Compositions comprising a mass of polyol
By using the crosslinking technology of cationic polymers and non-polymeric acids in the composition, the gel film is formed, and the problem of easy stickiness of polyol compositions is solved, achieving better cosmetic effects and texture.
Patent Information
- Application Number
- CN202380071424.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-11-17
- Filing Date
- 2023-09-15
- Publication Date
- 2025-05-13
AI Technical Summary
Compositions containing a large amount of polyols tend to become sticky and difficult to maintain beauty effects.
A gel film is formed to maintain the polyol by crosslinking the cationic polymer with the non-polymeric acid by crosslinking the cationic polymer with the non-polymeric acid to maintain the polyol by using a composition comprising a cationic polymer, a non-polymeric acid having two or more pKa values or a salt, a polyol and water.
Effectively reduces the viscosity of the composition, provides a smoother touch, and enhances beauty effects such as moisturizing effects by keeping the polyol on the keratin substance.
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Abstract
Description
Technical Field
[0001] The present invention relates to compositions comprising relatively large amounts of polyols and cosmetic methods of using the compositions. Background Art
[0002] Polyion complexes which may be in particulate form and which may be formed using cationic and anionic polymers are known.
[0003] For example, WO 2021 / 125069 discloses a composition that can be used for cosmetic treatment and, in one embodiment, comprises at least one polyion complex particle comprising at least one cationic polymer, at least one anionic polymer based on hyaluronic acid, and at least one non-polymeric acid or salt thereof having two or more pKa values. WO 2021 / 125069 also discloses a specific composition comprising 5% by weight of glycerol.
[0004] For example, WO 2022 / 131351 discloses a composition that can be used for cosmetic treatment and, in one embodiment, comprises at least one polyion complex particle comprising at least one cationic polymer, at least one anionic polymer, at least one non-polymeric acid or salt thereof having two or more pKa values, and at least one filler. WO 2022 / 131351 also discloses a specific composition comprising 5% by weight of glycerol.
[0005] Disclosure of the Invention
[0006] Polyols such as glycerol are commonly used for cosmetic purposes on keratinous materials such as skin. However, compositions containing large amounts (ie, 10% by weight or more relative to the total weight of the composition) of polyols such as glycerol tend to be sticky.
[0007] Therefore, an object of the present invention is to provide a composition which can show reduced viscosity while comprising a large amount (ie, 10 wt % or more relative to the total weight of the composition) of a polyol such as glycerol.
[0008] The above objects of the present invention can be achieved by a composition comprising:
[0009] (a) at least one cationic polymer;
[0010] (b) at least one non-polymeric acid or salt thereof having two or more pKa values;
[0011] (c) at least one polyol; and
[0012] (d) water,
[0013] The amount of (c) polyol in the composition is 10 wt % or more relative to the total weight of the composition.
[0014] The cationic polymer may be crosslinked using (b) a non-polymeric acid having two or more pKa values or a salt thereof (a).
[0015] (a) The cationic polymer may have at least one positively chargeable and / or positively charged moiety selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidine groups, imidazolyl groups, imino groups and pyridyl groups.
[0016] (a) The cationic polymer may be selected from cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride; (co)polyamines, such as chitosan and (co)polylysine; cationic (co)polyamino acids, such as collagen; cationic cellulose polymers; and salts thereof.
[0017] It may be preferred that (a) the cationic polymer is selected from polylysine, chitosan, and mixtures thereof.
[0018] The amount of (a) cationic polymer in the composition according to the invention may be 0.01% to 15% by weight, preferably 0.05% to 10% by weight and more preferably 0.1% to 5% by weight relative to the total weight of the composition.
[0019] (b) the non-polymeric acid or its salt having two or more pKa values may be an organic acid or its salt, preferably a hydrophilic organic acid or its salt or a water-soluble organic acid or its salt, and more preferably phytic acid or its salt, terephthalylidene dicamphorsulfonic acid or its salt, or a mixture thereof.
[0020] The amount of (b) non-polymeric acid having two or more pKa values or its salt in the composition according to the present invention may be 0.01 wt%-15 wt%, preferably 0.05 wt%-10 wt%, and more preferably 0.1 wt%-5 wt%, relative to the total weight of the composition.
[0021] Preferably, the (c) polyol is glycerol.
[0022] The amount of (c) polyol in the composition according to the present invention may be 95% by weight or less, relative to the total weight of the composition.
[0023] The composition according to the invention may further comprise (e) at least one anionic polymer.
[0024] (e) The anionic polymer may be selected from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and mixtures thereof, and more preferably hyaluronic acid and its salts, carboxymethylcellulose and its salts, and mixtures thereof.
[0025] The amount of (e) anionic polymer in the composition according to the invention may be 0.01% to 15% by weight, preferably 0.05% to 10% by weight and more preferably 0.1% to 5% by weight relative to the total weight of the composition.
[0026] The composition according to the present invention may be a cosmetic composition, preferably a care cosmetic composition, and more preferably a skin care cosmetic composition or a hair care cosmetic composition.
[0027] The present invention also relates to a cosmetic method for keratinous materials, comprising:
[0028] applying a composition according to the invention to a keratinous substance; and
[0029] The composition is dried to form a cosmetic film on the keratinous material.
[0030] Best Mode for Carrying Out the Invention
[0031] After diligent research, the inventors have discovered that it is possible to provide a composition that exhibits reduced viscosity while comprising a large amount (ie, 10 wt% or more relative to the total weight of the composition) of a polyol such as glycerol.
[0032] Therefore, the composition according to the invention comprises:
[0033] (a) at least one cationic polymer;
[0034] (b) at least one non-polymeric acid or salt thereof having two or more pKa values;
[0035] (c) at least one polyol; and
[0036] (d) water,
[0037] The amount of (c) polyol in the composition is 10 wt % or more relative to the total weight of the composition.
[0038] The composition according to the present invention can show reduced viscosity even if it contains a large amount of a polyol such as glycerol.
[0039] The viscosity of the composition according to the present invention is lower than that of a composition containing ingredient (c) in an amount of 10 wt% or more relative to the total weight of the composition, without ingredients (a) and (b).
[0040] Thus, the composition according to the present invention may provide an improved texture, such as a smoother feel.
[0041] Polyols such as glycerol are hydrophilic and, therefore, can be easily washed off the surface of keratinous materials with water. However, components (a) and (b) in the composition according to the present invention can form a gel film or coacervate which can sufficiently retain the polyol on a keratinous material such as the skin.
[0042] Therefore, the composition according to the invention may also provide enhanced cosmetic effects resulting from the polyols, such as enhanced moisturizing effects.
[0043] Hereinafter, the composition, method, etc. according to the present invention will be explained in a more detailed manner.
[0044] (Cationic polymer)
[0045] The composition according to the invention comprises (a) at least one cationic polymer.
[0046] There is no limitation on the type of (a) cationic polymer. Two or more different types of cationic polymers may be used in combination. Thus, a single type of cationic polymer or a combination of different types of cationic polymers may be used.
[0047] The cationic polymer has a positive charge density. (a) The charge density of the cationic polymer may be 0.01 meq / g to 20 meq / g, preferably 0.05 to 15 meq / g, and more preferably 0.1 to 10 meq / g.
[0048] It may be preferred that the molecular weight of the (a) cationic polymer is 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
[0049] Unless otherwise defined in the specification, "molecular weight" means number average molecular weight.
[0050] (a) The cationic polymer may have at least one moiety which may be positively charged and / or which is positively charged, which moiety is selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidine groups, imidazolyl groups, imino groups and pyridyl groups. The term (primary) "amino" herein means -NH 2 Group.
[0051] (a) The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two monomers and copolymers obtained from more than two monomers (eg terpolymers obtained from three monomers).
[0052] The (a) cationic polymer may be selected from natural cationic polymers and synthetic cationic polymers. Non-limiting examples of the (a) cationic polymer are as follows.
[0053] (1) Homopolymers and copolymers derived from acrylates and acrylamides or methacrylates and methacrylamides and comprising at least one unit selected from the group consisting of:
[0054]
[0055] in:
[0056] R 1 and R 2 may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl;
[0057] R 3 may be the same or different and are selected from hydrogen and CH 3 ;
[0058] The symbols A may be the same or different and are selected from a straight or branched chain alkyl group containing 1 to 6 carbon atoms (e.g. 2 to 3 carbon atoms) and a hydroxyalkyl group containing 1 to 4 carbon atoms;
[0059] R 4 , R 5 and R 6 may be the same or different, are selected from alkyl groups containing 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment are selected from alkyl groups containing 1 to 6 carbon atoms; and
[0060] X is an anion derived from an inorganic or organic acid, such as a methylsulfate anion; and a halogen ion, such as a chloride ion and a bromide ion.
[0061] The copolymers of the above family (1) may also contain at least one unit derived from a comonomer, which comonomer may be selected from acrylamide, methacrylamide, diacetone acrylamide, 1 -C 4 ) lower alkyl substituted acrylamides and methacrylamides, radicals derived from acrylic or methacrylic acid and their esters, vinyl lactams (eg vinyl pyrrolidone and vinyl caprolactam) and vinyl esters.
