USE OF POLYHYDROXYAROMATIC COMPOUNDS FOR THE TREATMENT OF FIBROUS AMINO ACID BASED SUBSTRATES

Abstract

This invention relates to the use of polyhydroxyaromatic compounds for the treatment of fibrous amino acid based substrates, preferred hair, new polyhydroxyaromatic compounds, aqueous compositions comprising the polyhydroxyaromatic compounds, cosmetic compositions comprising the polyhydroxyaromatic compounds, in particular hair care compositions, and a process for the treatment of hair comprising the use of said cosmetic compositions.

Claims

1-42. (canceled)

43. A method for the treatment of fibrous amino acid based substrates, preferable hair, which comprises the step of applying of compound of the formula:
R.sup.2(—F).sub.2-6 wherein R.sup.2 is selected from divalent to hexavalent aliphatic hydrocarbyl radicals, derived from the groups consisting of ethylene oxide-, propylene oxide- and/or butylene oxide-based polyethers, oligoglycerols, diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidylether, and F is selected from selected from:
—O—C(O)—R.sup.3—R.sup.4, and the groups F bind to a carbon atom of R.sup.2, R.sup.3 is selected from a single bond R.sup.4 is selected from the group consisting of di- and trihydroxy-substituted aromatic groups, for the treatment of fibrous amino acid-based substrates.

44. The method of claim 43, wherein R.sup.4 is selected from the group consisting of dihydroxyphenyl groups, such as 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl, and 3,5-dihydroxyphenyl, trihydroxyphenyl groups, such as 2,3,4-trihydroxyphenyl, 2,3,5-trihydroxyphenyl, 2,3,6-trihydroxyphenyl, 2,4,5-trihydroxyphenyl, 2,4,6-trihydroxyphenyl, and 3,4,5-trihydroxyphenyl, dihydroxynaphthyl groups, such as 6,7-dihydroxynaphthyl, 5,6-dihydroxynaphthyl, 1,7-dihydroxynaphthyl, 3,7-dihydroxynaphthyl, 1,3-dihydroxynaphthyl, and 1,4-dihydroxynaphthyl, and trihydroxynaphthyl groups, such as 4,6,7-trihydroxynaphthyl, and 1,5,6-trihydroxynaphthyl.

45. The method of claim 43, wherein R.sup.4 is 3,4,5-trihydroxyphenyl.

46. The method of claim 43, wherein R.sup.2 is derived from polyethylene glycols, polypropylene glycols, I mixed ethylene oxide and butylene oxide based copolyethers, mixed propylene oxide and butylene oxide based copolyethers, and mixed ethylene oxide and propylene oxide and butylene oxide based copolyethers, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, and the statistically distributed oligomeric condensation products of glycerol,

47. The method of claim 43, wherein R.sup.2 is derived from polyalkylene oxy groups 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, r1=0 to 32, s1=0 to 24, q2=0 or 1, r2=0 or 1, s2=0 or 1, and ρ(q2+r2+s2)=1, with the proviso that the sum of the carbon atoms in such polyalkylene oxide groups is 2 to 100, and oligoglycerols of the general formula:
[CH.sub.2CH(R.sup.7)CH.sub.2O].sub.t1—[CH.sub.2CH(R.sup.7)CH.sub.2)].sub.t2— with t1=0 to 32, t2=1, R.sup.7═OH or F, wherein F is as defined above, with the proviso that the sum of the carbon atoms is 2 to 100.

48. The method of claim 43, wherein R.sup.2 contains one or more groups —O—, and is substituted by one or more hydroxyl groups.

49. The method of claim 43, wherein the compound has the formula: ##STR00038## 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.

50. The method of claim 43, wherein the compound has the formula: ##STR00039## wherein one of R.sup.6 is hydroxy and one of R.sup.6 is a group of the formula ##STR00040## wherein F is as defined above and the dotted line is the bond to the carbon atom.

51. The method of claim 43, wherein the compound is a mixture of the following two isomers: ##STR00041## wherein F is as defined above.

52. The method of claim 43, wherein the compound has the formula: ##STR00042## herein x is from 1 to 10, preferably 1 to 5, and F is as defined above.

53. A compound of the formula:
R.sup.2(—F).sub.2-6 wherein R.sup.2 is selected from divalent to hexavalent aliphatic hydrocarbon radicals derived from the group consisting of ethylene oxide-, propylene oxide- and/or butylene oxide-based polyethers, oligoglycerols, diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidylether, and F is selected from selected from:
—O—C(O)—R.sup.3—R.sup.4, and the groups F bind to a carbon atom of R.sup.2, and wherein R.sup.3 is selected from a single bond, and R.sup.4 is selected from the group consisting of di- and trihydroxy-substituted aromatic groups.

54. A compound according to claim 53, which has the formula: ##STR00043## 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.

