Composition having enhanced stability

Abstract

To provide a composition which is stable with time even at high temperatures and is suitable for an eyeliner.SOLUTION: There is provided a composition comprising (a) at least one pigment, (b) at least one acrylic copolymer of at least two monomers selected from (meth)acrylic acid, an ester thereof and a salt thereof, (c) at least one polyurethane, and (d) water, wherein the mass ratio of (the amount of the acrylic copolymer (b) and the amount of the polyurethane (c)) / the amount of the pigment (a) is 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, and the pigment (a) is carbon black. The composition is stable with time at room temperature or even at high temperatures.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition suitable for keratinous materials, preferably a cosmetic composition, more preferably a make-up cosmetic composition, in particular an eyeliner, and to a method relating to said composition. [Background technology]

[0002] There have been cosmetic compositions intended as make-up for keratinous materials such as the skin and mucosal surfaces, in particular eye make-up products, such as eyeliners, in particular eyeliners in pencil form.

[0003] Generally, these cosmetic compositions are sought to conceal the natural skin color, for example for make-up purposes, and it is preferable that this concealment can last for an extended period of time.

[0004] WO2020 / 004239 discloses a composition suitable for eyeliner, which comprises carbon black and a specific film-forming copolymer, thereby providing a long-lasting concealing effect. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2020 / 004239 [Patent Document 2] U.S. Patent No. 3,383,351 [Patent Document 3] U.S. Patent No. 3,304,273 [Patent Document 4] U.S. Patent No. 3,523,095 [Patent Document 5] U.S. Patent No. 3,110,695 [Patent Document 6] German patent no. 1152536 [Patent Document 7] U.S. Patent No. 3,412,054 [Patent Document 8] DE 10 2008 051727 A1 [Patent Document 9] DE 10 2007 019184 [Patent Document 10] EP-A0916647 [Patent Document 11] DE-A2446440 [Non-patent literature]

[0006] [Non-Patent Document 1] ISO 16128-1:2016, part 1 [Non-Patent Document 2] DIN 65467 [Non-Patent Document 3] DIN ISO 4629 [Non-Patent Document 4] DIN EN ISO 2114 [Non-Patent Document 5] Ullmanns Encyclopadie der technischen Chemie, 4th edition, Volume 19, Verlag Chemie, Weinheim, pp. 31-38 [Non-Patent Document 6] Methoden der organischen Chemie (Houben-Weyl, Erweiterungs- und Folgebande zur 4. Auflage, Volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pp. 1671-1682 Summary of the Invention [Problem to be solved by the invention]

[0007] Meanwhile, there remains a need for improved compositions that possess enhanced stability, such as stability in viscosity over time, and particularly stability over time at elevated temperatures.

[0008] An object of the present invention is to provide a composition which is stable over time even at high temperatures and is suitable for use as an eyeliner. [Means for solving the problem]

[0009] The above objectives are: (a) at least one pigment; (b) at least one acrylic copolymer of at least two monomers selected from (meth)acrylic acid, its esters, and its salts; (c) at least one polyurethane; (d) Water and A composition comprising: a mass ratio of (the amount of (b) the acrylic copolymer and the amount of (c) the polyurethane) / (a) the pigment is 1.5 or more, preferably 2.0 or more, and more preferably 2.5 or more; (a) This can be achieved by the composition, wherein the pigment is carbon black.

[0010] The amount of the (a) pigment in the composition according to the present invention may be from 1 to 30% by mass, preferably from 3 to 20% by mass, and more preferably from 5 to 10% by mass, relative to the total mass of the composition.

[0011] (b) (Meth)acrylic acid esters for acrylic copolymers are C1-C 30 Alkyl (meth)acrylate with alkyl group, C6-C 10 It can be selected from aryl (meth)acrylates having an aryl group, and hydroxyalkyl (meth)acrylates having a C2 to C6 hydroxyalkyl group.

[0012] The amount of the (b) acrylic copolymer in the composition according to the present invention may be from 0.001% by mass to 30% by mass, preferably from 0.01% by mass to 20% by mass, and more preferably from 0.1% by mass to 10% by mass, based on the total mass of the composition.

[0013] (c) The polyurethane may include at least one hydrophobic moiety.

[0014] (c) The polyurethane may include at least one polysiloxane moiety.

[0015] (c) The polyurethane may be selected from the group consisting of polyurethane-6, polyurethane-35, polyurethane-93, polyurethane-99, and mixtures thereof.

[0016] The amount of (c) polyurethane in the composition according to the present invention may be from 1 to 40% by mass, preferably from 5 to 35% by mass, and more preferably from 10 to 30% by mass, based on the total mass of the composition.

[0017] The weight ratio of the amount of (c) polyurethane to the amount of (b) acrylic copolymer may be 4 or more, preferably 6 or more, and more preferably 8 or more.

[0018] The (b) acrylic copolymer and / or the (c) polyurethane may be in the form of particles.

[0019] The amount of (d) water in the composition according to the present invention may be 10% by mass to 60% by mass, preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 47% by mass, based on the total mass of the composition.

[0020] The composition according to the invention may comprise at least one surfactant in an amount of at most 0.5% by weight, preferably at most 0.3% by weight, more preferably at most 0.1% by weight, relative to the total weight of the composition, or the composition according to the invention may be free of any surfactant.

[0021] The composition according to the present invention may be a cosmetic composition, preferably a make-up composition, more preferably an eyeliner composition.

[0022] Another aspect of the present invention relates to a cosmetic method for making up keratinous materials, comprising the step of applying on the keratinous materials a composition according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] As a result of extensive investigations, the present inventors have discovered that it is possible to provide a composition which is stable over time even at high temperatures and which is suitable for eyeliners.

[0024] Therefore, the composition according to the invention (a) at least one pigment; (b) at least one acrylic copolymer of at least two monomers selected from (meth)acrylic acid, its esters, and its salts; (c) at least one polyurethane; (d) Water and A composition comprising: a mass ratio of (the amount of (b) the acrylic copolymer and the amount of (c) the polyurethane) / (a) the pigment is 1.5 or more, preferably 2.0 or more, and more preferably 2.5 or more; (a) the pigment is carbon black; It is a composition.

[0025] The composition according to the present invention is stable over time, whether at room temperature or at elevated temperatures. For example, the viscosity of the composition according to the present invention is stable over time, even at elevated temperatures.

[0026] The composition according to the present invention is stable in eyeliner.For example, when the composition according to the present invention is used as eyeliner, the amount of deposit of eyeliner from a cosmetic device such as a liquid pen type dispenser or package can be stable over time even under high temperature.The stability of the amount of deposit can reflect the stability of the mixture of (a) pigment, (b) acrylic polymer, and (c) polyurethane in the cosmetic device without causing clogging.

[0027] Therefore, the composition according to the present invention has excellent usability.

[0028] The compositions according to the invention can also provide keratinous materials, such as skin and mucosal surfaces, with excellent cosmetic benefits or properties, such as good color concealment and long-lasting makeup protection against sebum or water, such as that provided by sweat or rain.

[0029] Hereafter, the compositions and methods according to the present invention will be described in detail.

[0030] [Composition] (Pigments) The composition according to the present invention comprises (a) at least one pigment. If two or more pigments are used, they may be the same or different.

[0031] According to the present invention, the (a) pigment is carbon black.

[0032] The amount of the (a) pigment in the composition according to the present invention may be 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, based on the total mass of the composition.

[0033] On the other hand, the amount of the (a) pigment in the composition according to the present invention may be 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total mass of the composition.

[0034] Accordingly, the amount of the (a) pigment in the composition according to the present invention may be in the range of 1% by mass to 30% by mass, preferably 3% by mass to 20% by mass, and more preferably 5% by mass to 10% by mass, relative to the total mass of the composition.

[0035] It is preferred to use the (a) pigment in the form of a polymer dispersion, preferably an aqueous dispersion further comprising (b) an acrylic copolymer as described below.