[0062] Examples of copolymers of series (1) include, but are not limited to:
[0063] Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide,
[0064] copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride (described, for example, in European Patent Application No. 0080976),
[0065] Copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methylsulfate,
[0066] quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers (described, for example, in French Patents Nos. 2077143 and 2393573),
[0067] Dimethylaminoethyl methacrylate / vinyl caprolactam / vinyl pyrrolidone terpolymer,
[0068] Vinyl pyrrolidone / methacrylamidopropyl dimethylamine copolymer, quaternized vinyl pyrrolidone / dimethylaminopropyl methacrylamide copolymer, and
[0069] Methacryloyloxy (C 1 -C 4 )alkyltri(C 1 -C 4 ) alkylammonium salt crosslinked polymers, for example polymers obtained by homopolymerizing dimethylaminoethyl methacrylate quaternized with methyl chloride or copolymerizing acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, and after the homopolymerization or copolymerization crosslinking with a compound containing ethylenic unsaturation, for example methylenebisacrylamide.
[0070] (2) Cationic cellulose polymers, for example cellulose ether derivatives containing one or more quaternary ammonium groups (described, for example, in French Patent No. 1492597), for example the polymers sold under the names "JR" (JR400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose which have been reacted with an epoxide substituted with a trimethylammonium group.
[0071] Preferably, the cationic cellulose polymer has at least one quaternary ammonium group, preferably a trialkyl quaternary ammonium group, and more preferably a trimethyl quaternary ammonium group.
[0072] The quaternary ammonium group may be present in a quaternary ammonium group-containing group which may be represented by the following chemical formula (I):
[0073]
[0074] in
[0075] R 1 and R 2 Each represents C 1- C 3 an alkyl group, preferably a methyl group or an ethyl group, and more preferably a methyl group,
[0076] R3 Represents C 1- C 24 an alkyl group, preferably a methyl group or an ethyl group, and more preferably a methyl group,
[0077] X - represents an anion, preferably a halogen ion, and more preferably a chloride ion,
[0078] n represents an integer of 0-30, preferably 0-10, and more preferably 0, and
[0079] R 4 Represents C 1- C 4 The alkylene group is preferably an ethylene group or a propylene group.
[0080] The leftmost ether bond (—O—) in the above chemical formula (I) may be linked to the sugar ring of the polysaccharide.
[0081] Preferably, the quaternary ammonium group is -O-CH 2 -CH(OH)-CH 2 -N + (CH 3 ) 3 .
[0082] (3) Cationic cellulose polymers, such as cellulose copolymers and cellulose derivatives grafted with water-soluble quaternary ammonium monomers and described, for example, in U.S. Pat. No. 4,131,576, for example, hydroxyalkyl celluloses such as hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose grafted with, for example, a salt selected from methacryloylethyltrimethylammonium salt, methacrylamidopropyltrimethylammonium salt and dimethyldiallyl ammonium salt.
[0083] Commercial products corresponding to these polymers include, for example, those sold by National Starch under the name " L 200" and H 100" products for sale.
[0084] (4) Non-cellulose-based cationic polysaccharides (described in U.S. Pat. Nos. 3,589,578 and 4,031,307), such as guar gum, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride containing cationic trialkylammonium groups. Guar gum modified with a salt (e.g., hydrochloride) of 2,3-epoxypropyltrimethylammonium (guar hydroxypropyltrimonium chloride) can also be used.
[0085] Such products are sold, for example, by the company MEYHALL under the trade name C13S, C15, C17 and C162 for sale.
[0086] (5) polymers comprising piperazinyl units and divalent alkylene or hydroxyalkylene groups, the divalent alkylene or hydroxyalkylene groups comprising linear or branched chains optionally interrupted by at least one entity selected from oxygen, sulfur, nitrogen, aromatic rings and heterocycles; and also oxidation products and / or quaternization products of these polymers. Such polymers are described, for example, in French Patents Nos. 2162025 and 2280361.
[0087] (6) Water-soluble polyaminoamides, prepared, for example, by polycondensation of acidic compounds with polyamines; these polyaminoamides may be crosslinked by means of entities selected from the group consisting of epihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides; diunsaturated derivatives; dihalohydrins; bisazetidinium; dihaloacyldiamines; dialkyl halides; oligomers resulting from the reaction of difunctional compounds reacted with entities selected from the group consisting of dihalohydrins, bisazetidinium, dihaloacyldiamines, dialkyl halides, epihalohydrins, diepoxides and diunsaturated derivatives; the amount of crosslinking agent used ranges 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 function, they may be quaternized. Such polymers are described, for example, in French Patents Nos. 2252840 and 2368508.
[0088] (7) Polyaminoamide derivatives produced by condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents, such as adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers, wherein the alkyl group contains 1 to 4 carbon atoms, such as methyl, ethyl and propyl, and the alkylene group contains 1 to 4 carbon atoms, such as ethylene. 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.
[0089] (8) Polymers obtained by the reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and a saturated aliphatic dicarboxylic acid containing 3 to 8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid may range from 0.8:1 to 1.4:1; the polyaminoamide thus produced is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine groups of the polyaminoamide ranging from 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Pat. Nos. 3,227,615 and 2,961,347.
[0090] (9) Cyclized polymers of alkyldiallylamines and dialkyldiallylammoniums, for example homopolymers and copolymers containing as main component of the chain at least one unit selected from the group consisting of the units of formulae (Ia) and (Ib):
[0091]
[0092]
[0093] in:
[0094] k and t can be the same or different, equal to 0 or 1, and the sum k+t equals 1;
[0095] R 12 is selected from hydrogen and methyl;
[0096] R 10 and R 11 The alkyl radicals may be the same or different and are selected from alkyl radicals containing 1 to 6 carbon atoms, hydroxyalkyl radicals wherein the alkyl radicals contain, for example, 1 to 5 carbon atoms, and lower (C 1 -C 4 ) amide alkyl, or R 10 and R 11 may form a heterocyclic group together with the nitrogen atom to which they are attached, such as piperidinyl and morpholinyl; and
[0097] Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. These polymers are described, for example, in French Patent No. 2080759 and its Certificate of Supplement No. 2190406.
[0098] In one embodiment, R 10 and R 11 The groups may be the same or different and are selected from alkyl groups containing 1 to 4 carbon atoms.
[0099] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chlorides, such as those marketed by CALGON under the name " Dimethyldiallylammonium chloride homopolymer (polyquaternium-6) (and its low weight average molecular weight homologues) sold under the name " 550" copolymer of diallyldimethylammonium chloride and acrylamide.
[0100] A quaternary diammonium polymer comprising at least one repeating unit of formula (II):
[0101]
[0102] in:
[0103] R 13 , R 14 , R 15 and R 16 may be the same or different and are selected from aliphatic groups, alicyclic groups 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 may form together or individually with the nitrogen atom to which they are attached a heterocyclic ring which optionally contains a second heteroatom in addition to nitrogen, or R 13 , R 14 , R 15 and R 16 may be the same or different and are selected from a linear or branched C 1 -C 6 Alkyl: nitrile, ester, acyl, amide, -CO-OR 17 -E group and -CO-NH-R 17 -E group, where R 17 is an alkylene group, and E is a quaternary ammonium group;
[0104] A 1 and B 1 may be identical or different, and are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain at least one entity selected from the following groups, attached to or inserted in the main chain: an aromatic ring, an oxygen, a sulfur, a sulfoxide group, a sulfone group, a disulfide group, an amino group, an alkylamino group, a hydroxyl group, a quaternary ammonium group, a urea group, an amide group, and an ester group, and
[0105] X - is an anion derived from an inorganic or organic acid;
[0106] A 1 , R 13 and R 15 Together with the two nitrogen atoms to which they are attached, they can form a piperazine ring;
[0107] If A 1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene, then B 1 You can choose from:
[0108] -(CH 2 ) n -CO-E'-OC-(CH 2 ) n -
[0109] Wherein E' is selected from:
[0110] a) a diol residue of the formula -OZO-, wherein Z is selected from linear or branched hydrocarbon-based groups and groups of the formula:
[0111] -(CH 2 -CH 2 -O) x -CH 2 -CH 2 -
[0112] -[CH 2 -CH(CH 3 )-O] y -CH 2 -CH(CH 3 )-
[0113] wherein x and y may be the same or different and are selected from integers ranging from 1 to 4, which represent a definite and unique degree of polymerization, and numbers ranging from 1 to 4, which represent an average degree of polymerization;
[0114] b) bis(secondary diamine) residues, for example piperazine derivatives;
[0115] c) a bis(primary diamine) residue of the formula -NH-Y-NH-, wherein Y is selected from a linear or branched hydrocarbon-based group and a divalent group -CH 2 -CH 2 -SS-CH 2 -CH 2 -;as well as
[0116] d) a ureidene group of the formula -NH-CO-NH-.
[0117] In at least one embodiment, X - is an anion, such as chloride or bromide.
[0118] Polymers of this type are described, for example, in French Patent Nos. 2320330; 2270846; 2316271; 2336434; and 2413907; and in U.S. Patent Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261 ,002; No. 2,271,378; No. 3,874,870; No. 4,001,432; No. 3,929,990; No. 3,966,904; No. 4,005,193; No. 4,025,617; No. 4,025,627; No. 4,025,653; No. 4,026,945; and No. 4,027,020.
[0119] Non-limiting examples of such polymers include those comprising at least one repeating unit of formula (III):
[0120]
[0121] Where 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 may be the same or different and are integers ranging from 2 to 20, and X - It is an anion derived from an inorganic acid or an organic acid.
