USE OF POLYCARBOXYLIC ACID COMPOUNDS FOR THE TREATMENT OF FIBRIOUS AMINO ACID BASED SUBSTRATES, ESPECIALLY HAIR

Abstract

This invention relates to the use of polycarboxylic acid compounds, aqueous compositions comprising the same, cosmetic compositions comprising the same, in particular, hair care compositions, and their use for the treatment of hair, and a process for the treatment of hair comprising the use of said cosmetic compositions.

Claims

1.-44. (canceled)

45. A method for the color and shape treatment of hair, preferably for the color treatment of hair, which comprises the step of applying a polyorganosiloxane of formula (A) having an average number of 2 to 1000 siloxy units selected from the siloxy groups of the formulas: ##STR00082## wherein R is selected from R.sup.1 and R.sup.F, wherein R.sup.1 is selected from organic groups bound to the silicon atoms by a carbon atom, and two groups R.sup.1 may form a bridging group between two silicon atoms, R.sup.F is selected from organic groups different from R.sup.1 and is bound to the silicon atoms by a carbon atom, and R.sup.F contains at least one functional group F selected from:
OC(O)R.sup.3C(O)OH, and
NR.sup.4C(O)R.sup.3C(O)OH, and wherein the groups F bind to a carbon atom, wherein R.sup.3 is selected from a single bond or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms, which optionally contain one or more groups selected from O, C(O), C(S), tertiary amino groups ##STR00083## and quaternary ammonium groups ##STR00084## with the proviso that R.sup.3 is not CHCH, and R.sup.4 is selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00085## and quaternary ammonium groups ##STR00086## or a compound of formula (B):
R.sup.2(F).sub.2-18(B) wherein R.sup.2 is selected from divalent to octadecavalent, optionally substituted hydrocarbon radicals which have up to 100 carbon atoms, and may contain optionally one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00087## and quaternary ammonium groups ##STR00088## and F is as defined above, or salts of said polyorganosiloxanes of formula (A) or said compound of formula (B), to said hair.

46. A method according to claim 45, wherein the optional substituents of the groups R.sup.2, R.sup.3 and R.sup.4 are selected from the groups consisting of hydroxyl, amino and halogen, preferably hydroxyl and amino, and the number of the substituents may be up to 5, preferably 1 to 4.

47. A method according to claim 45, wherein R.sup.4 is selected from the group consisting of hydrogen, n-, iso-, or tert.-C.sub.1-C.sub.22-alkyl, C.sub.2-C.sub.22-alkoxyalkyl, C.sub.5-C.sub.30-cycloalkyl, C.sub.6-C.sub.30-aryl, C.sub.6-C.sub.30-aryl(C.sub.1-C.sub.6)alkyl, C.sub.6-C.sub.30-alkylaryl, C.sub.2-C.sub.22-alkenyl, C.sub.2-C.sub.22-alkenyloxyalkyl, which optionally can be each substituted by hydroxyl and halogen, and which optionally can contain one or more ether groups (O), preferably hydrogen or n-, iso-, or tert.-C.sub.1-C.sub.22-alkyl.

48. A method according to claim 45, wherein R.sup.2 in compound (B) is selected from divalent to decavalent, more preferred divalent to hexavalent, even more preferred divalent hydrocarbon radicals which have 2 to 30 carbon atoms, more preferred 2 to 20 carbon atoms, even more preferred 2 to 15 carbon atoms, even more preferred 2 to 15, specifically 2 to 12, more specifically 3 to 10 carbons atoms and may contain optionally one or more groups selected from O, NH, C(O), C(S), and wherein R.sup.2 may optionally be substituted by one or more hydroxyl groups.

49. A method according to claim 45, wherein R.sup.2 in compound (B) is selected from the group consisting of: divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, derived from aliphatic polyols having more than three carbon atoms such as alkane di-, tri- and tetraols, e.g. 1,6 hexandiol, trimethylolpropane, and pentaerythritol, divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, comprising at least one ether group, and optionally having one or more hydroxyl substituents, derived from polyalkyleneoxides, such as ethylene oxide-, propylene oxide- and/or butylene oxide-based polyethers, e.g. derived from polyethylene glycols, like diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol etc., or derived from polypropylene glycols, like dipropylene glycol (e.g, derived from 2,2-oxydi-1-propanol, 1,1-oxydi-2-propanol, and 2-(2-hydroxypropoxy)-1-propanol), tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, etc., derived from mixed ethylene oxide and butylene oxide based copolyethers, derived from mixed propylene oxide and butylene oxide based copolyethers, and derived from mixed ethylene oxide and propylene oxide and butylene oxide based copolyethers, divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, optionally comprising at least one ether group, and optionally having one or more hydroxyl substituents, derived from oligoglycerols, such as diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, and the statistically distributed oligomeric condensation products of glycerol, such as divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, derived from compounds comprising at least one glycidoxy group, such as diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidylether, divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, comprising at least one ether group, and optionally having one or more hydroxyl substituents, derived from polyol alkylene oxide addition products, e.g. the addition products of ethylene oxide and/or propylene oxide to polyols such as ethylene glycol, 1,2 propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, comprising at least one ether group, and optionally having one or more hydroxyl and/or amino substituents, derived from polyamine alkylene oxide addition products, e.g. the addition products of ethylene oxide and/or propylene oxide to ethylenediamine, diethylene triamine, or derived from alkylene oxide addition products of ethanol amine, divalent to octadecavalent, preferably divalent to hexavalent hydrocarbyl groups, more preferably divalent hydrocarbyl groups, comprising at least one ester group, and having one or more hydroxyl substituents, e.g. derived from polyesters, preferably derived from the condensation of di- to hexavalent carboxylic acids, e.g. maleic acid, succinic acid, adipic acid, sebacic acid, itaconic acid, tartaric acid, trimellitic acid with alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, and compounds comprising at least one glycidoxy group, such as glycidol, diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, in particular the condensation products of succinic acid, maleic acid and tartaric acid to glycerol diglycidyl ether, and preferably polyalkylene oxide groups, preferably of the general formula:
[CH.sub.2CH.sub.2O].sub.q1[CH.sub.2CH(CH.sub.3)O].sub.r1[CH.sub.2CH(C.sub.2H.sub.5)O].sub.s1{[CH.sub.2CH.sub.2].sub.q2[CH.sub.2CH(CH.sub.3)].sub.r2[CH.sub.2CH(C.sub.2H.sub.5)].sub.s2} with q1=0 to 49, preferred 0 to 10, more preferred 1 to 10, even more preferred 1 to 5, r1=0 to 32, preferred 0 to 10, more preferred 1 to 10, even more preferred 1 to 5, s1=0 to 24, preferred 0 to 10, more preferred 1 to 10, even more preferred 1 to 5, q2=0 or 1, r2=0 or 1, s2=0 or 1, and
(q2+r2+s2)=1, with the proviso that the sum of the carbon atoms in such polyalkylene oxide groups is 2 to 100, preferred 2 to 50, more preferred 2 to 30, even more preferred 2 to 20, specific 2 to 15, divalent to hexavalent hydrocarbyl groups, derived from oligoglycerols of the general formula:
[CH.sub.2CH(R.sup.6)CH.sub.2O].sub.t1[CH.sub.2CH(R.sup.6)CH.sub.2)].sub.t2 with t1=0 to 32, preferred 0 to 10, more preferred 1 to 10, even more preferred 1 to 5, specifically 1 and 2, t2=1, R.sup.6OH or F, wherein F is as defined above, preferably OC(O)R.sup.3C(O)OH, with the proviso that the sum of the carbon atoms is 2 to 100, preferred 2 to 50, more preferred 2 to 30, even more preferred 2 to 20, specific 2 to 15, divalent to hexavalent hydrocarbyl groups, comprising at least one ester group of the general formulae:
[CH.sub.2CH.sub.2O].sub.q1R.sup.7[CH.sub.2CH.sub.2O].sub.q1[CH.sub.2CH.sub.2].sub.q2 with q1 can be the same or different and are as defined above and q2=1 and
[CH.sub.2CH(R.sup.6)CH.sub.2O].sub.t1R.sup.7[CH.sub.2CH(R.sup.6)CH.sub.2O].sub.t1[CH.sub.2CH(R.sup.6)CH.sub.2)].sub.t2 with t1, t2 and R.sup.6 as defined above and R.sup.7 being selected from C(O)C(O)O, C(O)(CH.sub.2).sub.1-8C(O)O, such as being derived from succinic acid, adipic acid, sebacic acid, or C(O)(C.sub.6H.sub.4)C(O)O, i.e. derived from phthalic and terephthalic acid, C(O)CHCHC(O)O, C(O)C(CH.sub.2)CH.sub.2C(O)O, C(O)CH(OH)CH(OH)C(O)O, with the proviso that the sum of the carbon atoms is 2 to 100, preferred 2 to 50, more preferred 2 to 30, even more preferred 2 to 20, specific 2 to 15.