[0036] (acrylic copolymer) The composition according to the invention comprises (b) at least one acrylic copolymer. When two or more acrylic copolymers are used, they may be the same or different.

[0037] (b) The acrylic copolymer is a copolymer of at least two monomers selected from (meth)acrylic acid, its esters, and its salts.

[0038] (b) The acrylic copolymer can be prepared by polymerizing at least two monomers selected from (meth)acrylic acid, its esters, and its salts.

[0039] Styrene or α-methylstyrene is not used as a monomer for the (b) acrylic copolymer, and therefore the (b) acrylic copolymer does not contain units derived from styrene or α-methylstyrene.

[0040] (b) (meth)acrylic acid ester for acrylic copolymer is C1-C 30 Alkyl (meth)acrylate with alkyl group, C6-C 10 It is preferably selected from aryl (meth)acrylates having an aryl group, and hydroxyalkyl (meth)acrylates having a C2 to C6 hydroxyalkyl group.

[0041] Among the alkyl (meth)acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate.

[0042] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0043] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0044] Particularly preferred (meth)acrylic acid esters are alkyl (meth)acrylates.

[0045] According to the present invention, the alkyl group of the ester may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms.

[0046] (b) The (meth)acrylate salt for the acrylic copolymer can be selected from metal or ammonium salts of (meth)acrylic acid. The metal salt can be an alkali metal salt, such as a sodium salt or a potassium salt, or an alkaline earth metal salt, such as a magnesium salt or a calcium salt. (b) The (meth)acrylate salt for the acrylic copolymer can be selected from ammonium salts of (meth)acrylic acid.

[0047] (b) The acrylic copolymer may have at least one ammonium moiety or group, which may be present as an ammonium salt moiety or group as a pendant group, or may be present in the backbone of the chemical structure, such as the alkyl group of an alkyl (meth)acrylate.

[0048] (b) The acrylic copolymer may be a copolymer of at least one monomer selected from ammonium (meth)acrylate salts and at least one monomer selected from esters of (meth)acrylic acid.

[0049] (b) The acrylic copolymer may be an ammonium acrylate copolymer, such as Syntran PC5400 and Syntran KL219C sold by Interpolymer.

[0050] It may be preferred that the (b) acrylic copolymer is a copolymer of at least one monomer selected from esters of (meth)acrylic acid not having an ammonium moiety or group and at least one monomer selected from esters of (meth)acrylic acid not having an ammonium moiety or group.

[0051] It may be preferred that the (b) acrylic copolymer is an acrylate copolymer, such as Daitosol 3000SLPN-SD and Daitosol 3000VSD sold by Daito Chemical Industry Co., Ltd.

[0052] It may be preferable that the composition of the present invention contains two or more different acrylate copolymers.By combining two or more different acrylate copolymers, the pigment (a) which is carbon black can be more stably dispersed in the composition of the present invention.For example, the above Daitosol 3000SLPN-SD and Daitosol 3000VSD can be combined in a ratio of 10:1 to 1:1, preferably 3:1 to 1.5:1.

[0053] (b) The acrylic copolymer is preferably an Acrylates Copolymer (INCI name).

[0054] The (b) acrylic copolymer can be preferably combined with, in particular, the (a) pigment, for example, the (b) acrylic copolymer can be used as a dispersant for the (a) pigment.

[0055] (b) The acrylic copolymer may be in the form of particles. The particles may have a volume average particle size of 100 nm or less.

[0056] The amount of the (b) acrylic copolymer in the composition according to the present invention may be 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, based on the total weight of the composition. It may be even more preferred that the amount of the (b) acrylic copolymer in the composition according to the present invention is 1% by weight or more, based on the total weight of the composition.

[0057] On the other hand, the amount of (b) acrylic copolymer in the composition according to the present invention may be 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, based on the total weight of the composition. It may be even more preferable that the amount of (b) acrylic copolymer in the composition according to the present invention is 6% by weight or less, based on the total weight of the composition.

[0058] Accordingly, the amount of the (b) acrylic polymer in the composition according to the present invention may range from 0.001% to 30% by weight, preferably from 0.01% to 20% by weight, more preferably from 0.1% to 10% by weight, based on the total weight of the composition. It may even be more preferred that the amount of the (b) acrylic copolymer in the composition according to the present invention is from 1% to 6% by weight, based on the total weight of the composition.

[0059] (Polyurethane) The composition according to the invention comprises (c) at least one polyurethane. When two or more polyurethanes are used, they may be the same or different.

[0060] In one embodiment, (c) the polyurethane may comprise the reaction product of (i), (ii) and / or (iii) defined below.

[0061] The reaction product (i) has the formula:

[0062] [ka]

[0063] (In the formula, R1 is selected from divalent radicals of dihydroxyl functional compounds; R2 is selected from the hydrocarbon radicals of aliphatic or cycloaliphatic polyisocyanates; R3 is selected from the group of low molecular weight diols optionally substituted with ionic groups, n ranges from about 0 to about 5, and m is greater than about 1. The polymer may be any prepolymer according to the method of the present invention.

[0064] Suitable dihydroxyl compounds for providing the divalent group R1 include those having at least two hydroxyl groups and a number average molecular weight ranging from about 700 to about 16,000, for example, from about 750 to about 5,000. Non-limiting examples of high molecular weight compounds include polyester polyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides, polyhydroxy polyalkadienes, and polyhydroxy polythioethers. In various embodiments, polyester polyols, polyether polyols, and polyhydroxy polycarbonates can be selected. Mixtures of such compounds are also within the scope of the present disclosure.

[0065] The polyester diols can optionally be prepared from dihydric alcohols such as diols selected from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids, or anhydrides thereof; and aliphatic, cycloaliphatic or aromatic diols.

[0066] The aliphatic di- or polycarboxylic acid may be selected, for example, from succinic acid, fumaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, itaconic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, malonic acid, 2,2-dimethylmalonic acid, nonanedicarboxylic acid, decanedioic acid, dodecane-dioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norboranedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalene-dicarboxylic acid, 2,6-naphthalene-dicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, oxalic acid, o-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, or trimellitic acid. The acid anhydride may, in a further exemplary embodiment, be selected from o-phthalic anhydride, trimellitic anhydride, or succinic anhydride, or a mixture thereof. By way of non-limiting example only, the dicarboxylic acid may be adipic acid.

[0067] The dihydric alcohol can be selected, for example, from ethanediol, ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, cyclohexanedimethanol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, and mixtures thereof. Cycloaliphatic and / or aromatic dihydroxyl compounds can also be suitable as dihydric alcohols for the preparation of polyester polyols.

[0068] The polyester diols can also be selected from homopolymers or copolymers of lactones, which, at least in certain embodiments, are obtained by addition reaction of lactones or mixtures of lactones, such as butyrolactone, ε-caprolactone and / or methyl-ε-caprolactone, with suitable polyfunctional, e.g. difunctional, starter molecules, such as the dihydric alcohols listed above. In at least some embodiments, the corresponding polymers of ε-caprolactone can be selected.

[0069] Polyester polyols, such as polyester diols, R1 groups can be obtained by polycondensation of dicarboxylic acids, such as adipic acid, with polyols, such as diols, such as hexanediol, neopentyl glycol, and mixtures thereof.

[0070] Polycarbonates containing hydroxyl groups include those which are known per se and include, for example, the products obtained by reacting diols, such as (1,3)-propanediol, (1,4)-butanediol and / or (1,6)-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol, with diaryl carbonates, such as diphenyl carbonate or phosgene.

[0071] Optional polyether polyols can be obtained in any known manner by reacting starting compounds containing reactive hydrogen atoms with alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin, or with mixtures of these alkylene oxides.In at least certain embodiments, polyethers do not contain more than about 10% by weight of ethylene oxide units.For example, polyethers obtained without the addition of ethylene oxide can be selected.