[0122] (11) A polyquaternary ammonium polymer comprising units of formula (IV):
[0123]
[0124] in:
[0125] R 18 , R 19 , R 20 and R 21 may be the same or different and are selected from hydrogen, methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, -CH 2 CH 2 (OCH 2 CH 2 ) p OH group, wherein p is selected from an integer in the range of 0-6, with the proviso that R 18 , R 19 , R 20 and R 21 Different from hydrogen,
[0126] r and s may be the same or different and are selected from integers ranging from 1 to 6,
[0127] q is selected from an integer in the range of 0-34,
[0128] X - is an anion, such as a halide ion, and
[0129] A is selected from dihalide and -CH 2 -CH 2 -O-CH 2 -CH 2 -group.
[0130] Such compounds are described, for example, in European Patent Application No. 0122324.
[0131] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole.
[0132] Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines (e.g. polyethyleneimine), polymers comprising units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.
[0133] According to one embodiment of the invention, (a) the cationic polymer is selected from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold under the name "JR400" by the company UNION CARBIDE CORPORATION; cationic cyclized polymers, such as the product sold under the name SUPER TETRA CERTAIN by the company CALGON; 100. 550 and Homopolymers and copolymers of dimethyldiallylammonium chloride sold by S; guar gum modified with 2,3-epoxypropyltrimethylammonium salt; and quaternary ammonium polymers of vinylpyrrolidone and vinylimidazole.
[0134] (13) Polyamine
[0135] As (a) cationic polymers, it is also possible to use (co)polyamines, which may be homopolymers or copolymers having a plurality of amino groups. The amino groups may be primary, secondary, tertiary or quaternary amino groups. The amino groups may be present in the polymer backbone or in the side groups (if present) of the (co)polyamines.
[0136] As examples of (co)polyamines, mention may be made of chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate; (co)polyvinylpyridines, for example (co)poly-1-methyl-2-vinylpyridine; (co)polyimines, for example (co)polyethyleneimine; (co)polypyridines, for example (co)poly(quaternary pyridine); (co)polybiguanides, for example (co)polyaminopropyl biguanide; (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof.
[0137] It may be preferred that (a) the cationic polymer is selected from chitosan.
[0138] It may also be preferred that the (a) cationic polymer is selected from (co)polylysine.
[0139] 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 α-poly-L-lysine and ε-poly-L-lysine, which are commonly used as natural preservatives in food. Polylysine is a polymer electrolyte that is soluble in polar solvents such as water, propylene glycol and glycerol. Polylysine can be commercially available in various forms (e.g., poly-D-lysine and poly-L-lysine). Polylysine can be in the form of salts and / or solutions.
[0140] (14) Cationic polyamino acid
[0141] As (a) cationic polymer, it is possible to use a cationic polyamino acid, which may be a cationic homopolymer or a cationic copolymer having a plurality of amino groups and carboxyl groups. The amino group may be a primary amino group, a secondary amino group, a tertiary amino group or a quaternary amino group. The amino group may be present in the polymer backbone or side group (if present) of the cationic polyamino acid. The carboxyl group may be present in the side group (if present) of the cationic polyamino acid.
[0142] As examples of cationic polyamino acids, there can be mentioned cationized collagen, cationized gelatin, stearyldimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin, stearyldimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein and the like.
[0143] The following description relates to preferred embodiments of the (a) cationic polymer.
[0144] Preferably, the (a) cationic polymer is selected from cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride; (co)polyamines, such as chitosan and (co)polylysine; cationic (co)polyamino acids, such as cationized collagen; cationic cellulose polymers; and salts thereof.
[0145] It may be more preferred that the (a) cationic polymer is selected from polylysine, chitosan, and mixtures thereof.
[0146] The amount of (a) cationic polymer in the composition according to the present invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.
[0147] The amount of (a) cationic polymer in the composition according to the invention may be 15 wt% or less, preferably 10 wt% or less and more preferably 5 wt% or less, relative to the total weight of the composition.
[0148] The amount of (a) cationic polymer in the composition according to the invention may be 0.01% to 15% by weight, preferably 0.05% to 10% by weight and more preferably 0.1% to 5% by weight relative to the total weight of the composition.
[0149] (Anionic polymer)
[0150] The composition according to the invention may comprise (e) at least one anionic polymer.
[0151] If the composition according to the present invention comprises (e) anionic polymer, the (a) cationic polymer may form a polyion complex with the (e) anionic polymer.
[0152] There is no limitation on the type of (e) anionic polymer. Two or more different types of anionic polymers may be used in combination. Thus, a single type of anionic polymer or a combination of different types of anionic polymers may be used.
[0153] The anionic polymer has a positive charge density. If the (e) anionic polymer is a synthetic anionic polymer, the charge density of the (e) anionic polymer may be 0.1 meq / g to 20 meq / g, preferably 1 to 15 meq / g, and more preferably 4 to 10 meq / g, and if the (e) 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.
[0154] It may be preferred that the molecular weight of the (e) anionic polymer is 1,000 or more, preferably 3,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, and even more preferably 1,000,000 or more.
[0155] Unless otherwise defined in the specification, "molecular weight" may mean number average molecular weight.
[0156] (e) The anionic polymer may have at least one negatively chargeable and / or negatively charged moiety selected from sulfate, sulfate, sulfonic acid, sulfonate, phosphate, phosphate, phosphonic acid, phosphonate, carboxylic acid and carboxylate groups.
[0157] (e) The anionic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two monomers and copolymers obtained from more than two monomers (eg terpolymers obtained from three monomers).
[0158] (e) The anionic polymer may be selected from natural anionic polymers and synthetic anionic polymers.
[0159] (e) The anionic polymer may contain at least one hydrophobic chain.
[0160] The anionic polymer comprising at least one hydrophobic chain can be obtained by copolymerizing a monomer (a) selected from carboxylic acid comprising α,β-ethylenic unsaturation (monomer a') and 2-acrylamido-2-methylpropanesulfonic acid (monomer a") with a non-surface-active monomer (b) comprising ethylenic unsaturation other than (a) and / or a monomer (c) comprising ethylenic unsaturation obtained by reacting an acrylic monomer comprising α,β-monoethylenic unsaturation or an isocyanate monomer comprising monoethylenic unsaturation with a monohydroxy nonionic amphiphilic component or with a primary or secondary fatty amine.
[0161] Thus, anionic polymers with at least one hydrophobic chain can be obtained via two synthetic routes:
[0162] - or by copolymerization of monomers (a') and (c), or (a'), (b) and (c), or (a") and (c), or (a"), (b) and (c),
[0163] - or by copolymers formed from monomer (a'), or monomers (a') and (b), or (a") and (b) being modified (and in particular esterified or amidated) by a hydroxy nonionic amphiphilic compound or a primary or secondary fatty amine.
[0164] As 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may especially be made of those disclosed in the article “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” and in applications EP-A-0750899 and EP-A-1069172.
[0165] The carboxylic acid containing α,β-monoethylenic unsaturation constituting monomer (a′) may be selected from numerous acids and in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. It is preferably acrylic acid or methacrylic acid.
[0166] The copolymer may contain monomers (b) containing monoethylenic unsaturation which do not have surfactant properties. Preferred monomers are those which produce water-insoluble polymers when they are homopolymerized. They can be selected, for example, from acrylic acid, C 1 -C 4 Alkyl esters and methacrylate C 1 -C 4 Alkyl esters, for example 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, vinyl toluene, vinyl acetate, acrylonitrile and vinylidene chloride. Non-reactive monomers are preferred, these monomers being those in which a single alkenyl group is the only reactive group under polymerization conditions. However, monomers containing groups that react under the action of heat, for example hydroxyethyl acrylate, can be optionally used.
[0167] Monomer (c) is obtained by reaction of an acrylic monomer containing α,β-monoethylenic unsaturation (eg (a)) or an isocyanate monomer containing monoethylenic unsaturation with a monohydroxy nonionic amphiphilic compound or a primary or secondary fatty amine.
[0168] The monohydroxy nonionic amphiphilic compounds or primary or secondary fatty amines used to prepare the nonionic monomers (c) are well known. The monohydroxy nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds, which contain alkylene oxides forming the hydrophilic part of the molecule. The hydrophobic compound is generally composed of aliphatic alcohols or alkylphenols, in which a carbonaceous chain containing at least 6 carbon atoms constitutes the hydrophobic part of the amphiphilic compound.
[0169] Preferred monohydroxy nonionic amphiphilic compounds are compounds having the following formula (V):
[0170] R-(OCH 2 CHR') m -(OCH 2 CH 2 ) n -OH(V)
[0171] wherein R is selected from an alkyl or alkenyl group containing 6-30 carbon atoms, and an alkylaryl group having an alkyl group containing 8-30 carbon atoms, R' is selected from an alkyl group containing 1-4 carbon atoms, n is an average number ranging from about 1-150, and m is an average number ranging from about 0-50, provided that n is at least as large as m.
[0172] Preferably, in the compound of formula (V), the R group is selected from an alkyl group containing 12 to 26 carbon atoms, and wherein the alkyl group is C 8 -C 13The R' group is a methyl group; m=0 and n=1-25.
[0173] Preferred primary and secondary fatty amines are composed of one or two alkyl chains containing 6 to 30 carbon atoms.
