co)polystyrene sulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, (co)polyfumaric acid, maleic acid (co)polymer, and salts thereof.

[0134] The maleic acid copolymer may comprise one or more maleic acid comonomers, as well as one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing 2 to 20 carbon atoms, and styrene.

[0135] Therefore, "maleic acid copolymer" is understood to mean any polymer obtained by copolymerizing one or more maleic acid comonomers with one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, wherein the maleic acid comonomers are optionally partially or completely hydrolyzed. Preferably, hydrophilic polymers, i.e., polymers with a water solubility of 2 g / l or more, are used.

[0136] In an advantageous embodiment of the present 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.

[0137] The mass-average molar mass of the maleic acid copolymer may be between 1,000 and 500,000, preferably between 1,000 and 50,000.

[0138] The maleic acid copolymer is preferably a styrene / maleic acid copolymer, and more preferably a sodium styrene / maleic acid copolymer.

[0139] Preferably, a copolymer of styrene and maleic acid in a 50 / 50 ratio is used.

[0140] For example, you may use styrene / maleic acid (50 / 50) copolymer in the form of a 30% ammonium salt in water, sold by Cray Valley under the reference name SMA1000H®, or styrene / maleic acid (50 / 50) copolymer in the form of a 40% sodium salt in water, sold by Cray Valley under the reference name SMA1000HNa®.

[0141] The anionic polymer may preferably be selected from polysaccharides.

[0142] The anionic polymer may preferably be selected from the group consisting of hyaluronate, ι-carrageenan, Λ-carrageenan, algin, chondroitin sulfate, pectin, and mixtures thereof.

[0143] The amount of (b) anionic polymer in the composition according to the present invention may be 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, based on the total mass of the composition.

[0144] The amount of (b) anionic polymer in the composition according to the present invention may be 2% by mass or less, preferably 1.5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the composition.

[0145] The amount of (b) anionic polymer in the composition according to the present invention may be 0.001% to 2% by mass, preferably 0.005% to 1.5% by mass, and more preferably 0.01% to 1% by mass, based on the total mass of the composition.

[0146] (Non-polymeric acids or their salts) The composition according to the present invention comprises (c) at least one nonpolymer acid or a salt thereof. Two or more nonpolymer acids or salts may be used in combination. Therefore, a single type of nonpolymer acid or a salt thereof, or a combination of different types of nonpolymer acids or salts thereof, may be used.

[0147] The term "non-polymeric" here means that the acid is not obtained by polymerizing two or more monomers. Therefore, non-polymeric acids do not correspond to acids obtained by polymerizing two or more monomers, such as polyacrylic acid.

[0148] The term "salt" here refers to a salt formed by adding a suitable base to a nonpolymer acid, which can be obtained from the reaction of a nonpolymer acid with a base according to methods known to those skilled in the art. Examples of salts include metal salts, such as salts with alkali metals like Na and K, salts with alkaline earth metals like Mg and Ca, and ammonium salts.

[0149] (c) The molecular weight of the nonpolymeric acid or its salt is preferably less than 1000, preferably 900 or less, and more preferably 800 or less.

[0150] (c) Nonpolymeric acids or salts thereof may be contained in polyion complex particles.

[0151] (c) The nonpolymeric acid or salt thereof may be an organic or inorganic acid or salt thereof, preferably an organic acid or salt thereof, more preferably a hydrophilic or water-soluble organic acid or salt thereof.

[0152] (c) The nonpolymeric acid may have at least one acid group 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, and mixtures thereof.

[0153] (c) The nonpolymeric acid may be monovalent.

[0154] The monovalent nonpolymer acid can be selected from monocarboxylic acids, preferably hydroxyl acids, and more preferably alpha-hydroxy acids. Examples of alpha-hydroxy acids include lactic acid and glycolic acid.

[0155] (c) The nonpolymeric acid may be divalent.

[0156] (c) Nonpolymeric acids may preferably have two or more pKa values. The pKa value (acid dissociation constant) is well known to those skilled in the art and should be determined at a constant temperature such as 25°C. (c) Nonpolymeric acids or salts thereof having two or more pKa values ​​can function as crosslinking agents for cationic polymers.

[0157] (c) Nonpolymeric acids having two or more pKa values ​​may be selected from the group consisting of dicarboxylic acids, disulfonic acids, and diphosphonic acids, as well as mixtures thereof.