50. A method according to claim 45, wherein R.sup.2 in compound (B) contains one or more groups O, and is substituted by one or more hydroxyl groups.

51. A method according to claim 45, wherein the compound (B) is selected from the group consisting of: a compound, which has the formula: ##STR00089## wherein R.sup.5 is selected from the group consisting of hydroxy or F, wherein F is as defined above, with the proviso that at least two of R.sup.5 are F; a compound (B) which has the formula: ##STR00090## wherein one of R.sup.9 is hydroxy and one of R.sup.9 is a group of the formula ##STR00091## and wherein F is as defined above and the dotted line is the bond to the carbon atom; a mixture of the following two isomers: ##STR00092## wherein F is as defined above; and a compound which has the formula: ##STR00093## wherein x is from 1 to 10, preferably 1 to 5, and F is as defined above.

52. A method according to claim 45, wherein R.sup.3 in compound (A) or (B) is selected from the group consisting of a single bond and straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 18, preferably up to 12, more preferably up to 10 carbon atoms, and which optionally contain one or more groups selected from O, NH, C(O), and wherein R.sup.3 is optionally substituted by one or more groups selected from hydroxyl groups, amino groups, and carboxy groups.

53. A method according to claim 45, wherein R.sup.3 in compound (A) or (B) is derived from a dicarboxylic acid of the formula: ##STR00094## wherein R.sup.3 is as defined above, such as optionally substituted aliphatic, saturated or unsaturated or aromatic dicarboxylic acids, such as oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), glutaric acid (pentanedioic acid), adipic acid (hexanedioic acid), pimelic acid (heptanedioic acid), suberic acid (octanedioic acid), azelaic acid (nonanedioic acid), sebacic acid (decanedioic acid), undecanedioic acid, dodecanedioic acid, brassylic acid (tridecanedioic acid), thapsic acid (hexadecanedioic acid), glutaconic acid (pent-2-enedioic acid), citraconic acid ((2Z)-2-methylbut-2-enedioic acid), mesaconic acid ((2E)-2-methyl-2-butenedioic acid), itaconic acid (2-methylidenebmanedioic acid), tartronic acid (2-hydroxypropanedioic acid), mesoxalic acid (oxopropanedioic acid), malic acid (hydroxybutanedioic acid), tartaric acid (2,3-dihydroxybutanedioic acid), oxaloacetic acid (oxobutanedioic acid), aspartic acid (2-aminobutanedioic acid), -hydroxy glutaric acid (2-hydroxypentanedioic acid), arabinaric acid (2,3,4-trihydroxypentanedioic acid), acetonedicarboxylic acid (3-oxopentanedioic acid), -ketoglutaric acid (2-oxopentanedioic acid), glutamic acid (2-aminopentanedioic acid), diaminopimelic acid ((2R,6S)-2,6-diaminoheptanedioic acid), saccharic acid ((2S,3S,4S,5R)-2,3,4,5-tetrahydroxyhexanedioic acid), phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), terepthtalic acid ((benzene-1,3-dicarboxylic acid)), diphenic acid (2-(2-carboxyphenyl)benzoic acid), 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, norbornane dicarboxylic acid, and trimellitic acid, or R.sup.3 is derived from an aliphatic or aromatic tricarboxylic acid, wherein R.sup.3 is substituted with carboxyl group (COOH), such as citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid), isocitric acid (1-hydroxypropane-1,2,3-tricarboxylic acid), aconitic acid ((cis or trans prop-1-ene-1,2,3-tricarboxylic acid), propane-1,2,3-tricarboxylic acid; trimesic acid (benzene-1,3,5-tricarboxylic acid), the reaction products of carboxylic acid anhydrides, such as maleic anhydride and succinic anhydride, with amino acids and amino acid derivatives, such as b-alanine and asparagine, i.e. N-acetyl aspartic acid, N-maleoyl--alanine ((E)-4-(2-carboxyethylamino)-4-oxo-but-2-enoic acid), N-maleoyl-asparagine (4-amino-2-[[(E)-4-hydroxy-4-oxo-but-2-enoyl]amino]-4-oxo-butanoic acid).

54. A method according to claim 45, wherein F in compound (A) or (B) is selected from the group consisting of the formulas: ##STR00095## wherein the dotted line in the above formulae represents the bond to the oxygen atom, and wherein there are at least two groups F.

55. A method according to claim 45, wherein the polyorganosiloxane (A) comprises at least two groups R.sup.F.

56. A method according to claim 45, wherein the average number of siloxy units in the polysiloxane (A) is 2 to 300, preferably 2 to 30, even more preferred 2 to 20, even more preferred 2 to 15, specifically 2 to 12, more specifically 2 to 10, even more specifically 2 to 8.