[0174] The monomers used to form the nonionic urethane monomers (c) can be selected from a very diverse range of compounds. Any compound containing copolymerizable unsaturation (bonds) (such as acrylic, methacrylic or allylic unsaturation (bonds)) can be used. Monomer (c) can be obtained especially from isocyanates containing monoethylenic unsaturation (bonds) (such as especially α, α-dimethyl-meta-isopropenylbenzyl isocyanate).
[0175] Monomer (c) may be selected in particular from oxyethylenated (1 to 50 EO) C 6 -C 30 Acrylates, methacrylates or itaconates of fatty alcohols, such as steareth-20 methacrylate, oxyethylated (25EO) behenyl methacrylate, oxyethylated (20EO) monocetyl itaconate, oxyethylated (20EO) monostearyl itaconate, or polyoxyethylated (25EO) C 12 -C 24 Alcohol modified acrylate; and oxyethylenated (1 to 50EO) C 6 -C 30 Dimethyl-m-isopropenylbenzyl isocyanate of fatty alcohols, for example especially dimethyl-m-isopropenylbenzyl isocyanate of oxyethylated behenyl alcohol.
[0176] According to a specific embodiment of the present invention, the (e) anionic polymer is selected from an acrylic terpolymer obtained by (a) a carboxylic acid containing α,β-ethylenic unsaturation, (b) a non-surface-active monomer containing ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer (which is a reaction product of a monohydroxy nonionic amphiphilic compound and an isocyanate containing monoethylenic unsaturation).
[0177] As anionic polymers comprising at least one hydrophobic chain, mention may especially be made of acrylic acid / ethyl acrylate / alkyl acrylate terpolymers, such as the product sold under the name Acusol 823 by Rohm & Haas as a 30% aqueous dispersion; acrylates / steareth-20 methacrylate copolymers, such as the product sold under the name Aculyn 22 by Rohm & Haas; (meth)acrylic acid / ethyl acrylate / oxyethylated (25EO) behenyl methacrylate terpolymers, such as the product sold under the name Aculyn 28 by Rohm & Haas as an aqueous emulsion; acrylic acid / oxyethylated (20EO) monocetyl itaconate copolymers, such as the product sold under the name Structure 3001 by National Starch as a 30% aqueous dispersion; acrylic acid / oxyethylated (20EO) monostearyl itaconate copolymers, such as the product sold under the name Structure 2001 by National Starch as a 30% aqueous dispersion; acrylates / polyoxyethylated (25EO) C 12 -C 24 Alcohol-modified acrylate copolymers, for example the 30-32% copolymer latex sold under the name Synthalen W 2000 by 3V SA; or the dimethyl-meta-isopropenylbenzyl isocyanate terpolymer of methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol, for example the product disclosed in document EP-A-0 173 109 as a 24% aqueous dispersion and containing 40 ethylene oxide groups.
[0178] (e) The anionic polymer may also be polyester-5, for example, manufactured by EASTMANCHEMICAL under the name Eastman AQ TM The product sold by 55S Polymer has the following chemical formula.
[0179]
[0180] A: Dicarboxylic acid part
[0181] G: Diol part
[0182] SO 3 - Na + :Sodium Sulfonate
[0183] OH: Hydroxyl
[0184] Preferably, (e) the anionic polymer is selected from polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (such as carboxymethyl cellulose and cellulose gum); anionic (co)polyamino acids such as (co)polyglutamic acid; (co)poly(meth)acrylic acid; (co)polyamic acid; (co)polystyrene sulfonate; (co)poly(vinyl sulfate); dextran sulfate; chondroitin sulfate; (co)polymaleic acid; (co)polyfumaric acid; maleic acid (co)polymers; and their salts.
[0185] The maleic acid copolymer may comprise one or more maleic acid comonomers and one or more comonomers selected from the group consisting of vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing 2 to 20 carbon atoms, and styrene.
[0186] Thus, "maleic acid copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic acid comonomers, optionally partially or completely hydrolyzed, with one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing 2 to 20 carbon atoms such as octadecene, ethylene, isobutylene, diisobutylene or isooctene and styrene. It will be preferred to use hydrophilic polymers, that is to say polymers having a water solubility greater than or equal to 2 g / l.
[0187] In an advantageous aspect of the present invention, the maleic acid copolymer may have a molar fraction of maleic acid units between 0.1 and 1, more preferably between 0.4 and 0.9.
[0188] The weight average molar mass of the maleic acid copolymer may be between 1,000 and 500,000, and preferably between 1,000 and 50,000.
[0189] Preferably, the maleic acid copolymer is a styrene / maleic acid copolymer, and more preferably a sodium styrene / maleic acid copolymer.
[0190] It will be preferred to use a copolymer of styrene and maleic acid in a 50 / 50 ratio.
[0191] For example, the CrayValley Styrene / maleic acid (50 / 50) copolymer sold as a 30% ammonium salt in water or by Cray Valley under the designation Styrene / maleic acid (50 / 50) copolymer sold as a 40% sodium salt in water.
[0192] The use of styrene / maleic acid copolymers, such as sodium styrene / maleic acid copolymer, can improve the wettability of films prepared from the composition according to the present invention.
[0193] According to one embodiment of the present invention, it is preferred that the (e) anionic polymer is selected from hyaluronic acid and its derivatives.
[0194] Hyaluronic acid can be represented by the following chemical formula.
[0195]
[0196] In the context of the present invention, the term "hyaluronic acid" especially encompasses the basic unit of hyaluronic acid of the following formula:
[0197]
[0198] This is the smallest fraction of hyaluronic acid and contains disaccharide dimers (ie, D-glucuronic acid and N-acetylglucosamine).
[0199] In the context of the present invention, the term "hyaluronic acid and its derivatives" also includes linear polymers comprising the polymer units described above linked together in a chain via alternating β(1,4) glycosidic bonds and β(1,3) glycosidic bonds, having a molecular weight (MW) that can range between 380 Daltons and 13,000,000 Daltons. This molecular weight depends largely on the source from which the hyaluronic acid is obtained and / or the method of preparation.
[0200] In the context of the present invention, the term "hyaluronic acid and its derivatives" also includes hyaluronates. As salts, there may be mentioned alkali metal salts (eg sodium and potassium salts), alkaline earth metal salts (eg magnesium salts), ammonium salts, and mixtures thereof.
[0201] In the natural state, hyaluronic acid is present in the pericellular gel, the base material of the connective tissues of vertebrate organs (such as dermal tissue and epithelial tissue), and especially in the epidermis, synovial fluid, vitreous humor, human umbilical cord and cockscomb.
[0202] Therefore, the term "hyaluronic acid and its derivatives" includes all fractions or subunits of hyaluronic acid having a molecular weight, in particular within the molecular weight range reviewed above.
[0203] In the context of the present invention, preference is given to using hyaluronic acid fractions which have no inflammatory activity.
[0204] For an explanation of various hyaluronic acid fractions, reference may be made to the document “Hyaluronan fragments: an information-rich system”, R. Stern et al., European Journal of Cell Biology 58 (2006) 699-715, which reviews the biological activities of hyaluronic acid listed according to the molecular weight of hyaluronic acid.
[0205] According to a preferred embodiment of the invention, the molecular weight of the hyaluronic acid fraction suitable for the uses covered by the invention is between 50,000 Da and 5,000,000 Da, in particular between 100,000 Da and 5,000,000 Da, in particular between 400,000 Da and 5,000,000 Da. In this case, the term used is high molecular weight hyaluronic acid.
[0206] Alternatively, the hyaluronic acid fractions suitable for the uses encompassed by the present invention may have a molecular weight between 50,000 Da and 400,000 Da. In this case, the term medium molecular weight hyaluronic acid is used.
[0207] Still alternatively, the hyaluronic acid fraction suitable for the uses encompassed by 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.
[0208] Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, especially those in which all or some of the carboxyl groups of the acid functions are esterified with oxyethylated alkyl groups or alcohols (containing 1-20 carbon atoms), especially with a degree of substitution ranging from 0.5 to 50% at the level of D-glucuronic acid of hyaluronic acid.
[0209] Mention may be made in particular of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid. Such esters have been described in particular in D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998) 2101-2127.
[0210] The hyaluronic acid derivative may be, for example, acetylated hyaluronic acid or a salt thereof.
[0211] The molecular weights specified above are also valid for hyaluronate esters.
[0212] The hyaluronic acid may be, in particular, the hyaluronic acid supplied by Hyactive under the trade name CPN (MW: 10-150 kDa), the hyaluronic acid supplied by Soliance under the trade name Cristalhyal (MW: 1.1×10 6), hyaluronic acid supplied by Bioland under the name NutraHA (MW: 820000Da), hyaluronic acid supplied by Bioland under the name NutraAF (MW: 69000Da), hyaluronic acid supplied by Bioland under the name Oligo HA (MW: 6100Da), or hyaluronic acid supplied by Vam Farmacos Metica under the name D Factor (MW: 380Da).
[0213] It may be preferred that the (e) anionic polymer is selected from natural anionic polymers, and more preferably selected from polysaccharides.
[0214] It may be even more preferred that the (e) anionic polymer is selected from hyaluronic acid and its derivatives; cellulosic polymers and their salts, such as carboxymethylcellulose and cellulose gum (sodium carboxymethylcellulose); and mixtures thereof.
[0215] Therefore, (e) the anionic polymer can be selected from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and mixtures thereof, and more preferably hyaluronic acid and its salts (e.g. sodium hyaluronate), carboxymethylcellulose such as cellulose gum and its salts, and mixtures thereof.