[0072] Polyethers modified with vinyl polymers are also suitable according to various embodiments of the present disclosure.Products of this type can be obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers, as described, for example, in U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,095, 3,110,695, and German Patent No. 1,152,536.

[0073] Polythioethers that can be selected include the condensation products obtained from thioglycols themselves and / or from other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids and / or aminoalcohols. Depending on the co-components, the resulting products are either mixed polythioethers, polythioether esters or polythioether ester amides.

[0074] Optional polyacetals include, but are not limited to, compounds that can be prepared from aldehydes, such as formaldehyde, and glycols, such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-(dihydroxy)diphenyl-dimethylmethane, and (1,6)-hexane-diol. Polyacetals useful according to various non-limiting embodiments of the present disclosure can also be prepared by polymerizing cyclic acetals.

[0075] The optional polyhydroxy polyester amides and polyamines include, for example, predominantly linear condensation products obtained from saturated or unsaturated, polybasic carboxylic acids or anhydrides thereof, and from saturated or unsaturated, polyhydric amino alcohols, from diamines, or from polyamines, and mixtures thereof.

[0076] Optional monomers for the production of polyacrylates with hydroxyl functionality include acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate.

[0077] Mixtures of dihydroxy compounds may also be selected.

[0078] Optional polyisocyanates for imparting the hydrocarbon-based group R2 include, for example, organic diisocyanates having a molecular weight in the range of about 100 to about 1500, such as about 112 to about 1000, or about 140 to about 400.

[0079] The optional diisocyanates are selected from the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon group containing about 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon group containing about 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group containing about 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon group containing about 6 to 15 carbon atoms. Examples of organic diisocyanates that can be selected include, but are not limited to, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate, 1-isocyanato-3-isocyanato-methyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)-methane, 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane and bis(4-isocyanato-3-methylcyclohexyl)methane. Mixtures of diisocyanates can also be used.

[0080] In at least certain embodiments, the diisocyanate is selected from aliphatic and cycloaliphatic diisocyanates, such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, and mixtures thereof.

[0081] The use of a diol, e.g., a low molecular weight diol, R3, can, at least in certain embodiments, allow for reinforcement of the polymer chain. The expression "low molecular weight diol" refers to a diol having a molecular weight in the range of about 50 to about 800, e.g., about 60 to 700, or about 62 to 200. These can contain aliphatic, cycloaliphatic, or aromatic groups in various embodiments. In certain exemplary embodiments, the compound contains only aliphatic groups. The diol that can be selected can optionally have up to about 20 carbon atoms and can be selected from, for example, ethylene glycol, diethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, 1,3-butylene glycol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, hexane-1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof. For example, R3 can be derived from neopentyl glycol.

[0082] Optionally, the low molecular weight diol can contain ionic or potentially ionic groups. Suitable low molecular weight diols containing ionic or potentially ionic groups can be selected from those disclosed in U.S. Pat. No. 3,412,054. In various embodiments, the compounds can be selected from dimethylol butanoic acid (DMBA), dimethylol propionic acid (DMPA) and carboxyl-containing caprolactone polyester diols. When low molecular weight diols containing ionic or potentially ionic groups are selected, they can be used in an amount such that, for example, there is less than about 0.30 meq -COOH per gram of polyurethane in the polyurethane dispersion. In at least certain exemplary, non-limiting embodiments, low molecular weight diols containing ionic or potentially ionic groups are not used.

[0083] The reaction product (ii) has the formula: H2N-R4-NH2 (In the formula, R4 is selected from an alkylene or alkylene oxide group, said group not being substituted with an ionic or potentially ionic group; The chain extender may be selected from at least one chain extender according to the

[0084] Reaction product (ii) may be any of the alkylene diamines, such as hydrazine, ethylene-diamine, propylene diamine, 1,4-butylene diamine, and piperazine; and alkylene oxide diamines, such as dipropylamine diethylene glycol (DPA-DEG ​​available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexanediamine, isophorone-diamine, and 4,4-methylenedi(cyclohexylamine), and the like. and dipropylamine cyclohexane-1,4-dimethanol, and mixtures thereof.

[0085] The reaction product (iii) has the formula: H2N-R5-NH2 (In the formula, R5 is selected from alkylene groups substituted with ionic or potentially ionic groups. In at least certain exemplary embodiments, the compound may have an ionic or potentially ionic group and two isocyanate-reactive groups.

[0086] As used herein, ionic or potentially ionic groups include tertiary or quaternary ammonium groups; groups that contain groups that can be converted into groups such as carboxyl groups, carboxylate groups, sulfonic acid groups, and sulfonate groups. At least partial conversion of the groups that can be converted into the salt groups of the types listed can occur before or during mixing with water. Specific compounds include diaminosulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (AAS), or the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid.

[0087] In at least certain embodiments, R5 represents an alkylene group substituted with a sulfonic acid or sulfonate group. By way of example only, the compound is selected from the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid.

[0088] The polyurethane may be in the form of a latex, for example in the form of an aqueous polyurethane dispersion.

[0089] By way of non-limiting example, such polyurethane latex polymers include aqueous polyurethane dispersions comprising the reaction product of prepolymers, such as those sold by Bayer under the name BAYCUSAN®, such as, but not limited to, BAYCUSAN® C1000 (INCI name: Polyurethane-34), BAYCUSAN® C1001 (INCI name: Polyurethane-34), BAYCUSAN® C1003 (INCI name: Polyurethane-32), BAYCUSAN® C1004 (INCI name: Polyurethane-35) and BAYCUSAN® C1008 (INCI name: Polyurethane-48). In various exemplary embodiments, the polyurethane latex can be selected from, but is not limited to, aqueous polyurethane dispersion of isophthalic acid / adipic acid / hexylene glycol / neopentyl glycol / dimethylolpropanoic acid / isophorone diisocyanate copolymer (INCI name: Polyurethane-1, e.g., LUVISET® PUR, BASF), polycarbonate polyurethane, aliphatic polyurethane, and aliphatic polyester polyurethane (e.g., NEOREZ® series, DSM, e.g., NEOREZ® R989 and NEOREZ® R-2202).

[0090] (c) It may be preferred that the polyurethane contains at least one urea moiety.

[0091] In another embodiment, (c) the polyurethane may be a polyurethane / urea polymer constructed from a succinic acid-based polyester polyol.

[0092] The polyurethaneurea polymer comprises at least a) 5 to 40 wt. % of at least one aliphatic or aromatic polyisocyanate having a functionality of 2 or more; b) 40 to 90 wt. % of at least one polyester polyol composed of succinic acid and at least one dihydroxy compound, the carbon skeleton of which contains from 2 to 12 carbon atoms, having a functionality of 2 or more and a molar mass Mn of 400 to 8000 g / mol, c) 0.1 to 5 wt. % of at least one isocyanate-reactive compound having a functionality of 2 or greater and containing potential ionic groups; d) 0.1 to 17 wt. % of at least one polyamine having a molar mass Mn of 32 to 400 g / mol and a functionality of 1 to 3, e) optionally 0-15 wt. % of at least one non-ionic isocyanate-reactive hydrophilizing agent; f) optionally 0 to 7.0 wt. % of at least one polyhydroxy compound having a molar mass Mn of less than 400 g / mol and a functionality of 2 to 4; g) optionally 0 to 8.0 wt. % of at least one neutralizing agent for neutralizing the potential ionic groups of component c); The component The sum of components a) to g) is 100 wt% or less, and At least 50 wt. % of the components used to compose the polyurethaneurea polymer, in particular components a) to g), are derived from renewable sources in accordance with ISO 16128-1:2016, part 1; It may be composed of components.