57. A method according claim 45, wherein the organic groups R.sup.1 are independently selected from the group consisting of straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00096## and quaternary ammonium groups ##STR00097## and which are optionally substituted by one more groups selected from the group consisting of hydroxyl, halogen (like chlorine, fluorine), a polyether radical with up to 60 carbon atoms, or two radicals R.sup.1 from different siloxy moieties form a straight-chain, cyclic or branched, saturated, unsaturated or aromatic alkandiyl hydrocarbon radical which has 2 to 20 carbon atoms between two silicon atoms, which are optionally substituted by one or more hydroxyl groups or halogen atoms, and are linked to silicon by a carbon atom, more preferably R.sup.1 is selected from the group consisting of n-, iso-, or tert.-C.sub.1-C.sub.22-alkyl, C.sub.2-C.sub.22-alkoxyalkyl, C.sub.5-C.sub.30-cycloalkyl, C.sub.6-C.sub.30-aryl, C.sub.6-C.sub.30-aryl(C.sub.1-C.sub.6)alkyl, C.sub.6-C.sub.30-alkylaryl, C.sub.2-C.sub.22-alkenyl, C.sub.2-C.sub.22-alkenyloxyalkyl, which optionally can be each substituted by hydroxyl and halogen, and which optionally can contain one or more ether groups (O), still more preferably, the radicals R.sup.1 include: n-, iso-, or tert.-C.sub.1-C.sub.22-alkyl, C.sub.2-C.sub.22-alkoxyalkyl, C.sub.5-C.sub.30-cycloalkyl, C.sub.6-C.sub.30-aryl, C.sub.6-C.sub.30-aryl(C.sub.1-C.sub.6)alkyl, C.sub.6-C.sub.30-alkylaryl, C.sub.2-C.sub.22-alkenyl, C.sub.2-C.sub.22-alkenyloxyalkyl, which can be substituted by one or more, preferred up to five, groups selected from hydoxyl and halogen, preferred fluorine, and can contain one or more ether groups, i.e. H.sub.3C, CH.sub.3CH.sub.2, CH.sub.3CH.sub.2CH.sub.2, (CH.sub.3).sub.2CH, C.sub.8-C.sub.17- and C.sub.10H.sub.21, H.sub.2CCHO(CH.sub.2).sub.1-6, cycloaliphatic radicals, i.e. cyclohexylethyl, limonyl, norbonenyl, phenyl, tolyl, xylyl, benzyl and 2-Phenylethyl, halogen(C.sub.1-C.sub.10)alkyl, i.e. C.sub.fF.sub.fn+1CH.sub.2CH.sub.2 wherein f is 1 to 8, i.e. CF.sub.3CH.sub.2CH.sub.2, C.sub.4F.sub.9CH.sub.2CH.sub.2, C.sub.6F.sub.13CH.sub.2CH.sub.2, C.sub.2F.sub.5O(CF.sub.2CF.sub.2O).sub.1-10CF.sub.2, F[CF(CF.sub.3)CF.sub.2O].sub.1-5(CF.sub.2).sub.0-2, C.sub.3F.sub.7OCF(CF.sub.3) and C.sub.3F.sub.7OCF(CF.sub.3)CF.sub.2OCF(CF.sub.3), and still more preferred R.sup.1 is selected from the group consisting of methyl, vinyl, phenyl, 3,3,3-trifluoropropyl, most preferred R.sup.1 is methyl.

58. A method according to claim 45, wherein the polysiloxane (A) contains at least two radicals of the formula M.sup.F and/or D.sup.F: ##STR00098## wherein R.sup.1 and R.sup.F are as defined above.

59. A method according to claim 45, wherein the polysiloxane (A) is selected the group consisting of polysiloxanes of the formulas: ##STR00099## wherein R.sup.1 and R.sup.F are as defined above, and n1+n2 is 0 to 28, preferred 0 to 20, more preferred 0 to 15, and n2 is preferably 0, ##STR00100## wherein R.sup.1 and R.sup.F are as defined above, n1+n2 is 2 to 28, preferred 2 to 20, more preferred 2 to 15, even more preferred 5 to 15, with n22, preferred 2 to 28, more preferred 2 to 10, even more preferred 2 to 5, and ##STR00101## wherein R.sup.1 and R.sup.F are as defined above, n1+n2 is 3 to 7 with n22, preferred n1+n2 is 2 to 7, more preferred 2 to 5, even more preferred 3 to 5.

60. A method according to claim 45, wherein an aqueous composition comprising at least one of the polyorganosiloxane (A) and/or at least one of the compound (B) as defined is applied.

61. A method according to claim 60, wherein the aqueous composition comprises from 0.05 to 30 wt-%, preferably 0.1 to 20 wt-%, preferably 0.5 to 1.5 wt-%, more preferably 1 to 10 wt-% of at least one of the polyorganosiloxane (A) and/or at least one of the compound (B), based on the total weight of the aqueous compositions.

62. A method according to claim 60, wherein the aqueous composition optionally further comprises at least one surfactant which is selected from cationic, nonionic, betaine and anionic surfactants, preferably having a HLB value ranging from 1 to 20, preferred 7 to 20, more preferred 8 to 20.

63. A method according to claim 62, wherein the surfactant is present in an amount of from about 0.05% to about 15%, preferably from about 0.05% to about 5%, still more preferably from about 0.1% to about 5%, specifically from 0.1 to 3% by weight of the aqueous composition.

64. A method according claim 60, wherein the aqueous composition comprises at least one additional additive, selected from the group consisting of: a) organic diluents or solvents, b) proteins, preferably keratin, c) emollients or fatty substances, d) preservatives, e) skin protecting ingredients, conditioning agents, g) oxidizing agents, h) reducing agents, i) tannins, j) metal salts, k) further auxiliaries selected from pH adjusting agents, thickeners, lipids, amino acids, sugars, fragrances, sunscreen agents, vitamins, pearlescent agents, gelling agents, trace elements, sequestering agents, antioxidants, humectants, anti-hair loss agents, anti-dandruff agents, propellants, ceramides, polymers, in particular film-forming polymers, fillers, nacres, colorants, in particular pigments and dyes, and mixtures thereof, with the proviso that oxidizing agents and reducing agents are not present simultaneously in a given formulation.

65. A method according to claim 60, wherein the aqueous composition has the composition: TABLE-US-00015 Ingredient Weight-% polyorganosiloxane (A) 0.05 to 30%, preferably 0.1 to 20%, more preferably 0.5 to 15%, and/or compound (B) as more preferably 1 to 10% defined in claim 60 hydrocarbon or silicone 0 to 15%, preferably 0.05 to 5% based surfactant Water q.s. to add to 100% diluents/solvents 0 to 95, preferably 0.1 to 95%, preferred 10 to 95%, more preferred 20 to 95%, even more preferred 20 to 50% and 50 to 95% protein/preferred keratin 0 to 15, preferably 0 to 10, such as 0.01 to 5 emollients/fatty substance 0 to 15, preferably 0 to 10, more preferred 0 to 5%, such as 0.01 to 5% preservatives 0 to 5, preferably 0 to 3, more preferred 0 to 2%, such as 0.01 to 2.5% skin protecting ingredients 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 1%, specifically 0 to 0.1%, e.g. 0.01 to 5% conditioning agents 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 1%, specifically 0 to 0.1%, e.g. 0.01 to 5% oxidizing agents agents 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 2%, e.g. 0.01 to 5% reducing agents 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 2%, e.g. 0.01 to 5% tannins 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 2%, e.g. 0.01 to 5% metal salts, 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 2%, e.g. 0.01 to 5% hair dyeing agent 0 to 15%, preferred 0 to 10%. more preferred 0 to 5%, even more preferred 0 to 2%, e.g. 0.01 to 5% other auxiliary agents 0 to 15%, preferred 0 to 10%, more preferred 0 to 5%, even more preferred 0 to 2%, e.g. 0.01 to 5% wherein the wt-percentages relate to the complete weight of the aqueous compositions.

66. A method according to claim 60, wherein the aqueous composition is selected from a hair shampoo composition, hair care composition, hair condition composition, hair strengthening composition, hair coloration or dyeing composition, hair color deepening composition, hair combability improving composition, anti-frizz composition, hair rinse-off and leave-on compositions.

67. A method according to claim 60 which is for hair color retention, for hair color enhancement, for hair color deepening, or for hair color protection.

68. A method for the color treatment of hair according to claim 60, which comprises applying the aqueous compositions to said hair, and the step of dyeing the hair.