[0216] The amount of (e) anionic polymer in the composition according to the present invention may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, relative to the total weight of the composition.
[0217] The amount of (e) anionic polymer in the composition according to the present invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.
[0218] The amount of (e) anionic polymer in the composition according to the invention may be 0.01% to 15% by weight, preferably 0.05% to 10% by weight and more preferably 0.1% to 5% by weight relative to the total weight of the composition.
[0219] The total amount of (a) cationic polymer and (e) anionic polymer in the composition according to the present invention may be 0.1 wt% or more, preferably 0.5 wt% or more, and more preferably 1 wt% or more, relative to the total weight of the composition.
[0220] The total amount of (a) cationic polymer and (e) anionic polymer in the composition according to the present invention may be 20 wt% or less, preferably 15 wt% or less, and more preferably 10 wt% or less, relative to the total weight of the composition.
[0221] The total amount of (a) cationic polymer and (e) anionic polymer in the composition according to the invention may be 0.1% to 20% by weight, preferably 0.5% to 15% by weight and more preferably 1% to 10% by weight relative to the total weight of the composition.
[0222] The ratio of the amount such as chemical equivalent of (a) cationic polymer / (e) anionic polymer may be 0.05-18, preferably 0.1-10, and more preferably 0.5-5.0. In particular, it is preferred that the number of cationic groups of (a) cationic polymer / the number of anionic groups of (e) anionic polymer is 0.05-18, more preferably 0.1-10, and even more preferably 0.5-5.0.
[0223] (Non-polymeric acids with two or more acid dissociation constants)
[0224] The composition according to the invention comprises (b) at least one non-polymeric acid or salt thereof having two or more pKa values, i.e. at least one non-polymeric acid or salt thereof having two or more acid dissociation constants. The pKa values (acid dissociation constants) are well known to those skilled in the art and should be determined at a constant temperature such as 25°C.
[0225] (b) The non-polymeric acid having two or more pKa values may serve as a cross-linking agent for the (a) cationic polymer. The (a) cationic polymer may be ionically cross-linked by the (b) non-polymeric acid having two or more pKa values or a salt thereof.
[0226] The term "non-polymeric" here means that the acid is not obtained by polymerizing two or more monomers. Thus, a non-polymeric acid does not correspond to an acid obtained by polymerizing two or more monomers, such as a polycarboxylic acid.
[0227] It is preferred that the molecular weight of (b) the non-polymeric acid having two or more pKa values or its salt is 1,000 or less, preferably 800 or less, and more preferably 700 or less.
[0228] There is no restriction on the type of non-polymeric acid or its salt having two or more pKa values (b). Two or more different types of non-polymeric acid or its salt having two or more pKa values can be used in combination. Therefore, a single type of non-polymeric acid or its salt having two or more pKa values or a combination of non-polymeric acid or its salt having two or more pKa values of different types can be used.
[0229] The term "salt" here means a salt formed by adding a suitable base to a non-polymeric acid having two or more pKa values, which can be obtained by reacting a non-polymeric acid having two or more pKa values with a base according to methods known to those skilled in the art. As salts, metal salts, such as salts with alkali metals (such as Na and Ka), and salts with alkaline earth metals (such as Mg and Ca), and ammonium salts can be mentioned.
[0230] (b) The non-polymeric acid or its salt having two or more pKa values may be an organic acid or its salt, and is preferably a hydrophilic organic acid or its salt or a water-soluble organic acid or its salt.
[0231] (b) The non-polymeric acid having two or more pKa values may have at least two acid groups selected from the group consisting of carboxylic acid groups, sulfate groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, phenolic hydroxyl groups, and mixtures thereof.
[0232] (b) The non-polymeric acid having two or more pKa values may be a non-polymeric polyacid.
[0233] (b) The non-polymeric acid having two or more pKa values may be selected from dicarboxylic acids, disulfonic acids and diphosphoric acids, and mixtures thereof.
[0234] (b) a non-polymeric acid or a salt thereof having two or more pKa values may be selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and salts thereof; aspartic acid, glutamic acid, and salts thereof; terephthalylidene dicamphorsulfonic acid or salts thereof (Mexoryl SX), benzophenone-9; phytic acid and its salts; Red 2 (Amaranth), Red 102 (New Carmine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF), Green 3 (Fast Green FCF), Blue 1 (Brilliant Blue FCF), Blue 2 (Indigo Carmine), Red 201 (Lithol Ruby B), Red 202 (Lithol Ruby BCA), Red 204 (Lake Red CBA), Red 206 (Lithol Red CA), Red 207 (Lithol Red BA), Red 208 (Lithol Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Dark Maroon), Red 227 (Fast Acid Fuchsin), Yellow 203 (Quinoline Yellow WS), Green 201 (Alizarin Cyanine Green F), Green 204 (Pyranine Conc), Green 205 (Brilliant Green SF Light Yellow), Blue 203 (Patent Blue CA), Blue 205 (Sub-species Green FG), Red 401 (Purpleamine R), Red 405 (Permanent Re 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, isoascorbic acid, and salts thereof; cystine and salts thereof; EDTA and salts thereof; glycyrrhizic acid and salts thereof; and mixtures thereof.
[0235] It may be preferred that (b) the non-polymeric acid or its salt having two or more pKa values is selected from terephthalylidene dicamphorsulfonic acid or its salt (Mexoryl SX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and its salt, and mixtures thereof.
[0236] It may be more preferred that (b) the non-polymeric acid or salt thereof having two or more pKa values is selected from terephthalylidene dicamphorsulfonic acid or its salt (Mexoryl SX), phytic acid and its salt, and mixtures thereof.
[0237] The amount of (b) the non-polymeric acid having two or more pKa values or its salt in the composition according to the present invention may be 0.01 wt % or more, preferably 0.05 wt % or more, and more preferably 0.1 wt % or more, relative to the total weight of the composition.
[0238] The amount of (b) the non-polymeric acid or its salt having two or more pKa values in the composition according to the present invention may be 15 wt % or less, preferably 10 wt % or less, and more preferably 5 wt % or less, relative to the total weight of the composition.
[0239] The amount of (b) non-polymeric acid having two or more pKa values or its salt in the composition according to the present invention may be 0.01 wt%-15 wt%, preferably 0.05 wt%-10 wt%, and more preferably 0.1 wt%-5 wt%, relative to the total weight of the composition.
[0240] [Polyol]
[0241] The composition according to the invention comprises (c) at least one polyol. If two or more polyols are used, they may be identical or different.
[0242] The term "polyol" herein means an alcohol having two or more hydroxyl groups, and does not encompass sugars or their derivatives. Derivatives of sugars include sugar alcohols obtained by reducing one or more carbonyl groups of sugars; and sugars or sugar alcohols in which a hydrogen atom in one or more hydroxyl groups thereof has been replaced by at least one substituent such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group, or a carbonyl group.
[0243] The polyol used in the present invention is liquid at ambient temperature (eg, 25° C.) under atmospheric pressure (760 mmHg or 105 Pa).
[0244] (c) The polyol may be C 2-24 Polyol, preferably C 2-9 A polyol comprising at least 2 hydroxyl groups, and preferably 2 to 5 hydroxyl groups.
[0245] (c) The polyol may be a natural polyol or a synthetic polyol. The polyol may have a linear, branched or cyclic molecular structure.
[0246] (c) The polyol may be selected from glycerol and its derivatives, and diol and its derivatives. The polyol may be selected from glycerol, diglycerol, polyglycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentanediol, hexanediol, C 6 -C 24 Polyethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,5-pentanediol.
[0247] Preferably, (c) the polyol is glycerol.
[0248] The amount of (c) polyol in the composition used in the present invention is 10 wt % or more, preferably 15 wt % or more, and more preferably 20 wt % or more, relative to the total weight of the composition.
[0249] On the other hand, the amount of (c) polyol in the composition used in the present invention may be 95 wt % or less, preferably 60 wt % or less, and more preferably 30 wt % or less, relative to the total weight of the composition.
[0250] The amount of (c) polyol in the composition used in the present invention may range from 10 wt% to 95 wt%, preferably from 10 wt% to 60 wt%, and more preferably from 10 wt% to 30 wt%, relative to the total weight of the composition.
[0251] [water]
[0252] The composition according to the present invention comprises (d) water.
[0253] The amount of (d) water may be 1 wt% or more, preferably 30 wt% or more, and more preferably 50 wt% or more, relative to the total weight of the composition.
[0254] The amount of (d) water may be 90 wt% or less, preferably 50 wt% or less, and more preferably 10 wt% or less, relative to the total weight of the composition.
[0255] The amount of (d) water may be 1 wt% to 90 wt%, preferably 30 wt% to 90 wt%, and more preferably 50 wt% to 90 wt%, relative to the total weight of the composition.
[0256] [pH]
[0257] The pH of the composition according to the present invention may be 9.0 or lower, preferably 8.5 or lower, and more preferably 8.1 or lower.
[0258] The pH of the composition according to the present invention may be 3.0 or higher, preferably 3.3 or higher, and more preferably 3.5 or higher.
[0259] The pH of the composition according to the present invention may be 3.0-9.0, preferably 3.3-8.5, and more preferably 3.5-8.1.
[0260] At a pH of 3.0-9.0, the composition according to the present invention may be very stable.