55. A compound according to claim 53, wherein the compound has the formula: ##STR00044## wherein one of R.sup.6 is hydroxy and one of R.sup.6 is a group of the formula ##STR00045## wherein F is as defined above and the dotted line is the bond to the carbon atom.

56. A compound according to claim 53, wherein the compound is a mixture of the following two isomers: ##STR00046## wherein F is as defined above.

57. A compound according to claim 53, wherein the compound has the formula: ##STR00047## herein x is from 1 to 10, preferably 1 to 5, and F is as defined above.

58. An aqueous composition comprising the compound according to claim 53.

59. An aqueous composition according to claim 58 comprising at least one further component selected from the group consisting of surfactants, and metal salts.

60. The aqueous composition according to claim 59, comprising at least one surfactant.

61. The aqueous composition according to claim 59, wherein the weight ratio of said surfactant and/or metal salt to said inventive compound is at least 0.06.

62. The aqueous composition according to claim 59, comprising 0.05 to 30%, of said compound, wherein the percentage is per weight based on the total weight of the aqueous composition.

63. The aqueous composition according to claim 59, wherein the surfactant 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.

64. The aqueous composition according to claim 59, wherein the surfactant is selected from hydrocarbon-based or silicone-based emulsifiers.

65. The aqueous composition according to claim 59, wherein the surfactant is present in an amount of from about 0.05% to about 15%, by weight of the aqueous composition.

66. The aqueous composition according to claim 58, further comprising at least one additional additive, selected from the group consisting of a) organic diluents or solvents, b) proteins, c) emollients or fatty substances, d) preservatives, e) skin protecting ingredients, f) 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, fillers, nacres, colorants, and mixtures thereof, with the proviso that oxidizing agents and reducing agents are not present simultaneously in a given composition.

67. The aqueous composition according to claim 58 having the composition: TABLE-US-00005 Ingredient Weight-% at least one compound as defined in claim 1. 0.05 to 30 hydrocarbon or silicone based surfactant 0 to 15 water q.s. to add to 100 diluents/solvents 0 to 95, protein, 0 to 15, emollients/fatty substance 0 to 15, preservatives 0 to 5, skin protecting ingredients 0 to 15, conditioning agents 0 to 15, oxidizing agents 0 to 15, reducing agents 0 to 15, tannins 0 to 15, metal salts, such iron or zinc salts, 0 to 15, hair dyeing agent 0 to 15, further auxiliary agents 0 to 15, wherein the wt-percentages relate to the complete weight of the aqueous composition.

68. A cosmetic composition comprising at least one compound as defined in claim 43.

69. A cosmetic composition according to claim 68, which is a hair treatment composition.

70. A cosmetic composition according to claim 69, which is selected from the group consisting of a hair shampoo composition, hair care composition, hair conditioning composition, hair strengthening composition, hair coloration or dyeing composition, hair combability improving composition, anti-frizz composition, hair rinse-off and leave-on compositions.

71. A process for the treatment of hair which comprises the steps of providing a cosmetic composition according to claim 69, and applying said cosmetic composition to said hair.

72. A process for the treatment of hair according to claim 71, which further comprises the step of dyeing the hair.

73. A process for the treatment of hair which comprises the steps of contacting the hair with the cosmetic composition according to claim 68, optionally contacting the hair with a composition containing a metal salt of Fe and/or Zn, and drying the hair.

74. A method for the treatment of fibrous amino acid based substrates comprising contacting the fibrous amino acid based substrate with the aqueous composition of claim 58.

75. The method of claim 74 wherein the method is for at least one of strengthening of hair, for hair color retention, for hair color enhancement, for hair color protection, for shaping of hair, i.e. the curling and straightening of hair, for hair conditioning, for hair smoothening or softening, for improving manageability of the hair.

Description

EXAMPLES

Example 1

[0212] Synthesis of a Glycerol Diglycidyl Ether Based Gallic Acid Derivative

[0213] 54.1 g 1,3-butandediol, 15 g (0.088 mol —COOH) gallic acid and 0.46 g trimethylamine were mixed at room temperature and heated to 70° C. 8.18 g (0.080 mol epoxy groups) glycerol diglycidyl ether

##STR00031##

were added dropwise during 30 minutes. The mixture was heated to 90° C. for 12 hrs.The conversion on epoxy groups was 100% (1H-NMR).

[0214] A slightly yellowish transparent liquid containing the product essentially consisting of the following structure is obtained

##STR00032##

[0215] with

[0216] R.sub.1═

##STR00033##

[0217] and R2 is —OH or

##STR00034##

[0218] in a ratio 1:1.