69. A compound (B) of the formula:
R.sup.2(F).sub.2-18 wherein R.sup.2 is selected from divalent to octadecavalent, optionally substituted hydrocarbon radicals which have up to 100 carbon atoms, and may contain optionally one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00102## and quaternary ammonium groups ##STR00103## and F is selected from:
OC(O)R.sup.3C(O)OH, and
NR.sup.1C(O)R.sup.3C(O)OH, the groups F bind to a carbon atom of R.sup.2, wherein R.sup.1 is selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00104## and quaternary ammonium groups ##STR00105## R.sup.3 is selected from a single bond or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms, which optionally contain one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00106## and quaternary ammonium groups ##STR00107## with the proviso that R.sup.3 is not CHCH, and salts thereof.

70. A compound (B) according to claim 69, which is selected from the group of a compound of the formula: ##STR00108## wherein R.sup.5 is selected from the group consisting of hydroxy or F, wherein F is as defined above, with the proviso that at least two of R.sup.5 are F; a compound of the formula: ##STR00109## wherein one of R.sup.9 is hydroxy and one of R.sup.9 is a group of the formula ##STR00110## and wherein F is as defined above and the dotted line is the bond to the carbon atom; a mixture of the following two isomers: ##STR00111## wherein F is as defined above; and a compound of the formula: ##STR00112## wherein x is from 1 to 10, preferably 1 to 5, and F is as defined above.

71. A compound according to claim 69, wherein R.sup.3 is selected from the group consisting of a single bond and straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 18, preferably up to 12, more preferably up to 10 carbon atoms, and which optionally contain one or more groups selected from O, NH, C(O), and wherein R.sup.3 is optionally substituted by one or more groups selected from hydroxyl groups, amino groups, and carboxy groups.

72. A compound according to claim 69, wherein R.sup.3 is derived from a dicarboxylic acid of the formula: ##STR00113## wherein R.sup.3 is as defined above, such as optionally substituted aliphatic, saturated or unsaturated or aromatic dicarboxylic acids, such as oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), glutaric acid (pentanedioic acid), adipic acid (hexanedioic acid), pimelic acid (heptanedioic acid), suberic acid (octanedioic acid), azelaic acid (nonanedioic acid), sebacic acid (decanedioic acid), undecanedioic acid, dodecanedioic acid, brassylic acid (tridecanedioic acid), thapsic acid (hexadecanedioic acid), glutaconic acid (pent-2-enedioic acid), citraconic acid ((2Z)-2-methylbut-2-enedioic acid), mesaconic acid ((2E)-2-methyl-2-butenedioic acid), itaconic acid (2-methylidenebutanedioic acid), tartronic acid (2-hydroxypropanedioic acid), mesoxalic acid (oxopropanedioic acid), malic acid (hydroxybutanedioic acid), tartaric acid (2,3-dihydroxybutanedioic acid), oxaloacetic acid (oxobutanedioic acid), aspartic acid (2-aminobutanedioic acid), -hydroxy glutaric acid (2-hydroxypentanedioic acid), arabinaric acid (2,3,4-trihydroxypentanedioic acid), acetonedicarboxylic acid (3-oxopentanedioic acid), -ketoglutaric acid (2-oxopentanedioic acid), glutamic acid (2-aminopentanedioic acid), diaminopimelic acid ((2R,6S)-2,6-diaminoheptanedioic acid), saccharic acid ((2S,3S,4S,5R)-2,3,4,5-tetrahydroxyhexanedioic acid), phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), terepthtalic acid ((benzene-1,3-dicarboxylic acid)), diphenic acid (2-(2-carboxyphenyl)benzoic acid), 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, norbornane dicarboxylic acid, and trimellitic acid, or R.sup.3 is derived from an aliphatic or aromatic tricarboxylic acid, wherein R.sup.3 is substituted with carboxyl group (COOH), such as citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid), isocitric acid (1-hydroxypropane-1,2,3-tricarboxylic acid), aconitic acid ((cis or trans prop-1-ene-1,2,3-tricarboxylic acid), propane-1,2,3-tricarboxylic acid; trimesic acid (benzene-1,3,5-tricarboxylic acid), the reaction products of carboxylic acid anhydrides, such as maleic anhydride and succinic anhydride, with amino acids and amino acid derivatives, such as b-alanine and asparagine, i.e. N-acetyl aspartic acid, N-maleoyl--alanine ((E)-4-(2-carboxyethylamino)-4-oxo-but-2-enoic acid), N-maleoyl-asparagine (4-amino-2-[[(E)-4-hydroxy-4-oxo-but-2-enoyl]amino]-4-oxo-butanoic acid).

73. A compound according to claim 69, wherein F is selected from the group consisting of the formulas: ##STR00114## wherein the dotted line in the above formulae represents the bond to the oxygen atom, and wherein there are at least two groups F.

74. A polyorganosiloxane (A) having an average number of 2 to 1000 siloxy units selected from the siloxy groups of the formulas: ##STR00115## wherein R is selected from R.sup.1 and R.sup.F, wherein R.sup.1 is selected from organic groups bound to the silicon atoms by a carbon atom, and two groups R.sup.1 may form a bridging group between two silicone atoms, R.sup.F is selected from organic groups different from R.sup.1 and is bound to the silicon atoms by a carbon atom, and R.sup.F contains at least one functional group F selected from:
OC(O)R.sup.3C(O)OH, and
NR.sup.4C(O)R.sup.3C(O)OH, and wherein the groups F bind to a carbon atom, wherein R.sup.3 is selected from a single bond or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms, which optionally contain one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00116## and quaternary ammonium groups ##STR00117## with the proviso that R.sup.3 is not CHCH or CH.sub.2CH.sub.2, and R.sup.4 is selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from O, NH, C(O), C(S), tertiary amino groups ##STR00118## and quaternary ammonium groups ##STR00119##

Description

EXAMPLES

[0211] (The percentages refer to weight-% unless otherwise indicated).

Example 1

A Glycerol Diglycidyl Ether Based Succinic Acid Ester Derivative

[0212] In a 250 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 23.1 g (195.8 mmol) succinic acid, 122 g dipropylene glycol and 0.8 g triethylamine are mixed and heated to 90 C. 20 g (195.8 mmol epoxy groups) glycerol diglycidylether

##STR00059##

are added dropwise within 20 minutes. The mixture is kept at 90 C. for 12 hours. Afterwards, the transparent slightly yellow mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion of epoxy groups is 100%.

[0213] A product essentially consisting of the following isomers is obtained

##STR00060##

Example 2

[0214] Glycerol Diglycidylether with Three Succinic Ester Functions

[0215] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 10 g (97.9 mmol epoxy groups) of glycerol diglycidylether, 11.56 g succinic acid (97.9 mmol), 61.7 g methoxypropyl acetate and 0.53 g trimethylamine are mixed and heated to 90 C. for 15 hrs. Upon progression of the esterification reaction the mixture turns turbid. The conversion of the epoxide groups, as determined by means of .sup.1H NMR spectroscopy is 100%.

[0216] 4.9 g (48.9 mmol) succinic acid anhydride are added and the reaction continued at 90 C. for 6 hrs. Upon progression of this second esterification reaction the mixture turns transparent (slightly brownish). The conversion of the anhydride groups, as determined by means of .sup.1H NMR spectroscopy, is 100%.

[0217] 61.7 g 1,3-butanediol are added. The methoxypropyl acetate is removed under reduced pressure at 75 C./3 mm Hg.

[0218] A slightly brownish transparent liquid is obtained.