[0261] The pH of the composition according to the invention can be adjusted by adding at least one alkaline agent and / or at least one acid other than (b) a non-polymeric acid or a salt thereof having two or more pKa values. The pH of the composition according to the invention can also be adjusted by adding at least one buffer.
[0262] (Alkali)
[0263] The composition according to the invention may comprise at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.
[0264] The alkali agent may be an inorganic alkali agent, preferably, the inorganic alkali agent is selected from ammonia; alkali metal hydroxides; alkaline earth metal hydroxides; alkali metal phosphates and alkali metal monohydrogen phosphates, such as sodium phosphate or sodium monohydrogen phosphate.
[0265] As examples of inorganic alkali metal hydroxides, sodium hydroxide and potassium hydroxide may be mentioned. As examples of alkaline earth metal hydroxides, calcium hydroxide and magnesium hydroxide may be mentioned. As the inorganic alkaline agent, sodium hydroxide is preferred.
[0266] The alkali agent can be an organic alkali agent, and preferably, the organic alkali agent is selected from 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; and guanidine and its derivatives.
[0267] As examples of organic alkaline agents, mention may be made of alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine, and isopropanolamine; urea, guanidine and derivatives thereof; basic amino acids, such as lysine, ornithine or arginine; and diamines, such as those depicted in the following structure:
[0268]
[0269] Wherein R represents an optionally hydroxyl group or a C 1 -C 4 Alkyl substituted alkylene (eg propylene), and R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, an alkyl group or a C 1 -C 4 The hydroxyalkyl group may be exemplified by 1,3-propylenediamine and its derivatives, and preferably arginine, urea and monoethanolamine.
[0270] Depending on its solubility, the alkali agent may be used in a total amount of 0.01 wt% to 15 wt%, preferably 0.02 wt% to 10 wt%, more preferably 0.03 wt% to 5 wt%, relative to the total weight of the composition.
[0271] (acid)
[0272] The composition according to the invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.
[0273] As acid, any inorganic or organic acid commonly used in cosmetic products may be mentioned, preferably an inorganic acid. Monoprotic and / or polyprotic acids may be used. Monoprotic acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid and hydrochloric acid (HCl) may be used. HCl is preferred.
[0274] Depending on its solubility, the acid may be used in a total amount of 0.01% to 15% by weight, preferably 0.02% to 10% by weight, more preferably 0.03% to 5% by weight, relative to the total weight of the composition.
[0275] (Buffer)
[0276] The composition according to the invention may comprise at least one buffer. Two or more buffers may be used in combination. Thus, a single type of buffer or a combination of different types of buffers may be used.
[0277] As buffers, mention may be made of acetate buffers (e.g. acetic acid + sodium acetate), phosphate buffers (e.g. sodium dihydrogen phosphate + disodium hydrogen phosphate), citrate buffers (e.g. citric acid + sodium citrate), borate buffers (e.g. boric acid + sodium borate), tartrate buffers (e.g. tartaric acid + sodium tartrate dihydrate), Tris buffers (e.g. tris(hydroxymethyl)aminomethane) and Hepes buffer (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).
[0278] [Optional Ingredients]
[0279] In addition to the aforementioned essential ingredients (ingredients (a) to (d)), the composition according to the present invention may further contain optional ingredients within the range not impairing the effects of the present invention, such as (e) anionic polymers and ingredients commonly used in cosmetics, specifically, surfactants (especially nonionic surfactants) or emulsifiers, hydrophilic thickeners or hydrophobic thickeners, organic volatile solvents or organic non-volatile solvents other than ingredient (c), hydrophilic UV filters or hydrophobic UV filters, silicones and silicone derivatives, natural extracts obtained from animals or plants, oils, waxes, etc.
[0280] The composition according to the present invention may comprise the above optional ingredients in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight, and more preferably 0.1% to 10% by weight, relative to the total weight of the composition.
[0281] The composition according to the invention may comprise no surfactant or a limited amount (eg less than 0.1 wt. %, preferably less than 0.01 wt. % and more preferably less than 0.001 wt. %) of surfactant relative to the total weight of the composition.
[0282] [preparation]
[0283] The compositions according to the present invention may be prepared by mixing the essential and optional ingredients described above in conventional manner.
[0284] For example, the composition according to the present invention can be prepared by a method comprising the following steps:
[0285] (a) at least one cationic polymer, (b) at least one non-polymeric acid having two or more pKa values or a salt thereof, (c) at least one polyol and (d) water are mixed, wherein the amount of (c) polyol in the composition is 10% by weight or more relative to the total weight of the composition.
[0286] It is possible to further mix any of the optional ingredients. For example, (e) at least one anionic polymer may be mixed.
[0287] Mixing may be performed at any temperature, such as room temperature (eg 25°C), preferably without heating. The composition according to the present invention may be environmentally friendly since it may be prepared without any heating step.
[0288] Preferably, the cosmetic composition according to the present invention is in liquid form at room temperature (eg 25°C).
[0289] [membrane]
[0290] The composition according to the present invention can be used to easily prepare films.
[0291] Therefore, the present invention may also relate to a method for preparing a film, preferably a cosmetic film, optionally having a thickness of preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, comprising:
[0292] applying the composition according to the invention to a substrate, preferably a keratinous substance, and more preferably the skin and the hair; and
[0293] The composition is dried.
[0294] The upper limit of the thickness of the above film is not limited. Therefore, for example, the thickness of the above film may be 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less.
[0295] Therefore, the present invention may also relate to a film, preferably a cosmetic film, comprising:
[0296] (a) at least one cationic polymer;
[0297] (b) at least one non-polymeric acid having two or more pKa values or a salt thereof; and
[0298] (c) at least one polyol.
[0299] The film may further comprise (d) water.
[0300] The above film (preferably a cosmetic film) is resistant to water having a pH of 7 or lower, and can be removed with water having a pH higher than 7 (preferably 8 or higher, and more preferably 9 or higher).
[0301] In other words, the above film (preferably a cosmetic film) can have water resistance under neutral conditions or acidic conditions (e.g., pH 7 or less, preferably in the range of 6 or more and 7 or less, and more preferably in the range of 5 or more and 7 or less); while the above film (preferably a cosmetic film) can be removed under alkaline conditions (e.g., pH higher than 7, preferably 8 or more, and more preferably 9 or more). The upper limit of pH is preferably 13, more preferably 12, and even more preferably 11.
[0302] Therefore, the above film (preferably a cosmetic film) can have water resistance, and therefore, even if the surface of the keratin material is wetted by, for example, sweat and rain, it can remain on the keratin material (such as skin and hair). On the other hand, the above film (preferably a cosmetic film) can be easily removed from the keratin material under alkaline conditions. Therefore, the above film (preferably a cosmetic film) is difficult to remove with water, but can be easily removed with, for example, soap that can provide alkaline conditions.
[0303] Furthermore, even if the above film does not contain any cosmetically active ingredients, the film may have a cosmetic effect due to its properties, such as absorbing or adsorbing unpleasant odors, changing the appearance of keratinous materials (such as skin and hair), changing the touch of keratinous materials, and / or protecting keratinous materials from, for example, dust or pollutants.
[0304] Since the above film includes (c) at least one polyol such as glycerin, the film can have a cosmetic effect provided by (c) the polyol, for example, a moisturizing effect.
[0305] [Beauty uses and methods]
[0306] The composition according to the present invention can be used as a cosmetic composition, preferably a care cosmetic composition, and more preferably a skin care cosmetic composition or a hair care cosmetic composition.
[0307] Therefore, the cosmetic composition according to the present invention may be intended to be applied to a keratin material. The keratin material may be a keratin fiber. Keratin fiber here means a fiber containing keratin as a main component, examples of which include hair, eyelashes, eyebrows, etc. On the other hand, the keratin material may be the skin and mucous membranes, such as lips.
[0308] The composition according to the present invention can be preferably used as a leave-on cosmetic composition or a rinse-off cosmetic composition for keratin substances such as skin and hair.
[0309] "Leave-on" means here that the compositions according to the invention, after application to keratinous materials such as the skin and hair, are not removed from these materials.
[0310] "Rinse-off type" means here that the composition according to the present invention is removed from the keratinous material such as skin and hair by rinsing after application to the keratinous material. Rinsing can be carried out with water. Even after rinsing, the composition according to the present invention can remain to form a film or coating on the keratinous material such as skin and hair.
[0311] The present invention also relates to
[0312] A cosmetic method for keratinous materials such as skin and hair comprising:
[0313] applying a composition according to the invention to a keratinous substance; and
[0314] The composition is dried to form a cosmetic film on the keratinous substance,
[0315] as well as
[0316] A method for preparing a film, preferably a cosmetic film, comprising:
[0317] applying the composition according to the invention to keratinous substances such as skin and hair; and
[0318] The composition is dried.
[0319] By cosmetic method is meant here a non-therapeutic cosmetic method for caring for keratinous substances such as the skin and hair and / or for styling keratinous fibres such as the hair.
[0320] The invention may also relate to the use of a composition according to the invention for producing cosmetic films on keratin substances such as the skin and hair.
[0321] The present invention may also relate to the use of (a) at least one cationic polymer; and (b) at least one non-polymeric acid having two or more pKa values or a salt thereof in a cosmetic composition for keratinous materials such as skin and hair, in order to reduce the viscosity of the composition, the composition comprising: (c) at least one polyol; and (d) water, wherein the amount of (c) polyol in the composition is 10% by weight or more relative to the total weight of the composition.