[0093] The expression "derived from renewable sources" according to the present invention means that for the respective material, the source of the material is selected from which more than 90 wt%, or preferably more than 95 wt%, or preferably more than 99 wt% of the material referred to as "derived from renewable sources" originates from plants or fermentation processes, where only living organic matter and plants are included in the fermentation process to create a renewable source. The basis for the definition of the natural origin of these ingredients can also be found in ISO 16128-1:2016, part 1, page 2.

[0094] Preferably, at least a) 7.5 to 40 wt. % of at least one aliphatic or aromatic polyisocyanate having a functionality of 2 or more; b) 45 to 85 wt. % of at least one polyester polyol composed of succinic acid and at least two different dihydroxy compounds whose carbon skeleton contains 2 to 12 carbon atoms and having a functionality of 2 or more and a number average molar mass Mn of 400 to 8000 g / mol, c) 0.4 to 4.5 wt. % of at least one isocyanate-reactive compound having a functionality of 2 or greater and containing potential ionic groups; d) 0.25 to 15 wt. % of at least one polyamine having a molar mass of 32 to 400 g / mol and a functionality of 1 to 3, e) optionally 0-15 wt. % of at least one non-ionic isocyanate-reactive hydrophilizing agent; f) optionally 0 to 7.0 wt. % of at least one polyhydroxy compound having a molar mass n of less than 400 g / mol and a functionality of 2 to 4; g) optionally 0 to 8.0 wt. % of at least one neutralizing agent for neutralizing the potential ionic groups of component c); A polyurethaneurea polymer consisting of: The sum of components a) to g) is 100 wt% or less; It may be a polyurethaneurea polymer.

[0095] Particularly preferred are a) 10 to 30 wt. % of at least one aliphatic or aromatic polyisocyanate having a functionality of 2 or more; b) 50 to 80 wt. % of at least one polyester polyol composed of succinic acid and at least two different dihydroxy compounds whose carbon skeleton contains 2 to 12 carbon atoms and having a functionality of 2 or more and a number average molar mass Mn of 400 to 8000 g / mol, c) 0.75 to 4.0 wt. % of at least one isocyanate-reactive compound having a functionality of 2 or greater and containing potential ionic groups; d) 0.7 to 12 wt. % of at least one polyamine having a molar mass of 32 to 400 g / mol and a functionality of 1 to 3, e) optionally 0-15 wt. % of at least one non-ionic isocyanate-reactive hydrophilizing agent; f) optionally 0 to 7.0 wt. % of at least one polyhydroxy compound having a molar mass of less than 400 g / mol and a functionality of 2 to 4; g) optionally 0 to 8.0 wt. % of at least one neutralizing agent for neutralizing the potential ionic groups of component c); A polyurethaneurea polymer consisting of: The sum of components a) to g) is 100 wt% or less; It may be a polyurethaneurea polymer.

[0096] The number-average molar mass Mn of the polyester polyols can be determined by gel permeation chromatography in tetrahydrofuran at 23° C. against polystyrene standards.

[0097] The polyester polyols used for the present invention may have a glass transition temperature Tg, determined by DSC measurement according to DIN 65467, in the range of -80°C to 0°C, particularly preferably in the range of -70°C to -10°C, at a heating rate of 20 K / min.

[0098] Suitable polyisocyanates a) are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known per se to those skilled in the art.Suitable polyisocyanates a) are, for example, 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, isomeric bis-(4,4'-isocyanatocyclohexyl)methane or mixtures thereof with any desired isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, or hydrogenated 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), (S)-alkyl 2,6-diisocyanatohexanoates or (L)-alkyl 2,6-diisocyanatohexanoates.

[0099] The corresponding use of polyisocyanates with a functionality of more than 2 is also possible. These include modified diisocyanates with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures, as well as unmodified polyisocyanates with more than two NCO groups per molecule, such as 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4',4''-triisocyanate.

[0100] Preference may be given to polyisocyanates or polyisocyanate mixtures of the above-mentioned types which have only aliphatically and / or cycloaliphatically bound isocyanate groups with an average functionality of 2 to 4, preferably 2 to 2.6, particularly preferably 2 to 2.4.

[0101] The polyester polyols which can be used as compounds b) can have a number-average molecular weight Mn of 400 to 8000 g / mol, preferably 400 to 6000 g / mol, particularly preferably 400 to 3000 g / mol. The number-average molecular weight Mn of the polyester polyols can be determined by gel permeation chromatography against polystyrene standards in tetrahydrofuran at 23° C. Their hydroxyl number according to DIN ISO 4629 can be 22 to 400 mg KOH / g, preferably 30 to 300 mg KOH / g, particularly preferably 40 to 250 mg KOH / g, and they can have an OH functionality of 1 to 6, preferably 1.5 to 4.0, particularly preferably 1.9 to 2.1.

[0102] The polyester polyols b) can be prepared according to the prior art by polycondensation of preferably succinic acid, succinic anhydride and / or succinic esters with two different dihydroxy compounds having 2 to 12 carbon atoms and a functionality of at least 2, with molar masses of 62 to 300 g / mol, which can be branched or unbranched and whose hydroxyl groups are primary or secondary. The dihydroxy compounds can also contain ether groups. Preferably, the dihydroxy compounds can be selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,2-dodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and oligo-tetrahydrofurans with hydroxyl end groups. Particularly preferably, the two dihydroxy compounds can be selected from diols with a carbon skeleton of 3 to 6 carbon atoms, most particularly preferably from the group consisting of hexanediol, neopentyl glycol and 1,3-propanediol. The preparation of the polyester polyols b) can be carried out according to the prior art at elevated temperatures in the range of 150 to 250° C., with application of a vacuum of 1 to 100 mbar and / or under a stream of nitrogen, optionally using esterification or transesterification catalysts, the reaction being completed to the extent that the acid number according to DIN EN ISO 2114 is below a value of 5 mg KOH / g.

[0103] Succinic acid for the preparation of component b) can be obtained from renewable and renewable sources, the preparation process often proceeding via a starch or biomass fermentation process, as disclosed, for example, in DE 10 2008 051727 A1 and DE 10 2007 019184. Preferably, at least 50 wt.% of the succinic acid is based on renewable sources.

[0104] Further or additionally, at least a portion of the at least one dihydroxy compound of component b) may be derived from a renewable source, thus increasing the carbon fraction originating from renewable sources of the polyurethane / urea polymer for the present invention. Preferably, the at least one dihydroxy compound component b) may be selected from 1,4-butanediol, 1,3-propanediol, isopropanediol, 1,6-hexanediol, ethylene glycol, which are derived from renewable sources or a mixture of at least two of them.

[0105] Component c) contains potential ionic groups, which can be either cationic or anionic in nature. Compounds with cationic, anionic or non-ionic dispersing action are, for example, those that contain sulfonium, ammonium, phosphonium, carboxylate, sulfonate, phosphonate groups, or groups that can be converted into the above-mentioned groups by forming salts (potential ionic groups) or polyether groups, and that can be incorporated into macromolecules by the presence of isocyanate-reactive groups. Preferred suitable isocyanate-reactive groups are hydroxyl and amine groups.

[0106] Suitable ionic or potentially ionic compounds c) are, for example, mono- and di-hydroxycarboxylic acids, mono- and di-aminocarboxylic acids, mono- and di-hydroxysulfonic acids, mono- and di-aminosulfonic acids and mono- and di-hydroxyphosphonic acids or mono- and di-aminophosphonic acids and their salts, such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N-(2-aminoethyl)-β-alanine, 2-(2-amino-ethylamino)-ethanesulfonic acid, ethylenediamine-propyl- or -butyl-sulfonic acid, 1,2- or 1,3-propylenediamine-β-ethylsulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, addition products of IPDI and acrylic acid (EP-A 0 916 647, Example 1) and the alkali and / or ammonium salts thereof; Adducts of sodium sulfite with 2-butene-1,4-diol, sulfonic polyethers, propoxylated adducts of 2-butenediol with NaHSO3, as described, for example, in DE-A 2 446 440 (pages 5-9, formulae I-III), as well as structural units which can be converted into cationic groups, for example N-methyl-diethanolamine as hydrophilic chain-extending component. Preferred ionic or potentially ionic compounds are those which have carboxy or carboxylate and / or sulfonate groups and / or ammonium groups and have a functionality of 1.9 to 2.1. Particularly preferred ionic compounds have an amine functionality of 1.9 to 2.1 and contain sulfonate groups as ionic or potentially ionic groups, for example salts of N-(2-aminoethyl)-β-alanine, salts of 2-(2-amino-ethylamino)-ethanesulfonic acid or addition products of IPDI with acrylic acid (EP-A 0 916 647, example 1). Further or additionally, at least a portion of components c) can be derived from renewable sources, thus increasing the carbon fraction originating from renewable sources of the polyurethane / urea polymer for the present invention. Examples of these components c) derived from renewable sources are selected from the group consisting of malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine and lysine, or a mixture of at least two thereof.