[0219] A product essentially consisting of the following isomers is obtained

##STR00061##

with R.sup.1 being OH and OC(O)CH.sub.2CH.sub.2COOH in a ratio of 2:1.

Example 3

A Glycerol Diglycidyl Ether Based Adipic Acid Ester Derivative

[0220] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 10 g (97.9 mmol epoxy groups) of glycerol diglycidylether, 14.31 g adipic acid (97.9 mmol), 56.71 g 1,3-butanediol and 0.48 g trimethylamine are mixed and heated to 90 C. for 9.5 hrs. The conversion of the epoxide groups, as determined by means of .sup.1H NMR spectroscopy is 99.5%. A colorless transparent liquid is obtained.

[0221] A product essentially consisting of the following isomers is obtained:

##STR00062##

Example 4

[0222] Glycerol Diglycidylether with Two Succinic Ester Functions and Two Adipic Acid Ester Functions

[0223] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 14.31 g adipic acid (97.9 mmol), 56.71 g methoxypropyl acetate and 0.51 g trimethylamine are mixed and heated to 70 C. 10 g (97.9 mmol epoxy groups) of glycerol diglycidylether are added during 15 minutes. The initially turbid mixture turns clear. Afterwards, the temperature is increased to 90 C. and maintained for 11 hrs.

[0224] The conversion of the epoxide groups, as determined by means of .sup.1H NMR spectroscopy is 99%.

[0225] 9.79 g (97.9 mmol) succinic acid anhydride are added and the reaction continued at 90 C. for 6.5 hrs. The conversion of the anhydride groups, as determined by means of .sup.1H NMR spectroscopy, is 98%. Upon cooling to room temperature the target product precipitates from the solution.

[0226] 79.6 g 1,3-butanediol are added. The methoxypropyl acetate is removed under reduced pressure at 75 C./3 mm Hg.

[0227] A slightly yellowish transparent liquid is obtained.

[0228] A product essentially consisting of the following isomers is obtained:

##STR00063##

with R.sub.1 being OH and OC(O)CH.sub.2CH.sub.2COOH in the ratio of 1:2.

Example 5

A Triglycerol Based Itaconic Acid Ester Derivative

[0229] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 60 g methoxypropyl acetate, 10 g (41.6 mmol) triglycerol

##STR00064##

and 0.29 g triethylamine are mixed and heated to 70 C. 9.33 g (83.2 mmol) itaconic acid anhydride are added dropwise within 15 minutes. The mixture is heated to 90 C. for 18 hours. The initially yellow dispersion turns slightly reddish during the course of the reaction. The conversion of the anhydride is determined by means of .sup.1H NMR spectroscopy. The conversion of the anhydride is 100%. Afterwards, 60 g 1,3 butanediol are added and the methoxypropyl acetate removed at 70 C./20 mbar during 2 hrs. A slightly yellow transparent solution is obtained.

[0230] A product essentially consisting of the following structure

##STR00065##

with two of the R being:

##STR00066##

[0231] (wherein the dotted line is the bond to the oxygen atom)

and three being hydrogen, is obtained.

Example 6

A Glycerol Diglycidyl Ether Based Itaconic Acid Ester Derivative

[0232] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 10.76 g (82.7 mmol) itaconic acid, 60 g 1,3 butanediol and 0.29 g triethylamine are mixed and heated to 80 C. 8.45 g (82.7 mmol epoxy groups) glycerol diglycidylether are added dropwise within 20 minutes. The temperature increased to 86 C. It is further increased to 90 C. and kept there for 14 hours. Afterwards, the transparent colorless mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion of epoxy groups is 100%.

[0233] A product essentially consisting of the following isomers is obtained:

##STR00067##

with R.sub.1

##STR00068##

[0234] (wherein the dotted line is the bond to the oxygen atom).

Application Tests

Test Method

[0235] Test method for evaluation of the color retention is described in detail in US 2011/0219552 A1. The method determines the hair color changes before and after washes by Delta E. Color changes were measured by measuring CIE L*, a* and b* values (or CIELAB color space) on a HunterLab colorimeter.

[0236] The meaning of L*, a*, b* was elaborated in Practical Modern Hair Science Trefor Evans and R. Randall Wichett, Alluredbooks, Carol Stream, Ill., 2012. The L* value measures the lightness from L*=0 (black) to L*=100 (white). The color is measured by a* from negative value (green) to positive value (red) and b* from negative value (blue) to positive value (yellow). For example, a medium blonde has an L*, a*, b* value of L*=49, a*=12, b*=26 and a medium auburn has an L*, a*, b* value of L*=26, a*=13, b*=12. Delta E was calculated using the following equation to evaluate color change before and after washes.

Delta E=((L.sub.t*L.sub.0*).sup.2+(a.sub.t*a.sub.0*).sup.2+(b.sub.t*b.sub.0*).sup.2).sup.1/2

[0237] Where L.sub.0*, a.sub.0*, b.sub.0*, and L.sub.t*, a.sub.t*, b.sub.t* are measured CIE L*, a*, b* color parameters (or CIELAB color space) before and after washing, respectively.

[0238] The larger value of Delta E reflects greater change of color, so smaller Delta E is desired because it indicates less color loss after washing.

[0239] Similarly, color enhancement was calculated using the following equation to evaluate initial color depth increase with treatment.

Delta E=((L.sub.2*L.sub.1*).sup.2+(a.sub.2*a.sub.1*).sup.2+(b.sub.2*b.sub.1*).sup.2).sup.1/2

[0240] Where L.sub.2*, a.sub.2*, b.sub.2*, and L.sub.1*, a.sub.1*, b.sub.1* are measured CIE L*, a*, b* before washing color parameters with and without treatment respectively. Here larger Delta E is desired because it means more initial color enhancement.

Example 7

Example 7.1 Application on Color Enhancement and Color Retention of Single Bleached European Hair

[0241] The following treatment solution was prepared:

[0242] TS1 solution (polyglycerol succinic ester from example 1) approximately 50 ml was composed 3 g of the polyglycerol succinic ester from example 1, 7 g dipropylene glycol (that is 10 g solution of the polyglycerol succinic ester in dipropylene glycol obtained in example 1), and 40 g water.

[0243] The hair dye was a commercial hair dye Garnier Nutrisse Ultra Color R3, Light Intense Auburn, from L'Oreal.

Pre-Treatment with Aqueous Solution According to the Invention Before Dyeing of Hair

[0244] A bundle of 4 g single bleached European hair tress (Kerling International Haarfarbrik GMBH) was immersed in 50 g TS1 solution for 30 minutes. Then the hair was dried at room temperature overnight. The hair bundle was then washed by 10 wt-% SLES (Sodium Lauryl Ether Sulfate) for 3 times. Hair was dried and then dyed with Garnier R3 dye for 30 minutes following the standard dyeing procedure of Garnier R3.

[0245] The control tress was the tress treated by 50 ml water. And then washed with 10 wt-% SLES and dyed with Garnier R3 dye same as hair tress treated by crosslinking technology. The initial color was measured.

Post-Treatment with Aqueous Solution According to the Invention after Dyeing of Hair

[0246] A bundle of 4 g single bleached European hair tress (Kerling International Haarfarbrik GMBH) dyed with Garnier R3 dye for 30 minutes following the standard dyeing procedure of Garnier R3. Then the hair was dried by bonnet. The initial color was measured. The dried hair was immersed in 50 g TS1 solution for 30 minutes. Then the hair was dried at room temperature overnight. The hair bundle was then washed by 10 wt-% SLES (Sodium Lauryl Ether Sulfate) for 3 times. Hair was then dried.