[0322] The use according to the present invention can reduce the viscosity of a composition comprising components (c) and (d) by a combination of components (a) and (b) (optionally together with component (e)), wherein the amount of component (c) in the composition is 10% by weight or more relative to the total weight of the composition.
[0323] The explanations concerning ingredients (a) to (e) in the composition according to the invention apply to those in the use according to the invention. Example
[0324] The present invention will be described in a more detailed manner by way of examples. However, the examples should not be construed as limiting the scope of the present invention.
[0325] [Examples 1-4 and Comparative Examples 1-4]
[0326] [preparation]
[0327] Each of the compositions according to Examples 1 to 4 and the compositions according to Comparative Examples 1 to 4 was prepared by mixing at room temperature (25° C.) the ingredients shown in Table 1. The numerical values for the amounts of the ingredients in Table 1 are all based on “weight %” based on the raw materials.
[0328]
[0329] [Evaluate]
[0330] (Gel Film Formation)
[0331] The compositions according to Examples 1 to 4 and the compositions according to Comparative Examples 1 to 4 were each poured onto a Petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0332] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0333] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0334] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0335] 3: Slightly form a gel film
[0336] 2: Very slight gel film formation
[0337] 1: No gel film formed
[0338] They were then categorized in the following categories based on the average of the ratings.
[0339] 5: Very good
[0340] 4: Good
[0341] 3: General
[0342] 2: Poor
[0343] 1: Very bad
[0344] The results are shown in Table 1.
[0345] (texture)
[0346] The compositions according to Examples 1 to 4 and the compositions according to Comparative Examples 1 to 4 were each poured onto a Petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0347] Five experts evaluated the texture on the petri dishes according to the following scale:
[0348] 5: Not sticky (very smooth)
[0349] 4: Very slightly sticky (smooth)
[0350] 3: Slightly sticky
[0351] 2: Sticky
[0352] 1: Very sticky
[0353] They were then categorized in the following categories based on the average of the ratings.
[0354] 5: Very good
[0355] 4: Good
[0356] 3: General
[0357] 2: Poor
[0358] 1: Very bad
[0359] The results are shown in Table 1.
[0360] (Summarize)
[0361] The compositions according to Examples 1 to 4 formed gel films. The compositions according to Examples 1 and 2 formed better gel films than the compositions according to Examples 3 and 4.
[0362] The compositions according to Comparative Examples 1-4 were unable to form any gel.
[0363] Since the compositions according to Comparative Examples 2 and 4 did not include glycerin, the texture of the compositions was not evaluated.
[0364] Cationic polymers (polylysine and chitosan), crosslinkers (phytic acid or terephthalylidene dicamphor sulfonic acid), and glycerol have been shown to form gel films (coacervates) and reduce the inherent viscosity of glycerol.
[0365] [Example 5-6 and Comparative Example 5-6]
[0366] [preparation]
[0367] Each composition according to Examples 5-6 and a composition according to Comparative Examples 5-6 was prepared by mixing the ingredients shown in Table 2 at room temperature (25° C.) The numerical values for the amounts of the ingredients in Table 2 are all based on “weight %” based on the raw materials.
[0368] Table 2
[0369] Example 5 Example 6 Comparative Example 5 Comparative Example 6 Poly-L-lysine 2 2 2 2 Sodium Hyaluronate 1 - - - Cellulose Gum - 1 - 1 Phytic Acid 0.55 0.55 0.55 - glycerin 10 10 - 10 water Appropriate amount up to 100 Appropriate amount up to 100 Appropriate amount up to 100 Appropriate amount up to 100 pH 6.9 7.4 6.5 9.8 Gel film formation very good very good Very bad Very bad texture very good very good NA Very bad
[0370] [Evaluate]
[0371] (Gel Film Formation)
[0372] The composition according to Example 5-6 and the composition according to Comparative Example 5-6 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0373] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0374] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0375] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0376] 3: Slightly form a gel film
[0377] 2: Very slight gel film formation
[0378] 1: No gel film formed
[0379] They were then categorized in the following categories based on the average of the ratings.
[0380] 5: Very good
[0381] 4: Good
[0382] 3: General
[0383] 2: Poor
[0384] 1: Very bad
[0385] The results are shown in Table 2.
[0386] (texture)
[0387] The composition according to Example 5-6 and the composition according to Comparative Example 5-6 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0388] Five experts evaluated the texture on the petri dishes according to the following scale:
[0389] 5: Not sticky (very smooth)
[0390] 4: Very slightly sticky (smooth)
[0391] 3: Slightly sticky
[0392] 2: Sticky
[0393] 1: Very sticky
[0394] They were then categorized in the following categories based on the average of the ratings.
[0395] 5: Very good
[0396] 4: Good
[0397] 3: General
[0398] 2: Poor
[0399] 1: Very bad
[0400] The results are shown in Table 2.
[0401] (Summarize)
[0402] The composition according to Examples 5-6 formed a uniform gel film. The gel film spread over the entire surface of the culture dish.
[0403] The composition according to Comparative Example 5-6 could not form any gel.
[0404] Since the composition according to Comparative Example 5 did not include glycerin, the viscosity of the composition was not evaluated.
[0405] It has been demonstrated that anionic polymers (sodium hyaluronate and cellulose gum) can be added to cationic polymers (polylysine), crosslinkers (phytic acid) and glycerol to form gel films (coacervates) and that the gel films so formed are more preferred (more uniform).
[0406] [Examples 7-8 and Comparative Examples 7-8]
[0407] [preparation]
[0408] Each composition according to Examples 7-8 and the compositions according to Comparative Examples 7-8 was prepared by mixing the ingredients shown in Table 3 at room temperature (25° C.) The numerical values for the amounts of the ingredients in Table 3 are all based on “weight %” based on the raw materials.
[0409] Table 3
[0410] Example 7 Example 8 Comparative Example 7 Comparative Example 8 Poly-L-lysine 2 2 2 - Phytic Acid 0.55 0.55 - - glycerin 50 90 50 50 water Appropriate amount up to 100 Appropriate amount up to 100 Appropriate amount up to 100 Appropriate amount up to 100 pH 6.5 6.5 9.7 5.7 Gel film formation good good Very bad Very bad texture very good very good Very bad Very bad
[0411] [Evaluate]
[0412] (Gel Film Formation)
[0413] The composition according to Examples 7-8 and the composition according to Comparative Examples 7-8 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0414] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0415] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0416] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0417] 3: Slightly form a gel film
[0418] 2: Very slight gel film formation
[0419] 1: No gel film formed
[0420] They were then categorized in the following categories based on the average of the ratings.
[0421] 5: Very good
[0422] 4: Good
[0423] 3: General
[0424] 2: Poor
[0425] 1: Very bad
[0426] The results are shown in Table 3.
[0427] (texture)
[0428] The composition according to Examples 7-8 and the composition according to Comparative Examples 7-8 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0429] Five experts evaluated the texture on the petri dishes according to the following scale:
[0430] 5: Not sticky (very smooth)
[0431] 4: Very slightly sticky (smooth)
[0432] 3: Slightly sticky
[0433] 2: Sticky
[0434] 1: Very sticky
[0435] They were then categorized in the following categories based on the average of the ratings.
[0436] 5: Very good
[0437] 4: Good
[0438] 3: General
[0439] 2: Poor
[0440] 1: Very bad
[0441] The results are shown in Table 3.
[0442] (Summarize)
[0443] The compositions according to Examples 7-8 formed gels.
[0444] The composition according to Comparative Examples 7-8 could not form any gel.
[0445] It has been demonstrated that large amounts of glycerol can be used to form gel films (coacervates).
[0446] [Example 9 and Comparative Example 9]
[0447] [preparation]
[0448] Each composition according to Example 9 and each composition according to Comparative Example 9 was prepared by mixing at room temperature (25° C.) the ingredients shown in Table 4. The numerical values for the amounts of the ingredients in Table 4 are all based on “weight %” based on the raw materials.
[0449] Table 4
[0450] Example 9 Comparative Example 9 Poly-L-lysine 4 - Phytic Acid 1.1 - glycerin 10 10 water Appropriate amount up to 100 Appropriate amount up to 100 pH 6.7 6.3 Gel film formation good Very bad texture very good Very bad
[0451] [Evaluate]
[0452] (Gel Film Formation)
[0453] The composition according to Example 9 and the composition according to Comparative Example 9 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0454] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0455] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0456] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0457] 3: Slightly form a gel film
[0458] 2: Very slight gel film formation
[0459] 1: No gel film formed
[0460] They were then categorized in the following categories based on the average of the ratings.
[0461] 5: Very good
[0462] 4: Good
[0463] 3: General
[0464] 2: Poor
[0465] 1: Very bad
[0466] The results are shown in Table 4.
[0467] (texture)
[0468] The composition according to Example 9 and the composition according to Comparative Example 9 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0469] Five experts evaluated the texture on the petri dishes according to the following scale:
[0470] 5: Not sticky (very smooth)
[0471] 4: Very slightly sticky (smooth)
[0472] 3: Slightly sticky
[0473] 2: Sticky
[0474] 1: Very sticky
[0475] They were then categorized in the following categories based on the average of the ratings.
[0476] 5: Very good
[0477] 4: Good
[0478] 3: General
[0479] 2: Poor
[0480] 1: Very bad
[0481] The results are shown in Table 4.