[0107] The polyamines d) used for the chain extension may preferably have a functionality of 1 to 2, for example di- or polyamines and hydrazides, such as ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine; 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1,3- and 1,4-xylylenediamine, a,a,a',a'-tetramethyl-1,3- and -1,4-xylylenediamine and 4,4-diaminodicyclohexylmethane, dimethylethylenediamine, hydrazine or isomeric mixtures of adipic dihydrazide.

[0108] It is conceivable that component d) also essentially comprises compounds containing active hydrogens of different reactivity towards NCO groups, for example compounds which contain secondary amino groups in addition to primary amino groups, or compounds which contain OH groups in addition to (primary or secondary) amino groups. Examples are primary / secondary amines, such as 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, and also alkanolamines, such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol or neopentanolamine.

[0109] Preferred may be diethanolamine and / or hydrazine and / or isophorone diamine (IPDA) and / or ethylene diamine. Particularly preferred may be hydrazine and / or isophorone diamine and / or ethylene diamine. Most particularly preferred may be a mixture of hydrazine and IPDA.

[0110] Suitable compounds e) with non-ionic hydrophilizing action are, for example, polyoxyalkylene ethers containing at least one hydroxy or amino group. Such polyethers contain structural units derived from ethylene oxide in an amount of 30% by weight to 100% by weight. There are also suitable linear polyethers with a functionality of 1 to 2, but also those of the formula (I):

[0111] [ka]

[0112] (In the formula, R 1 and R 2 each independently of the others represents a divalent aliphatic, alicyclic or aromatic radical having 1 to 18 carbon atoms, which may be interrupted by oxygen and / or nitrogen atoms; R3 represents an alkoxy-terminated polyethylene oxide group. There are also compounds of the formula:

[0113] Compounds e) with non-ionic hydrophilic action are, for example, also monohydric polyalkylene oxide polyether alcohols having, as a statistical average, 5 to 70, preferably 7 to 55, ethylene oxide units per molecule and are obtainable in a manner known per se by alkoxylation of suitable starter molecules (for example Ullmanns Encyclopadie der technischen Chemie, 4th edition, Vol. 19, Verlag Chemie, Weinheim, pages 31-38).

[0114] Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexanes, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, for example diethylene glycol monobutyl ether. , unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anise alcohol or cinnamic alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis-(2-ethylhexyl)-amine, N-methyl- and N-ethyl-cyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols. Particularly preferred is the use of diethylene glycol monobutyl ether as starter molecule.

[0115] Suitable alkylene oxides for the alkoxylation reaction are in particular ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any desired sequence or in an addition mixture.

[0116] The number-average molar mass Mn of the alkylene oxide is 300 g / mol to 6000 g / mol, preferably 500 g / mol to 4000 g / mol, particularly preferably 750 g / mol to 3000 g / mol, with a functionality of 1. The number-average molecular weight Mn of the alkylene oxide is determined by gel permeation chromatography in tetrahydrofuran at 23° C. against polystyrene standards.

[0117] Suitable nonionic hydrophilizing monofunctional compounds e) of this type are, for example, monofunctional alkoxypolyethylene glycols, such as methoxypolyethylene glycols (MPEG Carbowax® 2000 or Methoxy PEG-40, molecular weight range 1800-2200, from The Dow Chemical Company), monofunctional polyether monoalkyl ethers, such as LB 25 from Bayer Material Science, composed of butanol and ethylene oxide and propylene oxide, with an average molar mass Mn of 2250 g / mol, monofunctional polyetheramines (Jeffamine® M 1000, PO / EO molar ratio 3 / 19, and M 2070, PO / EO molar ratio 10 / 31, from Huntsman Corp.).

[0118] Compounds e) which are preferably used are MPEG Carbowax® 2000, LB 25 or Jeffamine® M 2070. MPEG Carbowax® 2000 or LB 25 are particularly preferred.

[0119] The low molecular weight polyols f) which may optionally be used in the formation of the polyurethane resin generally provide reinforcement and / or branching of the polymer chain. Their molecular weight is preferably between 62 and 200 and their functionality is preferably between 2 and 3. Suitable polyols c) may contain aliphatic, cycloaliphatic or aromatic groups. For example, low molecular weight polyols having up to about 20 carbon atoms per molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof, as well as trimethylolpropane, glycerol or pentaerythritol may be mentioned here. It is also possible to use ester diols, such as δ-hydroxybutyl-δ-hydroxy-caproic acid ester, ω-hydroxyhexyl-γ-hydroxybutyric acid ester, adipic acid (β-hydroxyethyl) ester or terephthalic acid bis(β-hydroxyethyl) ester. Particular preference is given to hexanediol and / or trimethylolpropane and / or butanediol.

[0120] Neutralizing agents g) will be optionally used after or during the preparation of the polyurethane prepolymer from a), b) and c) if it does not contain amino groups, and optionally from e) and f) if it has not already been carried out in the starting molecule, to neutralize the potentially ionic groups c), the partial or complete formation of salts of which has an anionic and / or cationic dispersing action. In the case of anionic groups, bases are used for that purpose, such as ammonia, ammonium carbonate or hydrogen carbonate, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, potassium hydroxide or sodium carbonate, preferably triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine. The amount of base is 50-100%, preferably 60-90%, of the amount of anionic groups. In the case of cationic groups, dimethyl ester sulfate or succinic acid is used. If only compounds non-ionic hydrophilized with ether groups are used, the neutralization step is omitted. Neutralization can also be carried out simultaneously with dispersing if the dispersing water already contains the neutralizing agent.

[0121] The preparation of the polyurethane / urea polymer in the form of an aqueous dispersion can be carried out in one or more stages in a homogeneous phase or, in the case of a multi-stage reaction, partially in a dispersed phase. If polyaddition is carried out completely or partially, a dispersing, emulsifying or dissolving step is carried out. Then, optionally, further polyaddition or modification in the dispersed phase is carried out.

[0122] All processes known from the prior art can be used to prepare polyurethane / urea polymers in the form of aqueous dispersion, such as emulsifier / shear force, acetone, prepolymer mixing, melt emulsification, ketimine and solid spontaneous dispersion methods, or those derived therefrom.An overview of these methods can be found in Methoden der organischen Chemie (Houben-Weyl, Erweiterungs- und Folgebande zur 4.Auflage, Volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pages 1671-1682).Preference is given to the melt emulsification and acetone methods.Particular preference is given to the acetone method.

[0123] Usually, all or some of the components a) to g) that do not contain primary or secondary amino groups, and one or more polyisocyanates a) are placed in a reactor and optionally diluted with a solvent that is miscible with water but inert towards isocyanate groups, but preferably without solvent, and heated to an elevated temperature, preferably in the range of 50 to 120° C., to prepare the polyurethane prepolymer.

[0124] Suitable solvents are, for example, acetone, butanone, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl and 1-methyl-2-pyrrolidone, which can be added in portions at the beginning of the preparation as well as later. Acetone and butanone are preferred. For example, it is possible to carry out the reaction at normal pressure or at elevated pressure, above the normal boiling temperature of the optionally added solvent, for example acetone.