[0247] The control tress was Garnier R3 dyed tress treated by 50 ml water. The hair was then washed with 10 wt-% SLES and dried same as hair tress treated by crosslinking technology.

Wash Protocol

[0248] The 4 g hair tresses were put in 250 ml conical flask with 200 ml 2.5% SLES solution. The flask was shaked at 120 rpm 42 C. in Shel Lab shaking water bath for 5 minutes, (5 minutes wash equals 10 hand washes.) After 5 minutes, the hair was dried and the hair color was measured.

Pre-Treatment Benefits

Color Enhancement Delta E for Pre-Treatment

[0249]

TABLE-US-00002 Color Initial Color L*, a*, b* Enhancement L* a* b* Delta E Control 24.15 27.03 15.14 TS1 (polyglycerol succinic 22.75 19.31 9.27 9.88 ester from example 1)

[0250] The hair treated by the technology according to the invention before dyeing shows a color enhancement effect with darker initial color compared to the control.

Color Retention Benefit for Pre-Treatment

[0251]

TABLE-US-00003 Color Loss Delta E Control 12.50 TS1 ((polyglycerol succinic 7.20 ester from example 1)

[0252] The technology according to the invention (TS1 solution (polyglycerol succinic ester from example 1)) shows a color retention effect with lower color loss Delta E than for the control.

Post-Treatment Benefits

[0253] Post-treatment by polyglycerol succinic ester from example 1 kept the original color darkness with almost no change in L*.

TABLE-US-00004 Initial Color L*, a*, b* L* a* b* Hair without treatment 24.15 27.03 15.14 TS1 (polyglycerol succinic 24.46 21.7 11.12 ester from example 1)

Color Retention Benefit for Post-Treatment

[0254]

TABLE-US-00005 Color Loss Delta E Control 17.91 TS1 (polyglycerol succinic 5.28 ester from example 1)
shows a color retention effect with lower color loss Delta E than for the control.

[0255] Post-treatment by the technology according to the invention (TS1 solution (polyglycerol succinic ester from example 1)) reduced the color loss Delta E by more than 12 units.

Example 7.2 Post Bleach Treatment

[0256] 4 gram undamaged Dark brown hair tresses were obtained from Hair International Importers. A commercial bleaching lightener powder (9 grams) and a commercial 40 volume developer (11 grams) were mixed together. The bleaching composition was applied to the virgin dark brown hair tress, spread through and left on the hair tress for 50 min. After rinsing the dye from the tress with tap water, the tress was washed with a 10 wt % Sodium Laureth Sulfate (2 EO) solution and rinsed. The dried hair was immersed in 50 g TS1 solution for 30 minutes. Then the hair was dried at room temperature overnight. The hair bundle was then washed by 10 wt-% SLES (Sodium Lauryl Ether Sulfate) for 3 times. Hair was then dried.

[0257] This treatment is to strengthen the hair after bleaching.

Example 7.3: White Rinse Off Conditioner Formulation

[0258]

TABLE-US-00006 Part Chemical Name wt % A Water q.s. to 100 Lactic Acid 0.6 B Amidet APA-22 (Behenamidopropyl 2.2 Dimethylamine) from Kao Corporation C Kalcol 6850 (Cetostearyl alcohol) from 4.4 Kao Corporation D polyglycerol succinic ester from 7 example 1 30% solution in dipropylene glycol

[0259] 1. Part A. Lactic acid and water were mixed and heated to 80 C.

[0260] 2. Part B was added to part A and the mixture stirred for 1-3 hours at 80 C. to provide a homogeneous formulation.

[0261] 3. Part C was added to the mixture of A and B and stirred at 80 C. for 0.5 to 1 hour until Part C was completely molten and a homogeneous mixture was obtained.

[0262] 4. The heating source was removed while stirring continued until room temperature was reached.

[0263] 5. Part D was added to the mixture consisting of A+B+C and stirring continued until a homogeneous mixture was reached.

Example 7.4. Pearlescent Shampoo Formulation

[0264]

TABLE-US-00007 Part Component wt % A Sodium Laureth Sulfate 12 Cocamidopropyl Betaine 3 B Ethylene Glycol Distearate 1 Water 10 C Cocamide Monoethanolamide 1 Water 10 D Polyquaternium-6 0.06 ACULYN 38 from the Dow Chemical 3 Company (10 wt-% active) E polyglycerol succinic ester from example 7 1 30% solution in dipropylene glycol F Water q.s. to 100

[0265] Part A: The components of part A were mixed with an overhead mechanical stirrer at 600 rpm for 10 minutes.

[0266] Part B: 1 g ethylene glycol distearate and 10 g water were mixed with a magnetic stirrer at 200 rpm for 15 minutes.

[0267] Part C: 1 g cocamide monoethanolamide and 10 g water were mixed with a magnetic stirrer at 200 rpm for 15 minutes.

[0268] The components of part D were added to part A and stirred with an overhead mechanical stirrer at 600 rpm for 10 minutes. A mixture A+D was obtained.

[0269] Part B was added to the mixture A+D and stirred for 10 minutes at 600 rpm with a mechanical stirrer. Mixture A+D+B was obtained.

[0270] Part C was added to the mixture A+D+B and stirred for 10 minutes at 600 rpm with a mechanical stirrer. Mixture A+D+B+C was obtained.

[0271] Part E was added to the mixture A+D+B+C and stirred for 15 minutes at 600 rpm with a mechanical stirrer. Mixture A+D+B+C+E was obtained.

[0272] Part F was added last to the mixture A+D+B+C+E and the mixture stirred for 15 minutes at 600 rpm with a mechanical stirrer.

Example 7.5: Pearlescent Shampoo Non-Sulfate Version

[0273]

TABLE-US-00008 Part Component Wt % A Sodium Lauryl Sulfoacetate + 10.6 Disodium Laureth Sulfosuccinate Cetyl Betaine 3.3 B Cocamide Monoethanolamide 1.5 Water 10 C Hydroxypropyl Methylcellulose 1.5 Water 10 D Ethylene Glycol Distearate 1.5 Water 10 E Polyquaternium-10 0.15 F polyglycerol succinic ester from example 7 1 30% solution in dipropylene glycol G Water q.s. to 100

[0274] Part A: The components of part A were mixed with an overhead mechanical stirrer at 600 rpm for 10 minutes.

[0275] Part B: 1.5 g cocamide monoethanolamide was mixed with 10 g water (45 C.) with a magnetic stirrer at 200 rpm for 30 minutes.

[0276] Part C: 1.5 g hydroxypropyl methylcellulose powder was slowly added to 10 g water (45 C.) and stirred with a magnetic stirrer at 200 rpm for 30 minutes.

[0277] Part D: 1.5 g ethylene glycol distearate powder was slowly added to 10 g water (45 C.) and stirred with a magnetic stirrer at 200 rpm for 30 minutes.

[0278] Part B was slowly added to part A with mechanical stirring at 600 rpm for 5 minutes. Mixture A+B was obtained.

[0279] Part C was slowly added to part A+B with mechanical stirring at 600 rpm for 5 minutes. Mixture A+B+C was obtained.

[0280] Part D was slowly added to part A+B+C with mechanical stirring at 600 rpm for 5 minutes. Mixture A+B+C+D was obtained.