[0158] (c) Nonpolymeric acids or salts thereof having two or more pKa values ​​include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetate, tartaric acid, and their salts; aspartic acid, glutamic acid, and their salts; terephthalylidene dicamfersulfonic acid, or its salt (Mexoryl SX), benzophenone-9; phytic acid and its salts; Red 2 (amaranth), Red 102 (new coccine), Yellow 5 (taltrazine), Yellow 6 (sunset yellow FCF), Green 3 (fast green FCF), Blue 1 (brilliant blue FCF), Blue 2 (indigo carmine), Red 201 (lysole rubin B), Red 202 (lysole rubin BCA), Red 204 (lake red CBA), Red 206 (lysole red CA), Red 207 (lysole red BA), Red 208 (lysole red SR), Red 219 (brilliant lake red R), Red 220 (deep maroon), Red 227 (fast acid magenta), Yellow 203 (quinoline yellow -WS), Green 201 (Alizanin Cyanine Green F), Green 204 (Pyranine Concentrate), Green 205 (Light Green SF Yellow), Blue 203 (Patent Blue CA), Blue 205 (Alphazrin FG), Red 401 (Violamin R), Red 405 (Permanent Red F5R), Red 502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Green 401 (Naphthol Green B), Green 402 (Guinea Green B), and Black 401 (Naphthol Blue Black); folic acid, ascorbic acid, erythorbic acid, and their salts; cystine and its salts; EDTA and its salts; glycyrrhizin and its salts; and mixtures thereof may be selected from the group.

[0159] (c) The nonpolymeric acid may preferably be selected from the group consisting of phytic acid, citric acid, lactic acid, and mixtures thereof.

[0160] The amount of (c) nonpolymeric acid or salt thereof in the composition according to the present invention may be 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, based on the total mass of the composition.

[0161] The amount of (c) nonpolymeric acid or salt thereof in the composition according to the present invention may be 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, based on the total mass of the composition.

[0162] The amount of (c) nonpolymeric acid or salt thereof in the composition according to the present invention may be 0.001% to 1% by mass, preferably 0.005% to 0.5% by mass, and more preferably 0.01% to 0.1% by mass, based on the total mass of the composition.

[0163] [water] The composition according to the present invention comprises (d) water.

[0164] (d) Water may form the aqueous phase of the composition according to the present invention.

[0165] (d) The amount of water may be 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, based on the total mass of the composition.

[0166] (d) The amount of water may be 97% by mass or less, preferably 96% by mass or less, and more preferably 95% by mass or less, based on the total mass of the composition.

[0167] (d) The amount of water may be 60% to 97% by mass, preferably 70% to 96% by mass, and more preferably 80% to 95% by mass, based on the total mass of the composition.

[0168] [pH] The pH of the composition according to the present invention may be 3 to 9, preferably 3.5 to 8.5, and more preferably 4 to 8.

[0169] Polyion complexes can be very stable in the pH range of 3 to 9.

[0170] The pH of the composition according to the present invention can be adjusted by adding at least one alkaline agent and / or at least one acid other than (c) a nonpolymeric acid incorporated into the polyion complex. The pH of the composition according to the present invention can also be adjusted by adding at least one buffering agent.

[0171] (Alkaline agent) The composition according to the present invention may contain at least one alkaline agent. Two or more alkaline agents may be used in combination. Therefore, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

[0172] The alkaline agent may be an inorganic alkaline agent. The inorganic alkaline agent is preferably 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 monohydrogen phosphate.

[0173] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Sodium hydroxide is preferred as the inorganic alkali agent.

[0174] The alkaline agent may be an organic alkaline agent. The organic alkaline agent is preferably selected from the group consisting of monoamines and their derivatives; diamines and their derivatives; polyamines and their derivatives; basic amino acids and their derivatives; oligomers and their derivatives of basic amino acids; polymers and their derivatives of basic amino acids; urea and its derivatives; and guanidine and its derivatives.

[0175] Examples of organic alkaline agents include alkanolamines, such as mono-, di-, and tri-ethanolamines, and isopropanolamines; urea, guanidine, and their derivatives; basic amino acids, such as lysine, ornithine, or arginine; and diamines, such as those with the following structures:

[0176] [ka]

[0177] (In the formula, R represents an alkylene such as propylene that is optionally substituted with a hydroxyl group or a C1-C4 alkyl group, and R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group, or a C1-C4 hydroxyalkyl group.) Examples include those described in [reference], which can be exemplified by 1,3-propanediamine and its derivatives. Arginine, urea, and monoethanolamine are preferred.

[0178] Depending on its solubility, the alkaline agent may be used in a total amount of 0.01% to 10% by mass, preferably 0.05% to 5% by mass, and more preferably 0.1% to 1% by mass, relative to the total mass of the composition.

[0179] (acid) The composition according to the present invention may contain (a) at least one acid other than (d) the acid incorporated into the particles. Two or more acids may be used in combination. Therefore, a single type of acid or a combination of different types of acids may be used.

[0180] Examples of acids include any inorganic or organic acid commonly used in cosmetics, preferably inorganic acids. Monohydric acids and / or polyhydric acids may be used. Monohydric acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid, and hydrochloric acid (HCl) may be used. Lactic acid may be preferred in some cases.