[0125] Catalysts known to promote isocyanate addition reactions, such as triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, stannous dioctanoate, or dibutyltin dilaurate, may also be placed in the reaction vessel at the same time or added later, with dibutyltin dilaurate being preferred.

[0126] Any components (a) and / or (b)-(f) not containing primary or secondary amino groups that were not added at the beginning of the reaction are then metered therein. The ratio of isocyanate groups to isocyanate-reactive groups in the preparation of the polyurethane prepolymer is 0.90-4.00, preferably 1.20-3.00, particularly preferably 1.40-2.50. The reaction of components a) with b), c), e) and f) is carried out partially or completely, but preferably completely, based on the total amount of isocyanate-reactive groups. The degree of conversion is usually monitored by the following NCO content of the reaction mixture. At the end of it, both spectroscopic measurements, for example infrared or near infrared spectrum, determination of the refractive index and chemical analysis, for example titration of the removed sample, can be carried out. The polyurethane prepolymer containing free isocyanate groups is obtained without solvent or in solution. In a further process step, if this has not yet been carried out or has only been partially carried out, the prepolymer obtained is then dissolved with the aid of the above-mentioned solvents.

[0127] The possible NH2- and / or NH-functional components c) and d) are then reacted with the remaining isocyanate groups. This chain extension / termination can be carried out either in a solvent before dispersion, during dispersion, or in water after dispersion. Preferably, the chain extension is carried out before dispersion in water.

[0128] The degree of chain extension, i.e. the equivalent ratio of the NCO-reactive groups of the compound used for chain extension to the free NCO groups of the prepolymer, is 40-100%, preferably 60-100%, particularly preferably 70-100%.

[0129] The amine components c) and d), optionally in solution in water or in a solvent, can be used in the process individually or in mixtures, any sequence of addition being possible in principle.

[0130] When water or an organic solvent is additionally used as a diluent, the diluent content is preferably 70-95 wt %.

[0131] The preparation of the polyurethane / urea polymer in the form of an aqueous dispersion from the prepolymer can be carried out following the chain extension. At the end of it, the chain-extended dissolved polyurethane polymer is introduced into the dispersion water, optionally with significant shear, for example with vigorous stirring, or conversely, the dispersion water is stirred into the polymer solution. Preferably, water is added to the dissolved prepolymer.

[0132] The solvent still contained in the dispersion after the dispersion step is usually subsequently removed by distillation. Removal of the solvent during dispersion is likewise possible.

[0133] The solids content of the polyurethane / urea polymer in the form of an aqueous dispersion may be from 20 to 70 wt.-%, preferably from 30 to 65 wt.-%, particularly preferably from 32 to 62 wt.-%.

[0134] According to a preferred embodiment, component b) comprises the reaction product of succinic acid with at least one dihydroxy compound whose carbon skeleton contains from 2 to 12 carbon atoms and wherein the succinic acid is derived from a renewable source.

[0135] According to a preferred embodiment, the dihydroxy compound comprises 1,4-butanediol or 1,3-propanediol or both derived from renewable sources. According to a preferred embodiment, the polyurethane / urea polymer may be composed of 45-85 wt.%, or preferably 50-80 wt.%, of at least one polyester polyol composed of succinic acid and at least two different dihydroxy compounds, whose carbon skeleton contains 2-12 carbon atoms, with a functionality of 2 or more, and a molar mass Mn of 400-8000 g / mol, or preferably 500-6000 g / mol, or preferably 600-3000 g / mol.

[0136] According to a preferred embodiment, the polyurethane / urea polymer may be composed of 7.5-35 wt %, preferably 10-30 wt %, or preferably 15-25 wt % of at least one aromatic or aliphatic, preferably aliphatic, polyisocyanate. Preferably, the polyisocyanate is one of the aliphatic polyisocyanates listed above, particularly preferably HDI or IPDI.

[0137] According to a preferred embodiment, the polyurethane / urea polymer may be comprised of 0.5 to 4.5 wt %, or preferably 0.75 to 4.0 wt %, of at least one isocyanate-reactive compound containing potential ionic groups and having a functionality of 2 or greater.

[0138] According to a preferred embodiment, the polyurethane / urea polymer may consist of 0.25 to 15.0 wt. %, preferably 0.7 to 12 wt. %, of at least one polyamine having a molar mass Mn of 32 to 400 g / mol and a functionality of 1 to 3, preferably 1.5 to 2.5.

[0139] According to a preferred embodiment, the polyester polyols may have a glass transition temperature Tg in the range of -80°C to 0°C, determined by DSC measurement according to DIN 65467 at a heating rate of 20 K / min.

[0140] Examples of polyurethane / urea polymers include polyurethane-93 (eg, Baycusan® eco E1000 sold by Covestro), polyurethane-99, and mixtures thereof.

[0141] It may also be preferred that the (c) polyurethane contains at least one polysiloxane moiety.

[0142] In another embodiment, the (c) polyurethane may be a polysiloxane / polyurethane block copolymer.

[0143] The polysiloxane / polyurethane block copolymer has the formula (II): -OPO-CO-NH-R-NH-CO- (II) (In the formula, P is a polysiloxane segment; R is aliphatic C1-C 20 Hydrocarbon group, alicyclic C3~C 20 Hydrocarbon groups and aromatic C6-C 20 Hydrocarbon groups, e.g. C1-C 20 Alkylene group, C6-C 20 Arylene group, C3-C 20 a divalent radical selected from a cycloalkylene radical, a cycloalkylene radical, and combinations thereof, which radicals are optionally substituted. It may contain repeat units of the formula:

[0144] In a further embodiment, the polysiloxane segment P has the formula (III):

[0145] [ka]

[0146] (In the formula, The A groups may be the same or different and are selected from the group consisting of aromatic groups devoid of or substantially devoid of ethylenic unsaturation and monovalent C1-C 20 selected from hydrocarbon groups, Y is a divalent hydrocarbon group; z is an integer selected so that the mass average molecular weight of the polysiloxane segment is in the range of 300 to 10,000. You can choose from the following.

[0147] In another embodiment, the divalent group Y has the formula -(CH) a - (wherein a is an integer ranging from 1 to 10).

[0148] The A group can be, for example, C 1~8Alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl and octyl groups; C 3~8 Cycloalkyl groups, such as cyclohexyl groups; 6~10 Aryl groups, such as phenyl; C 7~10 Arylalkyl groups may be selected from, for example, benzyl and phenylethyl, and tolyl and xylyl groups.

[0149] Non-limiting examples of non-associative polyurethanes include dimethylolpropionic acid / isophorone diisocyanate / neopentyl glycol / polyester diol copolymer sold by BASF under the trade name Luviset® PUR (also known under the INCI name: Polyurethane-1) and dimethylolpropionic acid / isophorone diisocyanate / neopentyl glycol / polyester diol / silicone diamine copolymer sold by BASF under the trade name Luviset® Si PUR A (also known under the INCI name: Polyurethane-6).

[0150] (c) The polyurethanes may be used unneutralized and therefore in non-ionic form.

[0151] (c) The polyurethane may be in the form of particles. The particles may have a volume average particle size of 100 nm or less.

[0152] (c) The polyurethane is preferably selected from the group consisting of polyurethane-6, polyurethane-35, polyurethane-93, polyurethane-99, and mixtures thereof.

[0153] The amount of (c) polyurethane in the composition according to the present invention may be 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, based on the total weight of the composition.

[0154] On the other hand, the amount of (c) polyurethane in the composition according to the present invention may be 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, based on the total mass of the composition.

[0155] Accordingly, the amount of (c) polyurethane in the composition according to the present invention may be in the range of 1% by mass to 40% by mass, preferably 5% by mass to 35% by mass, and more preferably 10% by mass to 30% by mass, relative to the total mass of the composition.