[0281] Part E was added to part A+B+C+D with mechanical stirring at 600 rpm for 10 minutes. Mixture A+B+C+D+E was obtained.

[0282] Part F was added to the mixture A+B+C+D+E and mechanically stirred for 15 minutes at 600 rpm.

[0283] Finally, Part G was added and the mixture stirred at 600 rpm for 30 minutes.

Example 7.6: Anti-Frizz Shampoo

[0284]

TABLE-US-00009 Part Component wt % A Water 55 PEG-120 Methyl Glucose Dioleate 2 B Water 15.25 Sodium Laureth Sulfate 9 C Dissodium EDTA 0.1 Cocamidopropyl Betaine 10 Polyquaternium-7 0.5 Decyl Glucoside 1 Dexpanthenol 1 Phenoxyethanol 0.5 D polyglycerol succinic ester from example 7 1 30% solution in dipropylene glycol Tropicalism 18 from Givaudan S.A. 0.65

[0285] Part A: The components of part A were mixed with a magnetic stirrer at 200 rpm for 15 minutes.

[0286] Part B: The components of part B were mixed with a magnetic stirrer at 200 rpm for 15 minutes.

[0287] Part B was added to part A and the mixture stirred with an overhead mechanical stirrer at 500 rpm for 15 minutes.

[0288] The Components of part C were added to the mixture A+B and stirred with an overhead mechanical stirrer at 500 rpm for 1 hour.

[0289] The components of part D were mixed with a magnetic stirrer at 200 rpm for 15 minutes and afterwards added to the mixture A+B+C.

[0290] Finally, the complete mixture A+B+C+D was mixed with a mechanical stirrer at 500 rpm for 30 minutes.

Example 7.7: Water Based Spray Formulation

[0291] 1.5 wt % polyglycerol succinic ester from example 1
3.5 wt % dipropylene glycol,

1.25 wt % SLES,

[0292] 0.09 wt % NaOH (added as a 10 wt % active NaOH solution in water of pH 8)

Water q.s. to 100 wt %

Example 7.8: Isopropanol (IPA) Based Spray Formulation

[0293] 1.5 wt % polyglycerol succinic ester from example 1
3.5 wt % dipropylene glycol

IPA q.s. to 100%

Example 8: Treatment Gel and Cream Formulations

Example 8.1

[0294]

TABLE-US-00010 Formulation 1 2 3 4 5 Ingredients Wt % wt Wt % Wt % Wt % Carbopol 1382 1 1 Xanthan gum 0.1 0.1 0.5 Hydroxypropyl starch 4 phosphate Hydroxyethyl cellulose 1 polyglycerol succinic 10 10 10 10 5 ester from example 1 Dipropylene glycol 30 Butylene glycol 30 30 isopropanol 25 25 25 water q.s 100 q.s 100 q.s 100 q.s 100 q.s 100 NaOH 10% q.s pH 4 q.s pH 7 q.s pH 6.5 q.s pH 6.5 q.s pH 6.5

Example 8.2

[0295]

TABLE-US-00011 Ingredients Wt % Phospholipids (and) glycine soja oil 2 propanediol 3 polyglycerol succinic ester from example 1 10 Sodium acrylates copolymer and lecithin 1.7 Stearic acid 0.5 Behenyl alcohol 0.5 Isononyl isononaote 2 Glycerin and picea abies extract and alcohol 1 phenoxyethanol 0.5 Butylene glycol dicaprylate/dicaprate 2 water q.s to 100

Example 9

A Glycerol Diglycidyl Ether Based Tartaric Acid Ester Derivative

[0296] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 15 g (146.9 mmol epoxy groups) of glycerol diglycidylether, 22.05 g (146.9 mmol) tartaric acid, 0.56 g trimethylamine and 86.45 g dipropylene glycol are mixed and heated to 90 C. for 12 hrs. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is 100%.

[0297] A colorless product essentially consisting of the following isomers:

##STR00069##

with
R.sub.1 being OC(O)CH(OH)CH(OH)C(O)OH
is obtained.

Example 10

Glycerol Dig Lycidyl Ether Based N-Acetyl Aspartic Acid Ester Derivative

[0298] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 5 g (48.9 mmol epoxy groups) of glycerol diglycidylether, 8.58 g (48.9 mmol) N-acetyl aspartic acid:

##STR00070##

0.2 g trimethylamine and 54.3 g 1,3-butanediol are mixed and heated to 90 C. for 10 hrs. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is 100%.

[0299] A slightly yellowish product essentially consisting of the following isomers is obtained:

##STR00071##

with
R.sub.1 being OC(O)CH.sub.2CH(R*)C(O)OH or OC(O)CH(R*)CH.sub.2C(O)OH, wherein

R*NH(CO)CH.SUB.3..

Example 11

N-Maleoyl--alanine ((E)-4-(2-carboxyethylamino)-4-oxo-but-2-enoic acid)

[0300] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 17.8 g (200 mmol) of -alanine are dissolved in 40 g DI water at room temperature. 19.6 g (200 mmol) of maleic acid anhydride are added. The temperature increases from 22 to 36 C. within 20 minutes. The mixture turns into a turbid white dispersion. The temperature is adjusted at 22 C. for 3 hrs. Afterwards, the precipitate is filtered, washed 10 with 20 ml DI water and 3 with 20 ml cyclohexane. Finally, the volatiles are removed at 40 C./20 mm Hg. The structure of the material was confirmed by means of .sup.1H NMR spectroscopy.

[0301] 22 g of a white powder essentially consisting of the following structure are obtained.

N-Maleoyl--alanine ((E)-4-(2-carboxyethylamino)-4-oxo-but-2-enoic acid)

[0302] ##STR00072##

Example 12

Glycerol Diglycidyl Ether Based Derivative of N-Maleoyl -Alanine

[0303] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 10 g (53.4 mmol) of the N-maleoyl -alanine according to example 11, 60 g 1,3-butanediol and 0.23 g trimethylamine are mixed at room temperature and heated to 70 C. 5.45 g (53.4 mmol epoxy groups) of glycerol diglycidylether are added. The mixture is heated to 90 C. for 12 hrs. The mixture turns transparent during the heating process. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is 100%.

[0304] A reddish product essentially consisting of the following isomers is obtained:

##STR00073##

with
R.sub.1 being OC(O)CHCHC(O)NHCH.sub.2CH.sub.2C(O)OH or OC(O)CH.sub.2CH.sub.2NHC(O)CHCHC(O)OH.

Example 13

N-Maleoyl-asparagine (4-amino-2-[[(E)-4-hydroxy-4-oxo-but-2-enoyl]amino]-4-oxo-butanoic acid)

[0305] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 26.42 g (200 mmol) of asparagine are dispersed in 46 g DI water at room temperature. 19.6 g (200 mmol) of maleic acid anhydride are added. The mixture forms a white dispersion which is stirred at 23 C. for 5 hrs. Afterwards, the mixture is heated to 50 C. for 5.5 hrs. It forms a transparent solution. Volatiles are removed at 45 C./20 mm Hg. The sticky residue is twice washed with 2-propanol and volatile components removed at 45 C./20 mmHg. The structure of the material was confirmed by means of .sup.1H NMR spectroscopy.