[0181] Depending on its solubility, the acid may be used in a total amount of 0.01% to 10% by mass, preferably 0.05% to 5% by mass, and more preferably 0.1% to 1% by mass, relative to the total mass of the composition.

[0182] (buffering agent) The composition according to the present invention may contain at least one type of buffering agent. Two or more types of buffering agents may be used in combination. Therefore, a single type of buffering agent or a combination of different types of buffering agents may be used.

[0183] Examples of buffering agents include acetate buffers (e.g., acetic acid + sodium acetate), phosphate buffers (e.g., sodium dihydrogen phosphate + disodium hydrogen phosphate), citrate buffers (e.g., citric acid + sodium citrate), borate buffers (e.g., boric acid + sodium borate), tartaric acid buffers (e.g., tartaric acid + sodium tartrate dihydrate), Tris buffers (e.g., tris(hydroxymethyl)aminomethane), and Hepes buffers (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[0184] [Optional additives] Since the composition according to the present invention contains (d) water, the composition according to the present invention may contain at least one aqueous phase.

[0185] The aqueous phase may contain at least one C2-C6 monohydric alcohol. Two or more C2-C6 monohydric alcohols may be used in combination.

[0186] Suitable C2-C6 monohydric alcohols for the present invention may contain 2-5 carbon atoms, preferably 2-4 carbon atoms, and include, for example, ethanol, isopropanol, propanol, or butanol.

[0187] Ethanol and isopropanol, preferably ethanol, are very particularly suitable for the present invention.

[0188] The amount of C2-C6 monohydric alcohol in the composition according to the present invention may be 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total mass of the composition. On the other hand, the amount of C2-C6 monohydric alcohol in the composition according to the present invention may be 5% by mass or more, preferably 6% by mass or more, and more preferably 7% by mass or more, based on the total mass of the composition. For example, the amount of C2-C6 monohydric alcohol may be 5% to 20% by mass, preferably 6% to 15% by mass, and more preferably 7% to 10% by mass, based on the total mass of the composition.

[0189] The aqueous phase may contain polyhydric alcohols containing 2 to 8 carbon atoms, such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, diethylene glycol, pentylene glycol, hexylene glycol, glycerin, and mixtures thereof.

[0190] If present, the amount of polyhydric alcohol such as glycol in the aqueous phase according to the present invention may be in the range of 0.1% to 15% by mass, preferably 0.5% to 12% by mass, and more preferably 1% to 8% by mass, based on the total mass of the composition.

[0191] In addition to the components described above, the compositions according to the present invention may also contain components typically used in cosmetics, such as surfactants or emulsifiers, preservatives such as phenoxyethanol and caprylyl glycol, organic non-volatile solvents, and natural extracts derived from plants, to the extent that they do not impair the effects of the present invention.

[0192] The composition according to the present invention preferably does not contain pigments or dyes.

[0193] The composition according to the present invention may contain the above-mentioned optional additives in an amount of 0.01% to 50% by mass, preferably 0.05% to 30% by mass, and more preferably 0.1% to 10% by mass, based on the total mass of the composition.

[0194] However, the composition according to the present invention may contain a very limited amount of surfactant or emulsifier. The amount of surfactant or emulsifier in the composition according to the present invention may be 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, based on the total mass of the composition. It is particularly preferred that the composition according to the present invention does not contain a surfactant or emulsifier.

[0195] [Preparation] The composition of the present invention can be prepared by mixing the essential components described above and, if necessary, the optional components described above.

[0196] The methods and means for mixing the above essential and optional components are not limited. Any conventional methods and means can be used to mix the above essential components and optional components to prepare the composition according to the present invention.

[0197] [Form] The form of the composition according to the present invention is not limited. Thus, the composition according to the present invention may be in the form of a solution, gel or emulsion.

[0198] The composition of the present invention can be transparent.

[0199] The transparency can be measured by measuring the turbidity (for example, the turbidity can be measured using a round cell (diameter 25 mm and height 60 mm) and a 2100Q (commercially available from Hach Company) having a tungsten filament lamp capable of emitting visible light (between 400 and 800 nm, preferably between 400 and 500 nm)). The measurement can be carried out on the undiluted composition. The blank can be determined using distilled water.

[0200] The composition according to the present invention may have a turbidity of 250 NTU or less, preferably 150 NTU or less, more preferably 50 NTU or less.

[0201] [Methods and Uses] The present invention also relates to a beauty method for keratin substances, comprising applying the composition according to the present invention to a keratin substance, and drying the composition to form a cosmetic film on the keratin substance and a beauty method and a method for preparing a film, preferably a cosmetic film, comprising applying the composition according to the present invention to a keratin substance, and drying the composition and a method relating to the above.

[0202] Here, the keratin substance means a substance containing keratin as a main component, and examples thereof include skin, scalp, nails, lips, hair, etc.

[0203] Furthermore, the present invention also relates to (a) at least one cationic polymer, (b) at least one anionic polymer, (c) at least one non-polymeric acid or its salt, and a film, preferably a cosmetic film, containing at least one polyion complex, where the ratio of the amount of cations of the cationic polymer (a) to the amount of anions of the anionic polymer (b) is more than 0.3 and less than 0.8, and the ratio of the amount of cations of the cationic polymer (a) to the total amount of anions of the anionic polymer (b) and anions of the non-polymeric acid or its salt (c) is more than 0.2 and less than 0.5, (a) the charge density of the cationic polymer is more than 0.71 mmol / g, and (b) the charge density of the anionic polymer is more than 2.04 mmol / g and less than 10.64 mmol / g, and a film

[0204] The present invention may also relate to the use of the composition according to the present invention for the preparation of a cosmetic film on a keratin substance.

[0205] In this context, "beauty treatments" refer to non-therapeutic beauty treatments that focus on caring for keratin.

[0206] The above-mentioned film, preferably a cosmetic film, is resistant to water with a pH of 7 or less and can be removed with water with a pH greater than 7, preferably 8 or higher, and more preferably 9 or higher.

[0207] In other words, the above-mentioned film, preferably a cosmetic film, can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably between 6 and 7, more preferably between 5 and 7, while the above-mentioned film, preferably a cosmetic film, can be removed under alkaline conditions such as a pH greater than 7, preferably 8 or more, more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.

[0208] Therefore, the above-mentioned film, preferably a cosmetic film, can be water-resistant and thus can remain on keratinous substances such as skin even when the surface of the keratinous substance is wet, for example, by sweat and rain. On the other hand, the above-mentioned film, preferably a cosmetic film, can be easily removed from keratinous substances such as skin under alkaline conditions. Therefore, although the above-mentioned film, preferably a cosmetic film, is difficult to remove with water, it can be easily removed, for example, using soap that can create alkaline conditions.

[0209] Furthermore, even if the film does not contain any cosmetic active ingredients, the above-mentioned film may have cosmetic effects such as absorbing or adsorbing unpleasant odors, altering the appearance of keratinous substances such as skin, altering the texture of keratinous substances, and / or protecting keratinous substances from dirt or pollutants, due to the properties of the polyion complex in the film.

[0210] The present invention also, (d) In a composition containing water, (a) At least one cationic polymer, (b) At least one anionic polymer, and (c) At least one non-polymeric acid or its salt for forming at least one polyion complex particle having a particle size of less than 1000 nm, comprising (a) a cationic polymer, (b) an anionic polymer and (c) a non-polymeric acid or its salt, where the ratio of the amount of cations of the cationic polymer (a) to the amount of anions of the anionic polymer (b) is greater than 0.3 and less than 0.8, where the ratio of the amount of cations of the cationic polymer (a) to the total amount of anions of the anionic polymer (b) and anions of the non-polymeric acid or its salt (c) is greater than 0.2 and less than 0.5, where the charge density of the cationic polymer (a) is greater than 0.71 mmol / g, and (b) the charge density of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g, (relating to the use).

[0211] The above descriptions regarding (a)-(d) for the composition according to the present invention can be applied to the descriptions in the use according to the present invention. [Examples]

[0212] 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 present invention.

[0213] (Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-13) [Preparation] The compositions according to Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-13 were prepared by mixing the components shown in Tables 1-3. The amounts of each component used in the above preparation are shown in Tables 1-3. All the numerical values regarding the amounts of the components shown in Tables 1-3 are based on the "mass%" of the raw materials.

[0214] [Table 1]

[0215] [Table 2]

[0216] [Table 3]

[0217] [evaluation] (charge concentration) The charge concentration of each cation or anion component was calculated according to the following formula: Charge concentration [mmol / g] = (Number of charge-bearing or charge-bearing sites in the molecule) / (Molecular weight of the molecule containing counterions, if present) (In the formula, (If the molecule is in the form of a polymer, then the molecule means the repeating unit of the polymer.)

[0218] For example, if the molecule is phytic acid, it is known that the six acid groups in phytic acid have a pKa value of approximately 1.84, so the number of charged sites in phytic acid at pH 5 can be determined to be -6 (see Organic Synthetic Chemistry, Vol. 25, No. 2, pp. 167-179 (1967)). Since the molecular weight of phytic acid is 660, the charge concentration of phytic acid can be calculated as -6 / 660 = -0.00909 = -9.09 [mmol / g].

[0219] On the other hand, for example, if the molecule is poly-ε-lysine, the repeating unit of poly-ε-lysine can be represented as follows, and therefore, the number of sites that can have a charge in poly-ε-lysine can be determined to be 1. The primary amino group is charged under acidic conditions.

[0220] [ka]

[0221] Since the molecular weight of the repeating unit is 128, the charge concentration of poly-ε-lysine can be calculated as 1 / 128 = 0.00781 = +7.81 [mmol / g].