[0156] (mass ratio) In the present invention, the mass ratio of (the amount of (b) the acrylic copolymer and (c) the polyurethane) / (a) the pigment is 1.5 or more, preferably 2.0 or more, and more preferably 2.5 or more.

[0157] On the other hand, the mass ratio of (the amount of (b) the acrylic copolymer and the amount of (c) the polyurethane) / (a) the amount of the pigment may be 5 or less, preferably 4 or less, and more preferably 3 or less.

[0158] Therefore, the mass ratio of (the amount of (b) the acrylic copolymer and (c) the polyurethane) / (a) the pigment may be 1.5-5, preferably 2.0-4, and more preferably 2.5-3.

[0159] In the present invention, the mass ratio of the amount of (b) acrylic copolymer / the amount of (a) pigment may be 0.01 or more, preferably 0.05 or more, and more preferably 0.1 or more.

[0160] On the other hand, the mass ratio of the amount of (b) acrylic copolymer / the amount of (a) pigment may be 1 or less, preferably 0.8 or less, and more preferably 0.6 or less.

[0161] Therefore, the mass ratio of the amount of (b) the acrylic copolymer / the amount of (a) the pigment may be from 0.01 to 1, preferably from 0.05 to 0.8, and more preferably from 0.1 to 0.6.

[0162] In the present invention, the mass ratio of the amount of (c) polyurethane / the amount of (a) pigment may be 0.1 or more, preferably 0.5 or more, and more preferably 1 or more.

[0163] On the other hand, the mass ratio of the amount of (c) polyurethane / the amount of (a) pigment may be 5 or less, preferably 4 or less, and more preferably 3 or less.

[0164] Therefore, the mass ratio of the amount of (c) polyurethane / the amount of (a) pigment may be 0.1-5, preferably 0.5-4, and more preferably 1-3.

[0165] In the present invention, the weight ratio of the amount of (c) polyurethane / the amount of (b) acrylic copolymer may be 4 or more, preferably 6 or more, and more preferably 8 or more.

[0166] On the other hand, the mass ratio of the amount of (c) polyurethane / the amount of (b) acrylic copolymer may be 20 or less, preferably 15 or less, and more preferably 10 or less.

[0167] Therefore, the mass ratio of the amount of (c) polyurethane / the amount of (b) acrylic copolymer may be 4-20, preferably 6-15, and more preferably 8-10.

[0168] (water) The composition according to the present invention comprises (d) water, preferably deionized water.

[0169] The amount of (d) water in the composition according to the present invention may be 10% by mass or more, preferably 20% by mass or more, and more preferably 25% by mass or more, based on the total mass of the composition.

[0170] The amount of (d) water in the composition according to the present invention may be 60% by mass or less, preferably 50% by mass or less, and more preferably 47% by mass or less, based on the total mass of the composition.

[0171] The amount of (d) water in the composition according to the present invention may be 10% by mass to 60% by mass, preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 47% by mass, based on the total mass of the composition.

[0172] (Optional Additives) The composition according to the invention may also comprise any optional additives normally used in the field of cosmetics, for example selected from oils, solvents, gums, resins, hydrophilic thickeners, hydrophobic thickeners, antioxidants, film formers other than components (b) and (c) above, preservatives such as phenoxyethanol, fragrances, neutralizing agents, disinfectants, UV screening agents, cosmetic active agents such as vitamins, moisturizers, emollients or collagen protectants, and mixtures thereof.

[0173] The composition according to the present invention may also contain at least one alkaline agent, such as triethanolamine, tromethamine, aminomethylpropanediol, and aminomethylpropanol. The amount of the alkaline agent in the composition according to the present invention may be 0.05% by mass to 1% by mass, preferably 0.1% by mass to 0.5% by mass, based on the total mass of the composition. By adding the alkaline agent, the pigment (a), which is carbon black, can be more stably dispersed in the composition according to the present invention.

[0174] The composition according to the invention may also contain at least one water-miscible solvent, such as a lower monoalcohol containing 1 to 5 carbon atoms, a C3-C4 ketone or a C3-C4 aldehyde. A water-miscible solvent that may be preferably used is ethanol. The content of the water-miscible solvent may range from 0.1% to 15% by weight, better still from 1% to 8% by weight, relative to the total weight of the composition according to the invention.

[0175] It is routine for a person skilled in the art to adjust the nature and amounts of the abovementioned optional additives which may be present in the composition according to the invention so that the desired cosmetic properties are not affected by said additives.

[0176] It is preferred that the amount of surfactant in the composition according to the present invention is limited. When the amount of surfactant in the composition according to the present invention is limited, the composition according to the present invention can further enhance the long-lasting makeup effect.

[0177] The surfactant may be selected from cationic, anionic, amphoteric and nonionic surfactants, preferably anionic and nonionic surfactants, more preferably nonionic surfactants.

[0178] For example, the amount of surfactant in the composition according to the invention may be 0.5% by weight or less, preferably 0.3% by weight or less, more preferably 0.1% by weight or less, based on the total weight of the composition. Most preferably, the composition according to the invention does not contain any surfactant.

[0179] [Preparation] The compositions according to the present invention can be prepared by mixing the essential and optional ingredients described above in a conventional manner.

[0180] For example, the composition according to the present invention comprises: (a) at least one pigment which is carbon black; (b) at least one acrylic copolymer of at least two monomers selected from (meth)acrylic acid, its esters, and its salts; (c) at least one polyurethane; (d) Water and of The composition can be prepared by a method including a mixing step such that the mass ratio of (the amount of (b) the acrylic copolymer and the amount of (c) the polyurethane) / (a) the amount of the pigment is 1.5 or more, preferably 2.0 or more, and more preferably 2.5 or more.

[0181] Any of the optional ingredients can be further mixed.

[0182] It may be more preferred that the (a) pigment and (b) acrylic copolymer are first mixed with a portion of the (d) water to prepare an aqueous dispersion of the (a) pigment dispersed with the (b) acrylic polymer, which is then further mixed with the (c) polyurethane and preferably the remainder of the (d) water to obtain a composition according to the present invention.

[0183] Mixing can be carried out at any temperature, such as room temperature (e.g., 25° C.), preferably at a temperature of 30° C. or higher, preferably 40° C. or higher, more preferably 50° C. or higher. Further mixing with any of the optional ingredients listed above is preferred.

[0184] It is preferred that the cosmetic composition according to the present invention is in the form of a liquid, preferably a dispersion of (a) the pigment, more preferably an aqueous dispersion of (a) the pigment.

[0185] [Cosmetic Uses and Methods] The composition according to the present invention may be a cosmetic composition, preferably a makeup cosmetic composition (particularly an eye makeup cosmetic composition), more preferably an eyeliner.

[0186] The cosmetic composition according to the invention can be used for the cosmetic treatment, preferably the make-up, of keratinous materials such as the skin and mucosal surfaces, such as the edge of the eyelid.

[0187] For example, the composition according to the invention can be used for a cosmetic method for making up keratinous materials, such as the skin and mucosal surfaces, comprising the step of applying a composition according to the invention onto the keratinous material.

[0188] The composition according to the present invention can provide cosmetic effects, particularly makeup effects, such as concealing the natural color of keratinous materials, and can also provide a long-lasting makeup effect.

[0189] The present invention also provides (a) at least one pigment which is carbon black; (b) at least one acrylic copolymer of at least two monomers selected from (meth)acrylic acid, its esters, and its salts; (d) Water and of, The present invention also relates to the use of at least one polyurethane (c) in a composition for stabilizing said composition, the composition comprising said polyurethane (c) such that the mass ratio of (the amount of (b) acrylic copolymer and the amount of (c) polyurethane) / (a) pigment is 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more. EXAMPLES

[0190] The present invention will be described in a more detailed manner by examples.However, these examples should not be interpreted as limiting the scope of the present invention.The following examples are presented as non-limiting examples in the field of the present invention.