[0306] A colorless candy like material essentially consisting of the following structure is obtained

##STR00074##

Example 14

Glycerol Diglycidyl Ether Based Derivative of N-Maleoyl Asparagine

[0307] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 12.29 g (53.4 mmol) of the N-maleoyl asparagine according to example 13, 60 g 1,3-butanediol and 0.27 g trimethylamine are mixed at room temperature and heated to 70 C. 5.45 g (53.4 mmol epoxy groups) of glycerol diglycidylether are added. The mixture is heated to 90 C. for 12 hrs. A white dispersion is formed during the heating process. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is >99%.

[0308] A white dispersion essentially consisting of the following isomers is obtained:

##STR00075##

with
R.sub.1 being OC(O)CHCHC(O)NHCH(CH.sub.2C(O)NH.sub.2)C(O)OH or OC(O)CH(CH.sub.2C(O)NH.sub.2)NHC(O)CHCHC(O)OH.

[0309] The material is instantaneously soluble in DI water.

APPLICATIONS EXAMPLES

Example 15

Application on Color Enhancement and Color Retention of Single Bleached European Hair

[0310] The following treatment solution was prepared:

[0311] TS2 solution (glycerol diglycidyl ether based tartaric acid ester derivative from example 9) approximately 50 ml was composed of the glycerol diglycidyl ether based tartaric acid ester from example 9 3 g, 7 g 1,3 butanediol (that is 10 g solution of the glycerol diglycidyl ether based tartaric acid ester in 1,3 butanediol obtained in example 9), and 40 g water.

[0312] TS3 solution (glycerol diglycidyl ether based N-acetyl aspartic acid ester derivative from Example 10) approximately 50 ml was composed of the glycerol diglycidyl ether based N-acetyl aspartic acid ester from example 10 3 g, 12 g 1,3 butanediol (that is 15 g solution of the glycerol diglycidyl ether based tartaric acid ester in 1,3 butanediol obtained in example 10), and 35 g water.

[0313] TS4 solution (glycerol diglycidyl ether based derivative of N-maleoyl -alanine from Example 12) approximately 50 ml was composed of the glycerol diglycidyl ether based derivative of N-maleoyl -alanine from example 12 3 g, 12 g 1,3 butanediol (that is 15 g solution of the glycerol diglycidyl ether based derivative of N-maleoyl -alanine in 1,3 butanediol obtained in example 12), and 35 g water.

[0314] The hair dye was a commercial hair dye Garnier Nutrisse Ultra Color R3, Light Intense Auburn, from L'Oreal.

Post-Treatment with the Aqueous Solution According to Invention after the Dyeing Step

[0315] A bundle of 4 g single bleached European hair tress (Kerling International Haarfarbrik GmbH) dyed with Garnier R3 dye for 30 minutes following the standard dyeing procedure of Garnier R3. Then the hair was dried by bonnet. The initial color was measured. The dried hair was immersed in 50 g TS2 solution or TS3 solution or TS4 solution for 30 minutes. Then the hair was dried at room temperature overnight. The hair bundle was then washed by 10 wt-% SLES (Sodium Lauryl Ether Sulfate) for 3 times. Hair was then dried.

[0316] The control tress was Garnier R3 dyed tress treated by 50 ml water. The hair was then washed with 10 wt-% SLES and dried same as hair tress treated by crosslinking technology.

Wash Protocol

[0317] The 4 g hair tresses were put in 250 ml conical flask with 200 ml 2.5% SLES solution. The flask was shaken at 120 rpm 42 C. in Shel Lab shaking water bath for 5 minutes, (5 minutes wash equals 10 hand washes.) After 5 minutes, the hair was dried and the hair color was measured.

Post-Treatment Benefits

Color Enhancement (Deepening) for the TS2 Post-Treatment

[0318]

TABLE-US-00012 Before Wash Color Color L*, a*, b* Enhancement L* a* b* Delta E Before Treatment of TS2 26.74 29.75 17.74 After TS2 Treatment (glycerol 23.62 15.20 6.70 18.53 diglycidyl ether based tartaric acid ester derivative from example 9)

[0319] TS2 notably deepens the hair color tone upon a post-treatment protocol.

[0320] The TS3 and TS4 treatments do not deepen the color tone.

TABLE-US-00013 Before Wash Color L*, a*, b* L* a* b* Before Treatment of TS3 26.83 30.23 18.18 After TS3 Treatment (glycerol 27.33 24.78 14.27 diglycidyl ether based N-acetyl aspartic acid ester derivative from Example 10) Before Treatment of TS4 26.89 30.08 18.16 After TS4 Treatment (glycerol 28.29 26.45 15.42 diglycidyl ether based derivative of N-maleoyl -alanine from Example 12)

Color Retention Benefit for Post-Treatment

[0321]

TABLE-US-00014 Color Loss Delta E Control 17.91 TS2 (glycerol diglycidyl ether 10.35 based tartaric acid ester derivative from example 9) TS3 (glycerol diglycidyl ether 7.73 based N-acetyl aspartic acid ester derivative from Example 10) TS4 (glycerol diglycidyl ether 7.93 based derivative of N-maleoyl -alanine from Example 12)

[0322] The above table on the post-treatment results shows that TS2, TS3 and TS4 provide significant and visible color loss benefits over the control. While TS3 and TS4 provided color loss Delta E improvements of about 10 against the control, TS2 provided a color loss Delta E improvement of about 7.5.

Example 16

A Silicone Based Tartaric Acid Ester Derivative (Terminal)

[0323] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 15 g (39.7 mmol epoxy groups) of a silicone diepoxide of the structure

##STR00076##

5.96 g (39.7 mmol) tartaric acid, 0.31 g trimethylamine and 48.9 g 1,3-butanediol are mixed at room temperature under N.sub.2. The mixture is heated to 90 C. for 11 hours. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is 99%.

[0324] A colorless product essentially consisting of the following structure is obtained:

##STR00077##

with
x=5.3, and
R being OC(O)CH(OH)CH(OH)C(O)OH.

Example 17

A Silicone Based N-Acetyl Aspartic Acid Ester Derivative

[0325] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 10 g (26.5 mmol epoxy groups) of a silicone diepoxide of the structure

##STR00078##

4.64 g (26.5 mmol)N-acetyl aspartic acid, 0.22 g trimethylamine and 58.6 g 1,3-butanediol are mixed at room temperature under N.sub.2. The mixture is heated to 90 C. for 10 hours. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is 100%.

[0326] A brownish product essentially consisting of the following structure is obtained:

##STR00079##

with
x=5.3, and
R being OC(O)CH.sub.2CH(R*)C(O)OH or OC(O)CH(R*)CH.sub.2C(O)OH, wherein

R*NH(CO)CH.SUB.3..

Example 18

A Silicone Based Derivative of N-Maleoyl -Alanine

[0327] In a 100 ml three-necked flask, equipped with refluxing condenser, thermometer and magnetic stirrer, 10 g (26.5 mmol epoxy groups) of a silicone diepoxide of the structure

##STR00080##

4.95 g (26.5 mmol)N-maleoyl -alanine according to example 11, 0.23 g trimethylamine and 60 g 1,3-butanediol are mixed at room temperature under N.sub.2. The mixture is heated to 90 C. for 12 hours. Afterwards, the mixture is cooled to room temperature and the conversion of the epoxide groups determined by means of .sup.1H NMR spectroscopy. The conversion epoxy groups is 100%.

[0328] A reddish product essentially consisting of the following structure is obtained

##STR00081##

with
x=5.3 and
R being OC(O)CHCHC(O)NHCH.sub.2CH.sub.2C(O)OH or OC(O)CH.sub.2CH.sub.2NHC(O)CHCHC(O)OH.