[0482] (Summarize)
[0483] The composition according to Example 9 formed a gel.
[0484] The composition according to Comparative Example 9 could not form any gel.
[0485] It has been demonstrated that a large number of cationic polymers and / or a large number of cross-linking agents can be used to form gel films (coacervates).
[0486] [Examples 10-16]
[0487] [preparation]
[0488] Each composition according to Examples 10 to 16 was prepared by mixing at room temperature (25° C.) the ingredients shown in Table 5. The numerical values for the amounts of the ingredients in Table 5 are all based on “weight %” based on the raw materials.
[0489] Table 5
[0490]
[0491] [Evaluate]
[0492] (Gel Film Formation)
[0493] The compositions according to Examples 10-16 were each poured in an amount of 10 grams onto a petri dish and dried at 45° C. for 24 hours.
[0494] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0495] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0496] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0497] 3: Slightly form a gel film
[0498] 2: Very slight gel film formation
[0499] 1: No gel film formed
[0500] They were then categorized in the following categories based on the average of the ratings.
[0501] 5: Very good
[0502] 4: Good
[0503] 3: General
[0504] 2: Poor
[0505] 1: Very bad
[0506] The results are shown in Table 5.
[0507] (texture)
[0508] The compositions according to Examples 10-16 were each poured in an amount of 10 grams onto a petri dish and dried at 45° C. for 24 hours.
[0509] Five experts evaluated the texture on the petri dishes according to the following scale:
[0510] 5: Not sticky (very smooth)
[0511] 4: Very slightly sticky (smooth)
[0512] 3: Slightly sticky
[0513] 2: Sticky
[0514] 1: Very sticky
[0515] They were then categorized in the following categories based on the average of the ratings.
[0516] 5: Very good
[0517] 4: Good
[0518] 3: General
[0519] 2: Poor
[0520] 1: Very bad
[0521] The results are shown in Table 5.
[0522] (Summarize)
[0523] The compositions according to Examples 10-16 formed gels.
[0524] It has been demonstrated that the amount of cross-linking agent can be varied to form gel films (coacervates).
[0525] [Example 17 and Comparative Examples 10-14]
[0526] [preparation]
[0527] Each composition according to Example 17 and compositions according to Comparative Examples 10 to 14 was prepared by mixing at room temperature (25° C.) the ingredients shown in Table 6. The numerical values for the amounts of the ingredients in Table 6 are all based on “weight %” based on the raw materials.
[0528] Table 6
[0529]
[0530] [Evaluate]
[0531] (Gel Film Formation)
[0532] The composition according to Example 17 and the compositions according to Comparative Examples 10 to 16 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0533] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0534] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0535] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0536] 3: Slightly form a gel film
[0537] 2: Very slight gel film formation
[0538] 1: No gel film formed
[0539] They were then categorized in the following categories based on the average of the ratings.
[0540] 5: Very good
[0541] 4: Good
[0542] 3: General
[0543] 2: Poor
[0544] 1: Very bad
[0545] The results are shown in Table 6.
[0546] (texture)
[0547] The composition according to Example 17 and the compositions according to Comparative Examples 10 to 16 were each poured onto a petri dish in an amount of 10 g and dried at 45° C. for 24 hours.
[0548] Five experts evaluated the texture on the petri dishes according to the following scale:
[0549] 5: Not sticky (very smooth)
[0550] 4: Very slightly sticky (smooth)
[0551] 3: Slightly sticky
[0552] 2: Sticky
[0553] 1: Very sticky
[0554] They were then categorized in the following categories based on the average of the ratings.
[0555] 5: Very good
[0556] 4: Good
[0557] 3: General
[0558] 2: Poor
[0559] 1: Very bad
[0560] The results are shown in Table 6.
[0561] (Summarize)
[0562] The composition according to Example 17 formed a gel.
[0563] The compositions according to Comparative Examples 10-14 were unable to form any gel.
[0564] It has been demonstrated that the use of monoacids (HCl) does not allow the formation of gel films (coacervates). It is understood that the use of a multivalent cross-linking agent (such as phytic acid) is necessary.
[0565] Examples 18-23
[0566] [preparation]
[0567] Each composition according to Examples 18 to 23 was prepared by mixing at room temperature (25° C.) the ingredients shown in Table 7. The numerical values for the amounts of the ingredients in Table 7 are all based on “weight %” based on the raw materials.
[0568] Table 7
[0569]
[0570] [Evaluate]
[0571] (Gel Film Formation)
[0572] The compositions according to Examples 18-23 were each poured in an amount of 10 grams onto a petri dish and dried at 45° C. for 24 hours.
[0573] Five experts evaluated the formation of gel films in the culture dishes according to the following scale:
[0574] 5: Formation of a uniform gel film (the gel film appears evenly on the culture dish)
[0575] 4: A gel film is formed, but it is not uniform (the gel film is unevenly presented on the culture dish)
[0576] 3: Slightly form a gel film
[0577] 2: Very slight gel film formation
[0578] 1: No gel film formed
[0579] They were then categorized in the following categories based on the average of the ratings.
[0580] 5: Very good
[0581] 4: Good
[0582] 3: General
[0583] 2: Poor
[0584] 1: Very bad
[0585] The results are shown in Table 7.
[0586] (texture)
[0587] The compositions according to Examples 18-23 were each poured in an amount of 10 grams onto a petri dish and dried at 45° C. for 24 hours.
[0588] Five experts evaluated the texture on the petri dishes according to the following scale:
[0589] 5: Not sticky (very smooth)
[0590] 4: Very slightly sticky (smooth)
[0591] 3: Slightly sticky
[0592] 2: Sticky
[0593] 1: Very sticky
[0594] They were then categorized in the following categories based on the average of the ratings.
[0595] 5: Very good
[0596] 4: Good
[0597] 3: General
[0598] 2: Poor
[0599] 1: Very bad
[0600] The results are shown in Table 7.
[0601] (Summarize)
[0602] The compositions according to Examples 18-23 formed gels.
[0603] It has been demonstrated that gel films can be formed at a pH of at least below 8.1.
Claims
1. A composition comprising: (a) at least one cationic polymer, (b) at least one non-polymeric acid or salt thereof having two or more pKa values; (c) at least one polyol; and (d) water, Wherein, the amount of the (c) polyol in the composition is 10 wt % or more relative to the total weight of the composition.
2. The composition according to claim 1, wherein the (a) cationic polymer is crosslinked using the (b) non-polymeric acid having two or more pKa values or a salt thereof.
3. A composition according to claim 1 or 2, wherein the (a) cationic polymer has at least one positively chargeable and / or positively charged moiety selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidine groups, imidazolyl groups, imino groups and pyridyl groups.
4. A composition according to any one of claims 1 to 3, wherein the (a) cationic polymer is selected from cyclized polymers of alkyldiallylamines and cyclized polymers of dialkyldiallylammoniums, such as (co)polydiallyldialkylammonium chlorides; (co)polyamines, such as chitosan and (co)polylysine; cationic (co)polyamino acids, such as collagen; cationic cellulose polymers; and salts thereof.
5. The composition according to any one of claims 1 to 4, wherein the (a) cationic polymer is selected from polylysine, chitosan, and mixtures thereof.
6. The composition according to any one of claims 1 to 5, wherein the amount of the (a) cationic polymer in the composition is 0.01 wt%-15 wt%, preferably 0.05 wt%-10 wt%, and more preferably 0.1 wt%-5 wt%, relative to the total weight of the composition.
7. The composition according to any one of claims 1 to 6, wherein the (b) non-polymeric acid or salt thereof having two or more pKa values is an organic acid or salt thereof, preferably a hydrophilic organic acid or salt thereof or a water-soluble organic acid or salt thereof, and more preferably phytic acid or salt thereof, terephthalylidene dicamphorsulfonic acid or salt thereof, or a mixture thereof.
8. The composition according to any one of claims 1 to 7, wherein the amount of the (b) non-polymeric acid or its salt having two or more pKa values in the composition is 0.01 wt%-15 wt%, preferably 0.05 wt%-10 wt%, and more preferably 0.1 wt%-5 wt%, relative to the total weight of the composition.
9. The composition according to any one of claims 1 to 8, wherein the (c) polyol is glycerol.
10. The composition according to any one of claims 1 to 9, wherein the amount of the (c) polyol in the composition is 95 wt% or less relative to the total weight of the composition.
11. The composition according to any one of claims 1 to 10, wherein the composition further comprises (e) at least one anionic polymer.
12. The composition according to claim 11, wherein the (e) anionic polymer is selected from polysaccharides, preferably hyaluronic acid and its derivatives, cellulose polymers and their salts, and mixtures thereof, and more preferably hyaluronic acid and its salts, carboxymethylcellulose and its salts, and mixtures thereof.
13. The composition according to claim 11 or 12, wherein the amount of the (e) anionic polymer in the composition is 0.01 wt%-15 wt%, preferably 0.05 wt%-10 wt%, and more preferably 0.1 wt%-5 wt%, relative to the total weight of the composition.
14. The composition according to any one of claims 1 to 13, wherein the composition is a cosmetic composition, preferably a care cosmetic composition, and more preferably a skin care cosmetic composition or a hair care cosmetic composition.
15. A cosmetic method for keratinous materials, comprising: applying a composition according to any one of claims 1 to 14 to the keratinous substance; and The composition is dried to form a cosmetic film on the keratinous substance.
Citation Information
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