[0222] Please refer to the "Charge Concentration" column in Tables 1-3. The values ​​in the "Charge Concentration" column are absolute values.

[0223] (Polycation) The amount of cations in the cationic polymer was determined by multiplying the charge concentration of the cationic polymer by the amount of the cationic polymer.

[0224] The results are shown in the "Polycation" row of Tables 1-3.

[0225] (Polyanion) The amount of anions in the anionic polymer was determined by multiplying the charge concentration of the anionic polymer by the amount of the anionic polymer.

[0226] The results are shown in the "Polyanion" row of Tables 1-3.

[0227] (Low Mw anion) The amount of anions in the non-polymer (low molecular weight) anionic component was determined by multiplying the charge concentration of the non-polymer anionic component by the amount of the non-polymer anionic component.

[0228] The results are shown in the "Low Mw Anion" row of Tables 1-3.

[0229] (Polycation / Polyanion ratio) The ratio of the amount of cations in the cationic polymer to the amount of anions in the anionic polymer was determined by dividing the amount of cations in the cationic polymer by the amount of anions in the anionic polymer.

[0230] The results are shown in the "Polycation / Polyanion Ratio" row of Tables 1-3.

[0231] {Polycation / (Polyanion + Low Mw Anion) Ratio} The ratio of the amount of cations in the cationic polymer to the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component was determined by dividing the amount of cations in the cationic polymer by the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component.

[0232] The results are shown in the "Polycation / (Polyanion + Low Mw Anion) Ratio" row in Tables 1-3.

[0233] (exterior) The appearance of each composition prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-13 was observed visually. The results of the visual observation were classified as follows. U: Uniform (The appearance was uniform) A: Aggregates (The appearance was not uniform due to the presence of aggregates)

[0234] The results are shown in Tables 1-3.

[0235] The compositions according to Examples 1-1 to 1-6 had a uniform appearance, while the compositions according to Comparative Examples 1-1 to 1-13 had a non-uniform appearance due to aggregates present in the compositions.

[0236] (transparency) The turbidity of each composition prepared in Examples 1-1 to 1-6 was measured at room temperature (25°C) using a turbidimeter (2100Q portable, Hach Company).

[0237] The results are shown in Tables 1-3 as "NTU". The smaller the NTU value, the more transparent the composition.

[0238] The compositions from Examples 1-1 to 1-6 were transparent, while the compositions from Comparative Examples 1-1 to 1-13 were not transparent; therefore, their turbidity was not tested.

[0239] (particle size) The particle sizes in the compositions from Examples 1-1 to 1-6 were determined at room temperature (25°C) using a particle size analyzer (dynamic light scattering, ELSZ2000, Otsuka Corporation). The measurement data were fitted using the Marquardt method.

[0240] The results are shown in Tables 1-3.

[0241] The polyion complex particles in the compositions of Examples 1-1 to 1-6 were small, nano-sized, while the particle size in the compositions of Comparative Examples 1-1 to 1-13 could not be measured due to the presence of aggregates.

[0242] (summary) Polyion complex nanoparticles were obtained when the polycation / polyanion ratio was greater than 0.3 and less than 0.8, and the polycation / (polyanion + low Mw anion) ratio was greater than 0.2 and less than 0.5.

[0243] The particle size of the polyion complex particles ranged from approximately 30 nm to approximately 700 nm (see Examples 1-1 to 1-6).

[0244] When the polycation / polyanion ratio was 0.3 or less or 0.8 or more, and / or when the polycation / (polyanion + low Mw anion) ratio was 0.2 or less or 0.5 or more, aggregates were formed, and polyion complex nanoparticles were not obtained (see Comparative Examples 1-1 to 1-13).

[0245] (Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2) [Preparation] The compositions from Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2 were prepared by mixing the components shown in Table 4. The amounts of each component used in the above preparations are shown in Table 4. All numerical values ​​for the amounts of components shown in Table 4 are based on the "mass%" of the raw materials.

[0246] [Table 4A]

[0247] [Table 4B]

[0248] [evaluation] (charge concentration) The charge concentration of each cation or anion component was calculated according to the following formula: Charge concentration [mmol / g] = (Number of charge-bearing or charge-bearing sites in the molecule) / (Molecular weight of the molecule containing counterions, if present) (In the formula, (If the molecule is in the form of a polymer, then the molecule means the repeating unit of the polymer.)

[0249] Please refer to the "Charge Concentration" column in Table 4. The values ​​in the "Charge Concentration" column are absolute values.

[0250] (Polycation) The amount of cations in the cationic polymer was determined by multiplying the charge concentration of the cationic polymer by the amount of the cationic polymer.

[0251] The results are shown in the "Polycation" row of Table 4.

[0252] (Polyanion) The amount of anions in the anionic polymer was determined by multiplying the charge concentration of the anionic polymer by the amount of the anionic polymer.

[0253] The results are shown in the "Polyanion" row of Table 4.

[0254] (Low Mw anion) The amount of anions in the non-polymer (low molecular weight) anionic component was determined by multiplying the charge concentration of the non-polymer anionic component by the amount of the non-polymer anionic component.

[0255] The results are shown in the "Low Mw Anion" row in Table 4.

[0256] (Polycation / Polyanion ratio) The ratio of the amount of cations in the cationic polymer to the amount of anions in the anionic polymer was determined by dividing the amount of cations in the cationic polymer by the amount of anions in the anionic polymer.

[0257] The results are shown in the "Polycation / Polyanion Ratio" row of Table 4.

[0258] {Polycation / (Polyanion + Low Mw Anion) Ratio} The ratio of the amount of cations in the cationic polymer to the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component was determined by dividing the amount of cations in the cationic polymer by the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component.

[0259] The results are shown in the "Polycation / (Polyanion + Low Mw Anion) Ratio" row in Table 4.

[0260] (exterior) The appearance of each composition prepared in Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2 was observed visually. The results of the visual observation were classified as follows. U: Uniform (The appearance was uniform) SA: Some aggregates (the appearance was slightly non-uniform due to the aggregates) A: Aggregates (The appearance was not uniform due to the presence of aggregates)

[0261] The results are shown in Table 4.

[0262] The compositions from Examples 2-1 to 2-4 and Comparative Example 2-1 had a uniform appearance, while the composition from Comparative Example 2-2 had a non-uniform appearance due to aggregates present in the composition.

[0263] The compositions of Comparative Examples 2-5 and 2-6 contained some aggregates. However, their uniformity was acceptable.

[0264] (transparency) The turbidity of each composition from Examples 2-1 to 2-6 and Comparative Example 2-1 was measured at room temperature (25°C) using a turbidimeter (2100Q portable, Hach Company). The turbidity of the composition from Comparative Example 2-2 was too high and outside the detectable range, so its turbidity could not be measured.

[0265] The results are shown in Table 4 as "NTU". The smaller the NTU value, the more transparent the composition.

[0266] The compositions according to Comparative Examples 2-1 to 2-6 were transparent. The composition according to Comparative Example 2-1 was semi-transparent. The composition according to Comparative Example 2-2 was opaque.

[0267] (particle size) The particle sizes in the compositions of Examples 2-1 to 2-6 and Comparative Example 2-1 were determined at room temperature (25°C) using a particle size analyzer (dynamic light scattering, ELSZ2000, Otsuka Corporation). The measurement data were fitted using the Marquardt method. The particle size of the particles in the composition of Comparative Example 2-2 could not be obtained.

[0268] The results are shown in Table 4.

[0269] The polyion complex particles in the compositions of Examples 2-1 to 2-4 and Examples 2-5 and 2-6 were small, at the nanoscale, while the particles in the composition of Comparative Example 2-1 were large.

[0270] (summary) When the polyanion charge concentration was 2.04 mmol / g, nanoparticles could not be obtained (see Comparative Example 2-1).

[0271] On the other hand, when the charge concentration of the polyanion was greater than 2.04 mmol / g, nanoparticles were obtained (see Examples 2-1 to 2-4).

[0272] When the charge concentration of the polyanion was 5.00 mmol / g or higher, nanoparticles were obtained, but some aggregates were also formed (see Examples 2-5 and 2-6).

[0273] When the charge concentration of the polyanion was 10.64 mmol / g, aggregates were formed (see Comparative Example 2-2).

[0274] (Examples 3-1 and 3-2, and Comparative Example 3-1) [Preparation] The compositions of Examples 3-1 and 3-2, and Comparative Example 3-1, were prepared by mixing the components shown in Table 5. The amounts of each component used in the above preparations are shown in Table 5. All numerical values ​​for the amounts of components shown in Table 5 are based on the "mass%" of the raw materials.

[0275] [Table 5]

[0276] [evaluation] (charge concentration) The charge concentration of each cation or anion component was calculated according to the following formula: Charge concentration [mmol / g] = (Number of charge-bearing or charge-bearing sites in the molecule) / (Molecular weight of the molecule containing counterions, if present) (In the formula, (If the molecule is in the form of a polymer, then the molecule means the repeating unit of the polymer.)

[0277] Please refer to the "Charge Concentration" column in Table 5. The values ​​in the "Charge Concentration" column are absolute values.

[0278] (Polycation) The amount of cations in the cationic polymer was determined by multiplying the charge concentration of the cationic polymer by the amount of the cationic polymer.

[0279] The results are shown in the "Polycation" row of Table 5.

[0280] (Polyanion) The amount of anions in the anionic polymer was determined by multiplying the charge concentration of the anionic polymer by the amount of the anionic polymer.

[0281] The results are shown in the "Polyanion" row of Table 5.

[0282] (Low Mw anion) The amount of anions in the non-polymer (low molecular weight) anionic component was determined by multiplying the charge concentration of the non-polymer anionic component by the amount of the non-polymer anionic component.

[0283] The results are shown in the "Low Mw Anion" row of Table 5.

[0284] (Polycation / Polyanion ratio) The ratio of the amount of cations in the cationic polymer to the amount of anions in the anionic polymer was determined by dividing the amount of cations in the cationic polymer by the amount of anions in the anionic polymer.

[0285] The results are shown in the "Polycation / Polyanion Ratio" row of Table 5.

[0286] {Polycation / (Polyanion + Low Mw Anion) Ratio} The ratio of the amount of cations in the cationic polymer to the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component was determined by dividing the amount of cations in the cationic polymer by the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component.

[0287] The results are shown in the "Polycation / (Polyanion + Low Mw Anion) Ratio" row in Table 5.

[0288] (exterior) The appearance of each composition from Examples 3-1 and 3-2, and Comparative Example 3-1, was observed visually. The results of the visual observation were classified as follows. U: Uniform (The appearance was uniform) A: Aggregates (The appearance was not uniform due to the presence of aggregates)

[0289] The results are shown in Table 5.

[0290] The compositions according to Examples 3-1 and 3-2 had a uniform appearance, while the composition according to Comparative Example 3-1 had a non-uniform appearance due to aggregates present in the composition.

[0291] (transparency) The turbidity of each composition prepared in Examples 3-1 and 3-2 was measured at room temperature (25°C) using a turbidimeter (2100Q portable, Hach Company).

[0292] The results are shown in Table 5 as "NTU". The smaller the NTU value, the more transparent the composition.

[0293] The compositions from Examples 3-1 and 3-2 were transparent, while the composition from Comparative Example 3-1 was not transparent; therefore, its turbidity was not tested.

[0294] (particle size) The particle sizes in the compositions from Examples 3-1 and 3-2 were determined at room temperature (25°C) using a particle size analyzer (dynamic light scattering, ELSZ2000, Otsuka Corporation). The measurement data were fitted using the Marquardt method.

[0295] The results are shown in Table 5.

[0296] The polyion complex particles in the compositions of Examples 3-1 and 3-2 were small, nano-sized, while the particle size in the composition of Comparative Example 3-1 could not be measured due to the presence of aggregates.

[0297] (summary) When the charge concentration of the polyanion was 0.71 mmol / g, aggregates were formed, and nanoparticles could not be obtained (see Comparative Example 3-1).

[0298] When the charge concentration of the polycation was greater than 0.71 mmol / g, nanoparticles were obtained (see Examples 3-1 and 3-2).

[0299] (Examples 4-1 to 4-3) [Preparation] The compositions according to Examples 4-1 to 4-3 were prepared by mixing the components shown in Table 6. The amounts of each component used in the above preparations are shown in Table 6. All numerical values ​​for the amounts of components shown in Table 6 are based on the "mass%" of the raw materials.

[0300] [Table 6]

[0301] [evaluation] (charge concentration) The charge concentration of each cation or anion component was calculated according to the following formula: Charge concentration [mmol / g] = (Number of charge-bearing or charge-bearing sites in the molecule) / (Molecular weight of the molecule containing counterions, if present) (In the formula, (If the molecule is in the form of a polymer, then the molecule means the repeating unit of the polymer.)

[0302] Please refer to the "Charge Concentration" column in Table 6. The values ​​in the "Charge Concentration" column are absolute values.

[0303] (Polycation) The amount of cations in the cationic polymer was determined by multiplying the charge concentration of the cationic polymer by the amount of the cationic polymer.

[0304] The results are shown in the "Polycation" row of Table 6.

[0305] (Polyanion) The amount of anions in the anionic polymer was determined by multiplying the charge concentration of the anionic polymer by the amount of the anionic polymer.

[0306] The results are shown in the "Polyanion" row of Table 6.

[0307] (Low Mw anion) The amount of anions in the non-polymer (low molecular weight) anionic component was determined by multiplying the charge concentration of the non-polymer anionic component by the amount of the non-polymer anionic component.

[0308] The results are shown in the "Low Mw Anion" row in Table 6.

[0309] (Polycation / Polyanion ratio) The ratio of the amount of cations in the cationic polymer to the amount of anions in the anionic polymer was determined by dividing the amount of cations in the cationic polymer by the amount of anions in the anionic polymer.

[0310] The results are shown in the "Polycation / Polyanion Ratio" row of Table 6.

[0311] {Polycation / (Polyanion + Low Mw Anion) Ratio} The ratio of the amount of cations in the cationic polymer to the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component was determined by dividing the amount of cations in the cationic polymer by the sum of the amount of anions in the anionic polymer and the sum of the anions in the nonpolymer anionic component.

[0312] The results are shown in the "Polycation / (Polyanion + Low Mw Anion) Ratio" row in Table 6.

[0313] (exterior) The appearance of each composition prepared in Examples 4-1 to 4-3 was observed visually. The results of the visual observation were classified as follows. U: Uniform (The appearance was uniform) A: Aggregates (The appearance was not uniform due to the presence of aggregates)

[0314] The results are shown in Table 6.

[0315] The compositions produced by Examples 4-1 to 4-3 had a uniform appearance.

[0316] (transparency) The turbidity of each composition according to Examples 4-1 to 4-3 was measured at room temperature (25°C) using a turbidimeter (2100Q portable, Hach Company).

[0317] The results are shown in Table 6 as "NTU". The smaller the NTU value, the more transparent the composition.

[0318] The compositions prepared in Examples 4-1 to 4-3 were transparent.

[0319] (particle size) The particle sizes in the compositions from Examples 4-1 to 4-3 were determined at room temperature (25°C) using a particle size analyzer (dynamic light scattering, ELSZ2000, Otsuka Corporation). The measurement data were fitted using the Marquardt method.

[0320] The results are shown in Table 6.

[0321] The polyion complex particles in the compositions of Examples 4-1 to 4-3 were small, nano-sized.

[0322] (summary) Nanoparticles were obtained regardless of which nonpolymer acid was used (see Examples 4-1 to 4-3).

Claims

1. (a) at least one cationic polymer, (b) at least one anionic polymer, (c) at least one nonpolymeric acid or a salt thereof, (d) Water and A composition comprising, (a) The ratio of the amount of cations in the cationic polymer to (b) the amount of anions in the anionic polymer is 0.4 to 0.

7. (a) The ratio of the amount of cations in the cationic polymer to the sum of (b) the amount of anions in the anionic polymer and (c) the amount of anions in the nonpolymeric acid or its salt is 0.3 to 0.

4. (a) The charge concentration of the cationic polymer is greater than 0.71 mmol / g, (b) The charge concentration of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g, and (a) a cationic polymer, (b) an anionic polymer, and (c) a nonpolymeric acid or a salt thereof can form at least one polyion complex particle having a particle size of less than 1000 nm. composition.

2. (a) The composition according to claim 1, wherein the cationic polymer is selected from (co)polyamines.

3. (a) The composition according to claim 1 or 2, wherein the cationic polymer is selected from the group consisting of polylysine, chitosan, and mixtures thereof.

4. The composition according to any one of claims 1 to 3, wherein the amount of (a) a cationic polymer in the composition is 0.001 to 2% by mass of the total mass of the composition.

5. (b) The composition according to any one of claims 1 to 4, wherein the anionic polymer is selected from polysaccharides.

6. (b) The composition according to any one of claims 1 to 5, wherein the anionic polymer is selected from the group consisting of hyaluronate, ι-carrageenan, Λ-carrageenan, algin, chondroitin sulfate, pectin, and mixtures thereof.

7. The composition according to any one of claims 1 to 6, wherein the amount of (b) anionic polymer in the composition is 0.001% by mass to 2% by mass with respect to the total mass of the composition.

8. (c) The composition according to any one of claims 1 to 7, wherein the nonpolymer acid has two or more pKa values.

9. (c) The composition according to any one of claims 1 to 7, wherein the nonpolymeric acid is selected from the group consisting of phytic acid, citric acid, lactic acid and mixtures thereof.

10. The composition according to any one of claims 1 to 9, wherein the amount of (c) a nonpolymeric acid or a salt thereof in the composition is 0.001% by mass to 1% by mass with respect to the total mass of the composition.

11. The composition according to any one of claims 1 to 10, wherein the amount of (d) water in the composition is 60% by mass to 97% by mass with respect to the total mass of the composition.

12. The composition according to any one of claims 1 to 11, wherein the pH of the composition is 3 to 9.

13. This is a beauty method for keratin substances, A step of applying the composition according to any one of claims 1 to 12 to a keratin substance, The process involves drying the composition to form a cosmetic film on the keratin material. Beauty methods, including

14. (d) In a composition containing water, (a) at least one cationic polymer, (b) at least one anionic polymer, and (c) at least one nonpolymeric acid or a salt thereof of, (a) a cationic polymer, (b) an anionic polymer, and (c) a nonpolymeric acid or a salt thereof, for use in forming at least one polyion complex particle having a particle size of less than 1000 nm, (a) The ratio of the amount of cations in the cationic polymer to (b) the amount of anions in the anionic polymer is 0.4 to 0.

7. (a) The ratio of the amount of cations in the cationic polymer to the sum of (b) the amount of anions in the anionic polymer and (c) the amount of anions in the nonpolymeric acid or its salt is 0.3 to 0.

4. (a) The charge concentration of the cationic polymer is greater than 0.71 mmol / g, and (b) The charge concentration of the anionic polymer is greater than 2.04 mmol / g and less than 10.64 mmol / g. use.

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