Example 2

[0219] Synthesis of a Propylene Glycol Based Gallic Acid Derivative

[0220] 56.86 g 1,3-butandediol, 8.95 g (0.0526 mol —COOH) gallic acid and 0.28 g trimethylamine were mixed at room temperature and heated to 70° C. 10 g (0.0526 mol epoxy groups) of a glycidyl modified oligopropylene glycol derivative of the structure

##STR00035##

were added dropwise during 1 hr. The mixture was heated to 90° C. for 14 hrs.The conversion on epoxy groups was 100% (1H-NMR).

[0221] A yellowish transparent liquid containing the product essentially consisting of the following structure is obtained

##STR00036##

with R.sub.1′

##STR00037##

[0222] Applications

[0223] Measurement Methods:

[0224] Test Method for Measuring Color and Color Retention of Hair Dyes The test method for evaluation of the color retention is described in detail in US 2011/0219552 A1. The method determines the change in hair color (Delta E) before and after washing the hair. The color changes were determined by measuring the Hunter L, a and b values on a HunterLab colorimeter before and after washing the color treated hair tress. 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.sub.w=((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

[0225] Where L.sub.0, a.sub.0, b.sub.0, (initial color parameters) and L.sub.t, a.sub.t, b.sub.t (color parameters after washing) are measured Hunter L, a, b color parameters. The larger value of Delta E the greater change of color, so smaller Delta E is desired because it indicates less color loss after washing. Similarly, color enhancement was calculated using the following equation to evaluate initial color depth increase with treatment.

Delta E.sub.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

[0226] Where L.sub.2, a.sub.2, b.sub.2,(color parameters for treated colored hair) and L.sub.1, a.sub.1, b.sub.1 (color parameters for untreated colored hair) are measured without washing. Here a larger Delta E is desired because it means more initial color enhancement.

Example 3

Creamy Shampoo

[0227]

TABLE-US-00002 S. No INGREDIENTS % w/w Phase A 1 De-mineralized Water 21.75 2 Disodium EDTA 0.05 3 Carbopol ® Aqua SF-1 Polymer 6.5 4 Galaxy LES 45 Phase B 5 Triethanolamine 2 Phase C 6 Galaxy CAPB 5 7 Monemide TM CM 1 Phase D 8 Ginol 16 0.5 9 Galaxy 610 1.5 Phase E 10  Demineralized water 10 11  Jaguar C13S 0.1 Phase F 12  Merquat ™ 100 Polymer 0.5 13  Euxyl ® PE 9010 0.4 14  Sodium Chloride 0.7 Phase G 15  gallic acid derivative of example 2 5

[0228] Procedure: [0229] 1. In the main vessel prepare phase A: Dissolve Disodium EDTA in deionized water, add Carbopol Aqua SF-1 polymer and mix gently, add Galaxy LES and mix gently, [0230] 2. Neutralize the phase A with phase B up to pH 6.6 to 7.2 [0231] 3. Add phase C in to phase AB and mix well [0232] 4. Heat the batch up to 80° C., [0233] 5. Add phase D ingredients, and mix well at 80° C. until uniform dispersion. [0234] 6. Cool the batch up to 45° C. under stirring. [0235] 7. Premix phase E in a separate vessel (use warm water for the dispersion) [0236] 8. Add phase E to phase ABCD and mix well. [0237] 9. Add phase F ingredients as per given order, mix well after each addition. [0238] 10. Finally add phase G mix well & store in a container.

[0239] Application of Creamy Shampoo on the Dyed Hairs.

[0240] Single bleached platinum hair tresses from International hair importers were dyed using Garnier Red 6.6. Afterwards, washed and dried hair tresses were divided into two-halfs. One half was washed with the creamy shampoo containing the material according to example 2 whereas the other half was washed with the control shampoo (without the inventive additive). After drying, hair tresses ΔE values were recorded.

[0241] The above process was repeated six times.

TABLE-US-00003 ΔE ΔE No. of wash creamy shampoo containing Control shampoo without the cycles the compound of example 2 compound of the invention 1 1.25 3.74 2 1.7 2.41 3 2.41 3.14 4 4.03 3.8 5 4.9 5.45 6 5.22 7.45

Example 4

Creamy Shampoo

[0242] The experimental protocol outlined under example 3 was repeated using the inventive compound of example 1.

[0243] The following results (ΔE) were obtained:

TABLE-US-00004 ΔE creamy shampoo containing ΔE No. of wash the inventive material Control shampoo without cycles according to example 1 inventive additive 1 0.8 0.4 2 1.97 2.18 3 1.83 1.98 40 3.71 4 5 3.89 4.09 6 3.86 4.49

[0244] The lower ΔE values for the shampoos containing the compounds of the invention according to examples 1 and 2 after six washing cycles mean that less color was lost during the washing operations. The inventive ingredients improve the retention of the artificial hair color. Additionallly, it was observed that the tone of the red color on the hair tress half treated with the inventive materials was deeper and the color more homogeneously distributed compared to the second half treated with the control shampoo.