[0191] (Examples 1 to 3 and Comparative Example 1) [Preparation] The following compositions according to Examples 1-3 and Comparative Example 1 shown in Table 1 were prepared by mixing the components shown in Table 1 at room temperature (25° C.). All numerical amounts of components shown in Table 1 are based on "mass %" of active ingredient unless otherwise specified.

[0192] [Table 1A]

[0193] [Table 1B]

[0194] [evaluation] (viscosity stability) The viscosity of each of the compositions according to Examples 1 to 3 and Comparative Example 1 was measured using an ARES-RFS type rheometer at 25° C. and 100 s -1The bulk viscosity was measured at a shear rate of 24 hours after preparation of the composition (initial bulk viscosity), 1 month after preparation at 45°C (bulk viscosity after 1 month at 45°C), and 2 months after preparation at 45°C (bulk viscosity after 2 months at 45°C).

[0195] The change in viscosity at 2 months at 45° C. (bulk stability change after 2 months at 45° C.) was calculated by the following equation: Bulk stability change after 2 months at 45°C (%) = 100 x (bulk viscosity after 2 months at 45°C - initial bulk viscosity) / initial bulk viscosity

[0196] The "bulk stability change after 2 months at 45°C" values ​​were classified according to the following criteria: Very good: less than 10% Good: 10% to less than 25% Normal: 25% to less than 75% Defective: 75% or more

[0197] The results are shown in Table 1 in the row "Bulk stability score after 2 months."

[0198] (Early deposition) Each of the compositions according to Examples 1 to 3 and Comparative Example 1 was filled into a liquid pen-type package as an eyeliner. Five types of eyeliner samples were prepared for each of the compositions according to Examples 1 to 3 and Comparative Example 1. The deposition amount of the five types of eyeliner samples was measured by drawing 10 lines on the surface of a substrate and averaging them 24 hours after preparation (initial deposition average).

[0199] The average deposition amount was classified according to the following criteria: Very good: >20mg - 30mg Good: More than 10mg~20mg Normal: More than 5mg~10mg Defective: 5mg or less

[0200] The results are shown in Table 1 under the row "Initial Deposition Average Score."

[0201] (deposition stability) Each of the compositions according to Examples 1 to 3 and Comparative Example 1 was filled into a liquid pen-type package as an eyeliner. Five types of eyeliner samples were prepared for each of the compositions according to Examples 1 to 3 and Comparative Example 1. The deposition amounts of the five types of eyeliner samples were measured by drawing 10 lines on the surface of a substrate and averaging them one month after preparation at 45°C (average of deposition after one month at 45°C) and two months after preparation at 45°C (average of deposition after two months at 45°C).

[0202] The average change in deposition amount at 45° C. for 1 or 2 months (deposition change after 1 month or deposition change after 2 months) was calculated by the following equation: Volume change after 1 month (%) = 100 x (average volume after 1 month at 45°C - initial volume average) / initial volume average Volume change after 2 months (%) = 100 x (average volume after 2 months at 45°C - initial volume average) / initial volume average

[0203] The deposition change values ​​after one month and after two months were classified according to the following criteria. Very good: less than 25% Good: 25% to less than 50% Normal: 50% to less than 75% Defective: 75% or more

[0204] The results are shown in Table 1 in the rows "Deposition stability score after 1 month" and "Deposition stability score after 2 months."

[0205] (Long-lasting effect) Each of the compositions according to Examples 1 to 3 and Comparative Example 1 was filled into a liquid pen-type package as an eyeliner, and a line was drawn on the back of the hand of a panelist. After drying for 10 minutes, an artificial sebum having the composition shown in Table 2 was dropped onto the line, which was then rubbed with a finger 30 times. The appearance of the line was evaluated by visual observation. Very good: no flakes or stains observed Good: Almost no flakes or stains Normal: Small flakes or stains observed Bad: The line was not held

[0206] [Table 2]

[0207] The results are shown in Table 1 in the "persistence" row.

[0208] (Blackness) Each of the compositions according to Examples 1 to 3 and Comparative Example 1 was filled into a liquid pen-type package as an eyeliner, and five lines were drawn on the back of the hand of a panelist. The darkness of the lines was evaluated by visual observation. Very good: skin color completely concealed by black lines Good: Skin color concealed by black lines Normal: Most of the skin color is concealed by black lines Poor: Skin color was not concealed by the black lines

[0209] The results are shown in Table 1 in the row "Blackness Intensity."

[0210] (overview) The compositions according to Examples 1 to 3 of the present invention show excellent stability in terms of viscosity and deposition even after 2 months at high temperature. The compositions according to Examples 1 to 3 also show good cosmetic effects in terms of persistence or darkness, which reflects a concealing effect.

[0211] The composition according to Comparative Example 1, which does not contain any polyurethane and does not correspond to the present invention, shows good cosmetic effects in terms of durability and darkness, but shows poor stability in terms of viscosity and deposition amount.

Claims

1. (a) at least one pigment; (b) at least one acrylic copolymer of at least two monomers selected from (meth)acrylic acid, its esters, and its salts; (c) at least one polyurethane; (d) Water and A composition comprising: the mass ratio of (the amount of (b) the acrylic copolymer and the amount of (c) the polyurethane) to the amount of (a) the pigment is 1.5 or more, preferably 2.0 or more, and more preferably 2.5 or more; (a) the pigment is carbon black; composition.

2. 2. The composition according to claim 1, wherein the amount of the (a) pigment in the composition is 1% by mass to 30% by mass, preferably 3% by mass to 20% by mass, and more preferably 5% by mass to 10% by mass, relative to the total mass of the composition.

3. The (meth)acrylic acid ester for the (b) acrylic copolymer is C 1 ~C 30 Alkyl (meth)acrylate having an alkyl group, C 6 ~C 10 Aryl (meth)acrylate having an aryl group, and C 2 ~C 6 The composition of claim 1, wherein the hydroxyalkyl group is selected from hydroxyalkyl (meth)acrylates.

4. The composition according to claim 1, wherein the amount of the (b) acrylic copolymer in the composition is 0.001% by weight to 30% by weight, preferably 0.01% by weight to 20% by weight, and more preferably 0.1% by weight to 10% by weight, relative to the total weight of the composition.

5. The composition of claim 1 , wherein the (c) polyurethane comprises at least one urea moiety.

6. The composition of claim 1 , wherein the (c) polyurethane comprises at least one polysiloxane moiety.

7. 2. The composition of claim 1, wherein the (c) polyurethane is selected from the group consisting of polyurethane-6, polyurethane-35, polyurethane-93, polyurethane-99, and mixtures thereof.

8. The composition according to claim 1, wherein the amount of the (c) polyurethane in the composition is 1% by mass to 40% by mass, preferably 5% by mass to 35% by mass, and more preferably 10% by mass to 30% by mass, relative to the total mass of the composition.

9. 2. The composition according to claim 1, wherein the mass ratio of the amount of the (c) polyurethane to the amount of the (b) acrylic copolymer is 4 or more, preferably 6 or more, and more preferably 8 or more.

10. The composition of claim 1 , wherein the (b) acrylic copolymer and / or the (c) polyurethane are in the form of particles.

11. The composition according to claim 1, wherein the amount of (d) water in the composition is 10% by mass to 60% by mass, preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 47% by mass, relative to the total mass of the composition.

12. 2. The composition according to claim 1, comprising at least one surfactant in an amount of 0.5% by weight or less, preferably 0.3% by weight or less, more preferably 0.1% by weight or less, relative to the total weight of the composition, or comprising no surfactant at all.

13. The composition according to claim 1, which is a cosmetic composition, preferably a makeup composition, more preferably an eyeliner composition.

14. A cosmetic method for making up keratinous materials, comprising: Applying a composition according to any one of claims 1 to 13 onto the keratinous materials. Beauty methods, including: