WO2014174116A2 - Composition based on henna or indigo powder with a predispersion of oil, and hair dyeing process using this composition - Google Patents
Composition based on henna or indigo powder with a predispersion of oil, and hair dyeing process using this composition Download PDFInfo
- Publication number
- WO2014174116A2 WO2014174116A2 PCT/EP2014/058603 EP2014058603W WO2014174116A2 WO 2014174116 A2 WO2014174116 A2 WO 2014174116A2 EP 2014058603 W EP2014058603 W EP 2014058603W WO 2014174116 A2 WO2014174116 A2 WO 2014174116A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- weight
- composition
- predispersion
- butter
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 260
- 238000004043 dyeing Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 51
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000008569 process Effects 0.000 title claims abstract description 47
- 244000208060 Lawsonia inermis Species 0.000 title claims abstract description 44
- 210000004209 hair Anatomy 0.000 title claims description 41
- 239000004615 ingredient Substances 0.000 claims abstract description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 47
- 102000011782 Keratins Human genes 0.000 claims abstract description 45
- 108010076876 Keratins Proteins 0.000 claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 claims abstract description 45
- 229940097275 indigo Drugs 0.000 claims abstract description 42
- 241000196324 Embryophyta Species 0.000 claims abstract description 36
- -1 fatty alcohol esters Chemical class 0.000 claims description 87
- 239000003921 oil Substances 0.000 claims description 84
- 235000019198 oils Nutrition 0.000 claims description 80
- 235000014121 butter Nutrition 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 229920001296 polysiloxane Polymers 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- 229920006395 saturated elastomer Polymers 0.000 claims description 28
- 239000002736 nonionic surfactant Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- 244000283207 Indigofera tinctoria Species 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 15
- 239000011707 mineral Substances 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 14
- 239000003945 anionic surfactant Substances 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 150000002191 fatty alcohols Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- 239000007908 nanoemulsion Substances 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 10
- 239000004530 micro-emulsion Substances 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 235000021302 avocado oil Nutrition 0.000 claims description 9
- 239000008163 avocado oil Substances 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 235000019486 Sunflower oil Nutrition 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 8
- 239000002600 sunflower oil Substances 0.000 claims description 8
- 241001135917 Vitellaria paradoxa Species 0.000 claims description 7
- 235000018936 Vitellaria paradoxa Nutrition 0.000 claims description 7
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- 229940119170 jojoba wax Drugs 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000003240 coconut oil Substances 0.000 claims description 5
- 235000019864 coconut oil Nutrition 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000008159 sesame oil Substances 0.000 claims description 5
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- 229940057910 shea butter Drugs 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 239000000341 volatile oil Substances 0.000 claims description 5
- 241000454552 Astrocaryum murumuru Species 0.000 claims description 4
- 244000025272 Persea americana Species 0.000 claims description 4
- 239000000944 linseed oil Substances 0.000 claims description 4
- 235000021388 linseed oil Nutrition 0.000 claims description 4
- 239000010773 plant oil Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
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- 235000011236 Persea americana var americana Nutrition 0.000 claims description 3
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- 239000004359 castor oil Substances 0.000 claims description 3
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- 235000005687 corn oil Nutrition 0.000 claims description 3
- 239000002285 corn oil Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000008169 grapeseed oil Substances 0.000 claims description 3
- 239000010468 hazelnut oil Substances 0.000 claims description 3
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- 239000004006 olive oil Substances 0.000 claims description 3
- 235000008390 olive oil Nutrition 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 239000003760 tallow Substances 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012284 Bertholletia excelsa Nutrition 0.000 claims description 2
- 244000205479 Bertholletia excelsa Species 0.000 claims description 2
- 240000007817 Olea europaea Species 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
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- 240000003935 Sclerocarya birrea Species 0.000 claims description 2
- 235000001836 Sclerocarya caffra Nutrition 0.000 claims description 2
- 241000907903 Shorea Species 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000010478 argan oil Substances 0.000 claims description 2
- 239000010480 babassu oil Substances 0.000 claims description 2
- 239000010636 coriander oil Substances 0.000 claims description 2
- 235000019197 fats Nutrition 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 239000010466 nut oil Substances 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000012453 solvate Substances 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 2
- 235000014826 Mangifera indica Nutrition 0.000 claims 3
- 240000007228 Mangifera indica Species 0.000 claims 3
- 235000004936 Bromus mango Nutrition 0.000 claims 2
- 240000007154 Coffea arabica Species 0.000 claims 2
- 241000631153 Diploknema butyracea Species 0.000 claims 2
- 241001427678 Madhuca Species 0.000 claims 2
- 235000009827 Prunus armeniaca Nutrition 0.000 claims 2
- 244000018633 Prunus armeniaca Species 0.000 claims 2
- 235000009184 Spondias indica Nutrition 0.000 claims 2
- 235000019489 Almond oil Nutrition 0.000 claims 1
- 244000144725 Amygdalus communis Species 0.000 claims 1
- 235000011437 Amygdalus communis Nutrition 0.000 claims 1
- 235000000016 Astrocaryum murumuru Nutrition 0.000 claims 1
- 244000231729 Astrocaryum tucuma Species 0.000 claims 1
- 241001522729 Bassia <hydrozoan> Species 0.000 claims 1
- 235000006232 Bassia longifolia Nutrition 0.000 claims 1
- 235000013162 Cocos nucifera Nutrition 0.000 claims 1
- 244000060011 Cocos nucifera Species 0.000 claims 1
- 235000007460 Coffea arabica Nutrition 0.000 claims 1
- 241000173371 Garcinia indica Species 0.000 claims 1
- 244000020551 Helianthus annuus Species 0.000 claims 1
- 235000003222 Helianthus annuus Nutrition 0.000 claims 1
- 241000208467 Macadamia Species 0.000 claims 1
- 241000208473 Macadamia ternifolia Species 0.000 claims 1
- 235000003539 Madhuca indica Nutrition 0.000 claims 1
- 235000005058 Madhuca longifolia Nutrition 0.000 claims 1
- 240000004212 Madhuca longifolia Species 0.000 claims 1
- 241001188755 Madhuca longifolia var. latifolia Species 0.000 claims 1
- 235000017011 Mandorlo dulce Nutrition 0.000 claims 1
- 244000076313 Mandorlo dulce Species 0.000 claims 1
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- 240000002134 Pentadesma butyracea Species 0.000 claims 1
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- 241001646710 Shorea stenoptera Species 0.000 claims 1
- 235000002290 Shorea stenoptera Nutrition 0.000 claims 1
- 244000299461 Theobroma cacao Species 0.000 claims 1
- 235000009470 Theobroma cacao Nutrition 0.000 claims 1
- 241000274602 Virola sebifera Species 0.000 claims 1
- 235000014787 Vitis vinifera Nutrition 0.000 claims 1
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- 239000008168 almond oil Substances 0.000 claims 1
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- 229940087559 grape seed Drugs 0.000 claims 1
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- 239000008346 aqueous phase Substances 0.000 abstract description 14
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- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 abstract description 2
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- 150000001875 compounds Chemical class 0.000 description 39
- 241001062009 Indigofera Species 0.000 description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 34
- 125000000129 anionic group Chemical group 0.000 description 26
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- 239000000975 dye Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
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- 239000000982 direct dye Substances 0.000 description 13
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
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- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012165 plant wax Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229940068977 polysorbate 20 Drugs 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical class OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- PVEFEIWVJKUCLJ-UHFFFAOYSA-N sulfuric acid;toluene Chemical compound OS(O)(=O)=O.CC1=CC=CC=C1 PVEFEIWVJKUCLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- UUJLHYCIMQOUKC-UHFFFAOYSA-N trimethyl-[oxo(trimethylsilylperoxy)silyl]peroxysilane Chemical compound C[Si](C)(C)OO[Si](=O)OO[Si](C)(C)C UUJLHYCIMQOUKC-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical class OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4993—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
- A61K8/9783—Angiosperms [Magnoliophyta]
- A61K8/9789—Magnoliopsida [dicotyledons]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95
Definitions
- the invention relates to a composition for dyeing keratin fibres, comprising i) at least 1 % and preferably at least 5% of red henna (Lawsonia inermis, alba) powder and/or of powder of indigo-producing plant(s), ii) at least one oil, iii) optionally at least one surfactant, and iv) water or an aqueous phase, preferably water, it being understood that the ingredients ii), iii) and iv) are predispersed together and the ingredient(s) i) and the said predispersion are then mixed together; the invention also relates to a composition comprising the said composition and a supplement of water or of aqueous phase, the process for dyeing keratin fibres using the said compositions, and to the use of the said compositions for dyeing keratin fibres.
- the first known as oxidation dyeing or permanent dyeing, consists in using one or more oxidation dye precursors, more particularly one or more oxidation bases optionally combined with one or more couplers.
- Oxidation bases are usually selected from ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, can give rise via a process of oxidative condensation to coloured species, which remain trapped within the fibre.
- the shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen especially from aromatic meta- diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.
- the second dyeing method comprises the application of direct dyes, which are coloured and colouring molecules that have affinity for fibres. Given the nature of the molecules used, they tend rather to remain on the surface of the fibre and penetrate relatively little into the fibre, when compared with the small molecules of oxidation dye precursors.
- the main advantages of this type of dyeing are that it does not require any oxidizing agent, which limits the degradation of the fibres, and that it does not use any dyes that have particular reactivity, resulting in limitation of the intolerance risks.
- the first hair dyes were semi-permanent.
- One of the most well known natural dyes is that derived from the henna plant. Henna is still be used in feminine beauty enhancement for colouring the hair or the nails, or for dyeing leather, silk and wool, etc. It is also be used traditionally for various important events, celebrations and beliefs.
- Red henna consists of leaves of shrubs of the genus Lawsonia from the family of Lythraceae, which is based on the principle of dyeing with the active agent lawsone: 2- hydroxy-1 ,4-naphthoquinone.
- This dye affords an orange-red coloration on grey hair, and a "warm” i.e. coppery to red colour on chestnut-brown hair.
- the dyeing process using henna is difficult to perform.
- a kind of "paste” (often referred to as a "poultice") is first made from ground or powdered henna leaves, which is then diluted at the time of use with warm water, and the said paste is then applied to the keratin fibres.
- Indigo is derived from indican and may be prepared from various plants known as indigo-producing plants such as Indigofera tinctoria, Indigo suffruticosa, Isatis tinctoria, etc. (see Kirk-Othmer Encyclopedia of Chemical Technology, updated on 17/04/2009, DOI: 10.1002/0471238961.0425051903150618.a01.pub2).
- the indigo-producing plants are generally chopped and soaked in hot water, heated, fermented and oxidized in the open air to liberate the purple-blue coloured indigo (see Chem. Rev. 201 1 , 111 , 2537-2561 , pp. 2537-2561 ).
- Indigo is the result of the fermentation and then oxidization of indican (glycosyl precursor).
- the indigo molecule is insoluble in water.
- the problem is that dyeing using the indigo plant is difficult because the uptake of the colour into the keratin fibres is very poor. This dye affords a blue coloration on grey hair, and a "cold” colour of ash to violet colour on chestnut-brown hair.
- the dyeing process using indigo leaves is difficult to perform.
- a kind of "paste" (often referred so as a poultice) is first made from ground or powdered leaves of indigo plant (or Indian indigo or dyer's indigo) or dyer's pastel (Isatis tinctoria), which needs to have been fermented, and which is then diluted at the time of use with warm water, and the said paste is then applied to the keratin fibres.
- the leave-on time is very long with henna or indigo. It may vary from several tens of minutes to several hours (overnight) depending on the desired intensity, with no ability to control the result. The result varies as a function of the fibres to be dyed and of the indigo or henna raw material used.
- metal salts as mordants for improving the coloration of henna ⁇ Ullmann's Encyclopedia, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a12 571 .pub2 and US 2010/03133362). It is also known practice to use metal salts to improve the dyeing of indigo (vat dyes - see Chem. Rev. 201 1 , 111 , 2537- 2561 , pp. 2537-2561 ). The use of these agents requires great know-how, multiplies the steps of the process, is not always friendly towards the integrity of the fibre (cosmetically unfriendly) and may disrupt subsequent cosmetic treatments.
- Another solution is to use dye powder, optionally in the presence of excipients in fine powder form (DE 195 48 291 ).
- these powders are conditioned in sachets or blister packs (DE 101 31 385). If the packaging of the said powder happens to become broken, a large amount of raw material is lost into the air and cannot be recovered. Added to the problem of the loss of raw material is that linked to the fineness of the particles for users.
- the particles in the atmosphere can cause respiratory problems or allergies such as rhinitis for the users, sellers of extracts or natural dyeing professionals (Allergy, J. Scibilia, E. Galdi, G. Biscaldi, G. Moscato, 52, 231 -232, (1997)).
- henna leaf powder for example, optionally in the presence of excipients in powder form (DE 299 02 432).
- these powders are conditioned in sachets or blister packs. If the packaging of the dye powder happens to become broken, a large amount of raw material is lost into the air and cannot be recovered.
- Added to the problem of the loss of raw material is that linked to the pulverulence for users as indicated previously. Specifically, in the form of fine particles, henna or indigo becomes suspended in the atmosphere and can cause respiratory problems or allergies such as rhinitis for the users, sellers of extracts or natural dyeing professionals (Allergy, J. Scibilia, E. Galdi, G. Biscaldi, G. Moscato, 52, 231 - 232, (1997)).
- iii) optionally at least one surfactant, preferably a nonionic and/or anionic surfactant; and iv) water or an aqueous phase, preferably water; it being understood that the ingredients ii), iii) and iv) are predispersed together to form a predispersion, and the ingredient(s) (i) are then dispersed in the said predispersion or the said predispersion is dispersed in the said ingredient(s) i).
- surfactant preferably a nonionic and/or anionic surfactant
- the predispersion comprising the ingredients ii), iii) and iv) is an emulsion of water-in-oil type. More particularly, the predispersion is a microemulsion or even a nanoemulsion, preferably of water-in-oil type.
- the above composition is a ready-to-use composition, i.e. it may be used as such at the time of use, without requiring supplementary addition of water. It may advantageously be in the form of a poultice.
- composition of the invention may be used subsequently, optionally after storage with or without subsequent addition of water.
- a subject of the invention is also a process for preparing the preceding composition, which consists in preparing a predispersion comprising ingredients ii), iii) and iv) of the composition and then in mixing the ingredient(s) i) with the said predispersion.
- a subject of the invention is also a process for dyeing keratin fibres, especially the hair, using the composition as defined previously.
- compositions and the process using the composition according to the invention have the advantage of dyeing keratin fibres, especially human keratin fibres, with strong, chromatic colorations that are resistant to washing, perspiration, sebum and light, and that are moreover long-lasting, without impairing the said fibres. Furthermore, the colorations obtained using the composition and the process give uniform colours from the root to the end of a fibre (little coloration selectivity). Furthermore, the application of the composition does not give off any raw material dust (dust-free). The composition is easy to use, in total safety and with no risk of staining. In addition, the composition and the active agent(s) (henna and/or indigo natural dyes) remain stable on storage. The treated keratin fibres have a very pleasant cosmetic aspect, their integrity is respected.
- composition or the poultice derived from the composition as defined below of the invention is particularly creamy and/or shows excellent adhesion to the hair.
- the composition comprises as first ingredient i) red henna in powder form, preferably as fine particles.
- the henna powder may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US).
- the size of the henna powder particles is fine.
- a particle size of less than or equal to 500 ⁇ is more particularly intended.
- the powder consists of fine particles with sizes inclusively between 50 and 300 ⁇ and more particularly between 10 and 200 ⁇ .
- the said henna particles preferentially have a moisture content of between 0 and 10% by weight relative to the total weight of the powders.
- the composition according to the invention comprises red hen a powder in an amount ranging from 1 % to 85% by weight, relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and more particularly from 10% to 75% relative to the total weight of the composition.
- the final composition comprises red hen a powder in an amount ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition.
- the composition comprises as first ingredient i) a powder of indigo-producing plant(s), preferably as fine particles.
- Indigofera such as Indigofera tinctoria, Indigo suffraticosa, Indigofera articulata
- Isatis such as Isatis tinctoria
- Persicaria such as Polygonum tinctorium (Persicaria tinctoria);
- Calanthe such as Calanthe veratrifolia
- Baphicacanthus such as Baphicacanthus cusia.
- the indigo-producing plant is of the genus Indigofera and more particularly is Indigofera tinctoria.
- Use may be made of all or part (in particular the leaves especially for Indigofera tinctoria) of the indigo-producing plant.
- the indigo-producing plant powder may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US).
- the size of the indigo-producing plant powder particles is fine.
- a particle size of less than or equal to 500 ⁇ is more particularly intended.
- the powder consists of fine particles with sizes inclusively between 50 and 300 ⁇ and more particularly between 10 and 200 ⁇ .
- the said indigo-producing plant particles preferentially have a moisture content of between 0 and 10% by weight relative to the total weight of the powders.
- the composition according to the invention comprises indigo- producing plant powder in an amount ranging from 1 % to 85% by weight, relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and preferentially from 10% to 75% relative to the total weight of the composition.
- the final composition comprises indigo- producing plant powder in an amount ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition.
- the composition comprises as first ingredient i) a mixture of red henna powder as defined previously and of indigo-producing plant powder, preferably as fine particles, as defined previously.
- the composition according to the invention comprises the mixture of powders in an amount ranging from 1 % to 85% by weight, relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and preferentially from 10% to 75% relative to the total weight of the composition.
- the final composition comprises the mixture of powders in an amount ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition.
- Predispersion, emulsion, microemulsion and nanoemulsion are particularly ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition.
- the predispersion of the invention uses the ingredients ii) and iv), and optionally iii), as defined below, which are thus predispersed.
- predispersed means that the ingredients ii), iv) and optionally iii) are mixed with iv) water or the aqueous phase of the composition of the invention so as to obtain a "dispersion", which is preferably stable at room temperature and at atmospheric pressure, before being mixed with the ingredient i), and with the optional remainder of water, the said predispersion possibly containing the optional ingredients as described below.
- the predispersion comprises at least one surfactant
- a preemulsion when it will be referred to as a preemulsion.
- the term "dispersed” means that the solid ingredient (such as the ingredient i)) is distributed in the mixture of ingredients ii), iv) and optionally iii) without being dissolved.
- the term “emulsion” means the mixture of a liquid
- the mean size of the droplets of the emulsion according to the invention is preferably between 10 nm and 100 ⁇ and preferably between 20 nm and 50 ⁇ . This is the mean diameter D(3.2), which may be measured especially using a laser particle sizer.
- these emulsions When the emulsion droplets size is less than or equal to 200 nm, these emulsions will be referred to as nanoemulsions or microemulsions, the first being thermodynamically unstable and the second being thermodynamically stable.
- the emulsion may be direct, i.e. of oil-in-water (O/W) type, and the emulsion is then in the form of an aqueous continuous phase (or outer phase) in which is distributed a discontinuous fatty phase (or inner phase: oil + optionally solid fatty substances).
- O/W oil-in-water
- the emulsion has a mean size of greater than 200 nm, and is an inverse emulsion, i.e. of water-in-oil (W/O) type, the emulsion then being in the form of a continuous fatty phase (or outer phase: oil + optionally solid fatty substances) in which is distributed a discontinuous aqueous phase (or inner phase).
- W/O water-in-oil
- the emulsion of the invention is prepared via standard processes for preparing emulsions or dispersions, which are well known to those skilled in the art (see, for example, 'Emulsions", Kirk-Othmer Encyclopedia of Chemical Technology, Edward Kostansek, published Online on 13/07/2012, DOI: 10.1002/0471238961.051321 1206180902.a01.pub3, point 3 "Preparation").
- microemulsions may be obtained by simple hot or cold mixing of the water, oils and surfactants, provided that the mixing lies within the correct zone of the phase diagrams.
- nanoemulsions are obtained via standard methods known to those skilled in the art
- the production of the nanoemulsions may take place by lying within adequate zones of the phase diagrams and using powerful stirring devices such as high-pressure homogenizers. It may also be performed via phase inversion techniques that are well known to those skilled in the art.
- the preemulsion according to the invention is a preemulsion of water or of aqueous phase in oil, i.e. of W/O type.
- the predispersion of the invention is free of any surfactant.
- free of surfactants means free of any non-polymeric compound with an HLB value of greater than or equal to 1 .
- the predispersion comprises at least one surfactant, i.e. the ingredient iii) as defined previously. It is then referred to as a preemulsion as indicated above.
- the predispersion comprises at least one stabilizing polymer compound, which is preferably silylated, such as those based on polydimethylsiloxane PDMS and/or on SMDI and polyalkylene glycol, especially polyethylene glycol and polypropylene glycol.
- This or these stabilizing polymer compound(s) may represent from 0.1 % to 20%, preferably from 0.5% to 15% by weight and better still from 1 % to 10% by weight, relative to the total weight of the said predispersion.
- the ready-to-use composition applied to the keratin fibres is not a compact solid.
- composition of the invention the final composition in the event of supplementary addition of water or the predispersion comprise one or more oils preferably of plant origin.
- o/7 means a "fatty substance” that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg).
- the viscosity at 25°C is preferably less than 1200 cps and better still less than 500 cps (defined, for example, from the Newtonian plateau determined using an ARG2 rheometer from TA Instruments equipped with a spindle with cone-plate geometry 60 mm in diameter and with an angle of 2 degrees over a shear stress range of from 0.1 Pa to 100 Pa).
- fatty substance means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They have in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups.
- the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
- the oils are chosen from non-silicone oils and in particular C 6 -Ci 6 hydrocarbons or hydrocarbons containing more than 16 carbon atoms and in particular alkanes; oils of animal origin; triglyceride oils of plant origin; essential oils; fluoro oils or glycerides of synthetic origin, fatty alcohols; fatty acid and/or fatty alcohol esters other than triglycerides, and silicone oils.
- the oils do not comprise any C 2 -C 3 oxyalkylene units or any glycerolated units.
- the oils are not fatty acids which, in salified form, give water-soluble soaps.
- the oils that may be used as second ingredient ii) in the composition in accordance with the invention may be silicones.
- the silicones may be volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified with organic groups, having a viscosity from 5x10 "6 to 2.5 m 2 /s at
- the silicone is chosen from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMSs), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amino groups and alkoxy groups.
- PDMSs polydimethylsiloxanes
- organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amino groups and alkoxy groups.
- Organopolysiloxanes are defined in greater detail in Walter Noll's "Chemistry and
- the silicones are more particularly chosen from those with a boiling point of between 60°C and 260°C, and even more particularly from:
- cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
- Use is preferably made of non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the organofunctional groups above, and mixtures thereof.
- silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups.
- the viscosity of the silicones is measured at 25°C according to ASTM
- oils of the 200 series from the company Dow Corning such as DC200 with a viscosity of 60 000 mm 2 /s;
- CTFA dimethiconol
- the fatty alcohols, acids, amides and esters that may be used as second ingredient ii) in the composition in accordance with the invention are in the form of oils.
- fatty alcohols, amides, esters and acids which are liquid (oils), more particularly have at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising 6 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
- the ingredient ii) may represent an ester of a C-I-C-IO alcohol and of a C 6 -C 3 o fatty acid such as R-C(0)-0-R' with R representing a linear or branched C 6 -C 3 o alkyl or linear or branched C 6 -C 30 alkenyl group, comprising one or two unsaturations, and R representing a linear or branched C1-C10 alkyl group.
- R represents a linear C10-C20 alkyl group and R' represents a Ci-C 6 alkyl group that is preferably branched, such as isopropyl myristate.
- the ingredient ii) represents one or more amides of a C 6 -C 3 o fatty acid and of a primary or secondary, preferably primary, C1-C10 amine, such as those of formula R"-C(0)-N(R a )-R"' with R" representing a linear or branched C 6 -C 30 alkyl or linear or branched C 6 -C 30 alkenyl group, comprising one or two unsaturations, which may be substituted with one or more hydroxyl groups, or (di)(Ci-C 6 )(alkyl)amino, and '" representing a linear or branched C1-C1 0 alkyl group, R a representing a hydrogen atom or an alkyl group as defined for R'".
- R" represents a C14-C2 0 alkenyl group
- R a represents a hydrogen atom
- R'" represents a Ci-C 6 alkyl group optionally substituted with (di)(Ci-C 4 )(alkyl)amino such as oleylamidopropyldimethylamine.
- C 6 -Ci 6 alkanes they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
- the linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam ® .
- liquid fatty acid triglycerides containing from 6 to 30 carbon atoms for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol ® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
- fluoro oils mention may be made of perfluoromethylcyclopentane and perfluoro-1 ,3-dimethylcyclohexane, sold under the names Flutec ® PC1 and Flutec ® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050 ® and PF 5060 ® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl ® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-(trifluoromethyl)perfluoromorpholine sold under the name PF 5052 ® by the company 3M.
- Flutec ® PC1 and Flutec ® PC3 by
- the ingredient(s) ii) are other than essential oils.
- the oil(s) are chosen from C 6 -Ci 6 alkanes, polydecenes, liquid esters of a fatty acid and/or of a fatty alcohol, and liquid fatty alcohols, or mixtures thereof.
- the fatty substance is chosen from liquid petroleum jelly, C 6 -Ci 6 alkanes and polydecenes.
- the oil(s) are chosen from mineral oils such as liquid petroleum jelly.
- the oils, ingredient ii) are chosen from oils of natural origin and particularly oils of plant origin, such as jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, corn oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil and rapeseed oil.
- oils of natural origin such as jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, corn oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil and rapeseed oil.
- the oil(s), ingredient ii), of the invention are chosen from sunflower oil, avocado oil, olive oil, sesame oil and jojoba oil, and are more preferentially chosen from avocado oil and sunflower oil.
- the above plant oils in are in a mixture with one or more esters of a C1-C1 0 alcohol and of a C 6 -C 3 o fatty acid such as R-C(0)-0-R' with R representing a linear or branched C 6 -C 30 alkyl or linear or branched C 6 -C 30 alkenyl group, comprising one or two unsaturations, and R representing a linear or branched C-I-C-IO alkyl group; preferentially, R represents a linear Ci 0 -C 2 o alkyl group and R' represents a preferably branched Ci-C 6 alkyl group, such as isopropyl myristate.
- R-C(0)-0-R' with R representing a linear or branched C 6 -C 30 alkyl or linear or branched C 6 -C 30 alkenyl group, comprising one or two unsaturations, and R representing a linear or branched C-I-C-IO alkyl group
- R
- the above oils of plant origin are in a mixture with one or more amides of a C6-C30 fatty acid and of a primary or secondary, preferably primary, C-I-C-IO amine, such as those of formula R"-C(0)-N(Ra)-R"' with R" representing a linear or branched C6-C30 alkyl or linear or branched C 6 -C 30 alkenyl group, comprising one or two unsaturations, which may be substituted with one or more hydroxyl groups, or (di)(Ci-C 6 )(alkyl)amino, and R'" representing a linear or branched C1-C1 0 alkyl group, Ra representing a hydrogen atom or an alkyl group as defined for R'".
- a primary or secondary, preferably primary, C-I-C-IO amine such as those of formula R"-C(0)-N(Ra)-R"' with R" representing a linear or branched C6-C30 al
- R" represents a C14-C2 0 alkenyl group
- Ra represents a hydrogen atom
- R'" represents a Ci-C 6 alkyl group optionally substituted with (di)(Ci-C 4 )(alkyl)amino such as oleylamidopropyldimethylamine.
- the oil(s) of the invention are non-silicone oils.
- non-silicone o/V means an oil not containing any silicon atoms (Si) and the term “silicone o/V means an oil containing at least one silicon atom.
- the predispersion of the invention before addition of the ingredient(s) i) comprises from 30% to 90% by weight and preferably 40% to 75% by weight of one or more oils relative to the total weight of the said predispersion.
- composition according to the invention comprises from 1 0% to 85% by weight, preferably from 1 5% to 80% by weight and better still from 20% to 75% by weight of one or more oils relative to the total weight of the said composition.
- the composition comprises from 1 0% to 60% by weight, preferably from 1 5% to 50% by weight and better still from 20% to 40% by weight of one or more oils relative to the total weight of the said final composition.
- Fatty substance other than oils butters, waxes or resins
- the composition of the invention also comprise one or more fatty substances other than the oil(s) ii) as defined previously.
- the composition comprises one or more butters, preferably of plant origin.
- the term “butter” (also known as a "pasty fatty substance”) means a lipophilic fatty compound which undergoes a reversible solid/liquid change of state and which comprises, at a temperature of 25°C and at atmospheric pressure (760 mmHg), a liquid fraction and a solid fraction.
- the starting melting point of the pasty compound may be less than 25°C.
- the liquid fraction of the pasty compound, measured at 25°C, may represent 9% to 97% by weight of the compound. This liquid fraction at 25°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
- the butter(s) have an end melting point of less than 60°C.
- the butter(s) have a hardness of less than or equal to 6 MPa.
- the pasty fatty substances have, in the solid state, an anisotropic crystal organization, which is visible by X-ray observation.
- the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in Standard
- the melting point of a pasty substance or of a wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.
- DSC differential scanning calorimeter
- sample preparation and measurement protocols are as follows:
- the measurements are performed on the abovementioned calorimeter.
- the oven is flushed with nitrogen. Cooling is performed by an RCS 90 heat exchanger.
- the sample is then subjected to the following protocol: it is first placed at a temperature of 20°C, and then subjected to a first temperature rise passing from 20°C to 80°C, at a heating rate of 5°C/minute, then is cooled from 80°C to -80°C at a cooling rate of 5°C/minute and finally subjected to a second temperature rise passing from -80°C to 80°C at a heating rate of 5°C/minute.
- the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of butter is measured as a function of the temperature.
- the melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
- the end melting point corresponds to the temperature at which 95% of the sample has melted.
- the liquid fraction by weight of the butter at 25°C is equal to the ratio of the heat of fusion consumed at 25°C to the enthalpy of fusion of the butter.
- the heat of fusion of the pasty compound is the heat consumed by the compound in order to pass from the solid state to the liquid state.
- the butter is said to be in the solid state when all of its mass is in crystalline solid form.
- the butter is said to be in the liquid state when all of its mass is in liquid form.
- the heat of fusion of the butter is equal to the integral of the entire melting curve obtained using the abovementioned colorimeter, with a temperature rise of 5 or 10°C/minute, according to Standard ISO 1 1357-3:1999.
- the heat of fusion of the butter is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
- the heat of fusion consumed at 25°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 25°C, constituted of a liquid fraction and a solid fraction.
- the liquid fraction of the butter measured at 32°C preferably represents from 30% to 100% by weight of the compound, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the compound.
- the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
- the liquid fraction of the butter measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound.
- the heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.
- sample preparation and measurement protocols are as follows:
- composition according to the invention or the butter is placed in a mould 75 mm in diameter, which is filled to about 75% of its height.
- the mould is placed in a Votsch VC0018 programmable oven, where it is first placed at a temperature of 80°C for 60 minutes, then cooled from 80°C to 0°C at a cooling rate of 5°C/minute, and then left at the stabilized temperature of 0°C for 60 minutes, and then subjected to a temperature rise ranging from 0°C to 20°C, at a heating rate of 5°C/minute, and then left at the stabilized temperature of 20°C for 180 minutes.
- the compression force measurement is taken using a TA TX2i texturometer from Swantech.
- the spindle used is chosen according to the texture:
- the measurement comprises three steps:
- the hardness value measured during the first step corresponds to the maximum compression force measured in newtons divided by the area of the texturometer cylinder expressed in mm 2 in contact with the butter or the composition according to the invention.
- the hardness value obtained is expressed in megapascals or MPa.
- the particular butter(s) are of plant origin, such as those described in Ullmann's Encyclopedia of Industrial Chemistry ("Fats and Fatty Oils", A. Thomas, published online: 15/06/2000, DOI: 10.1002/14356007.a10_173, point 13.2.2.2. Shea Butter, Borneo Tallow, and Related Fats (Vegetable Butters)).
- the weight content of Ci 6 fatty acid triglycerides is less than 23%.
- the weight content of Ci 6 fatty acid triglycerides ranges from 0 to 22%, better still from 0 to 15% and even better still from 2% to 12%.
- the butter(s) according to the invention are chosen from murumuru butter, ucuuba butter, shorea butter, illipe butter, shea butter and cupuagu butter, and even more preferentially from murumuru butter and ucuuba butter.
- the waxes may be fatty alcohols or fatty esters that are solid at room temperature and at atmospheric pressure.
- the composition comprises as third constituent one or more solid fatty alcohols.
- the fatty alcohols that are suitable for use in the invention are more particularly chosen from linear saturated alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and a mixture thereof (cetearyl alcohol). As regards the solid fatty acid esters and/or fatty alcohols, mention may preferably be made of esters of saturated linear fatty acids and of saturated linear fatty alcohols, such as cetyl palmitate, stearyl stearate or cetyl stearate.
- the composition comprises as third constituent one or more waxes, other than the fatty alcohols and fatty esters mentioned above, preferably of plant origin.
- the non-silicone wax(es) are chosen in particular from carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite, plant waxes, such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute flower waxes, such as the blackcurrant blossom essential wax sold by Bertin (France), or animal waxes, such as beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy raw materials that can be used according to the invention are in particular marine waxes, such as that sold by the company Sophim under the reference M82, polyethylene waxes or polyolefin waxes in general.
- the composition comprises one or more silicone waxes, resins or gums.
- the silicone gums that may be used in accordance with the invention are especially polydialkylsiloxanes and preferably polydimethylsiloxanes with high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent.
- This solvent can be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane or tridecane, or mixtures thereof.
- Products that can be used more particularly in accordance with the invention are mixtures such as:
- CTFA hydroxy-terminated polydimethylsiloxane or dimethiconol
- CFA cyclic polydimethylsiloxane
- the product SF 1236 is a mixture of a gum SE 30 defined above, with a viscosity of 20 m 2 /s and of an oil SF 96 with a viscosity of 5x10 "6 m 2 /s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.
- organopolysiloxane resins that may be used in accordance with the invention are crosslinked siloxane systems containing the following units:
- R represents an alkyl containing 1 to 16 carbon atoms.
- R denotes a C C 4 lower alkyl group, more particularly methyl.
- the fatty substance(s) other than the oil(s) ii) do not comprise any C 2 -C 3 oxyalkylene units or any glycerolated units and are other than fatty acids.
- the fatty substance(s) other than the oil(s) ii) are chosen from butters.
- the predispersion of the invention before addition of the ingredient(s) i) may comprise one or more fatty substances other than the oil(s) ii) in an amount ranging from 0.1 % to 50% by weight, more particularly from 1 % to 40% by weight, preferentially from 2% to 30% by weight and more preferentially from 3% to 20% by weight relative to the weight of the said predispersion.
- composition according to the invention may comprise one or more fatty substances other than the oil(s) ii) in an amount ranging from 0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and preferentially from 1 % to 10% by weight relative to the weight of the said composition.
- the final composition may comprise one or more fatty substances other than the oil(s) ii) in an amount ranging from 0.1 % to 20% by weight, more particularly from 0.5% to 10% by weight and preferentially from 1 % to 5% by weight relative to the weight of the said final composition.
- the composition of the invention, the final composition in the event of supplementary addition of water or the predispersion comprise one or more surfactants, i.e. ingredient(s) iii).
- This or these surfactant(s) may be chosen from nonionic, anionic, cationic and amphoteric surfactants.
- the ingredient iii) represents one or more amphoteric surfactants.
- amphoteric surfactant(s) that may be used in the present invention may be chosen especially from optionally quaternized secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
- the ingredient(s) iii) are in the predispersion and/or the compositions of the invention and are chosen from the compounds of respective structures (B1) and (B2) below:
- R a represents a Ci 0 -C 3 o alkyl or alkenyl group derived from a carboxylic acid R a C(0)OH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
- R b represents a ⁇ -hydroxyethyl group
- R c represents a carboxymethyl group
- ⁇ M + represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine, and
- X represents an organic or mineral anionic counterion, preferably chosen from halides, acetates, phosphates, nitrates, (CrC 4 )alkyl sulfates, (Ci-C 4 )alkyl- or (d- C 4 )alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate;
- Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group
- X' represents the group -CH 2 -C(0)OH, -CH 2 -C(0)OZ ⁇ -CH 2 -CH 2 -C(0)OH, -CH 2 -CH 2 - C(0)OZ', or a hydrogen atom;
- ⁇ Y' represents the group -C(0)OH, -C(0)OZ ⁇ -CH 2 -CH(OH)-S0 3 H or the group -CH 2 -
- Z' represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
- R a ' represents a Ci 0 -C 3 o alkyl or alkenyl group of an acid R a C(0)OH preferably present in hydrolysed linseed oil or coconut oil, an alkyl group, in particular of Ci 7 and its iso form, or an unsaturated Ci 7 group.
- Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group.
- the compounds of this type are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.
- Examples that may be mentioned include the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol ® C2M Concentrate or under the trade name Miranol Ultra C 32 and the product sold by the company Chimex under the trade name Chimexane HA (to be transferred into PR231 ).
- the ingredient(s) iii) are in the predispersion and/or the compositions of the invention and are chosen from the compounds of respective structure (B'2) below: R a "-N(H)-CH(Y")-(CH 2 ) n -C(0)-N(H)-(CH 2 ) n -N(R d )(R e ) (B'2) in which formula (B'2):
- Y represents the group -C(0)OH, -C(0)OZ", -CH 2 -CH(OH)-S0 3 H or the group -CH 2 - CH(OH)-S0 3 -Z";
- R d and R e represent, independently of each other, a Ci-C 4 alkyl or hydroxyalkyl radical
- Z represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
- R a " represents a Ci 0 -C 30 alkyl or alkenyl group of an acid
- ⁇ n and n' denote, independently of each other, an integer ranging from 1 to 3.
- the ingredient iii) represents one or more surfactants chosen from the compounds of formula (B3) and also the optional salts thereof with organic or mineral acids or bases, and solvates thereof such as hydrates:
- R1 denotes a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising from 6 to 100 carbon atoms and in particular from 6 to 50 carbon atoms, which may be interrupted with one or more heteroatoms, divalent groups, or combinations thereof chosen from -0-, -C(O)- and -N(R)-; with R denoting a hydrogen atom or a CrC 4 alkyl radical, and R 1 also possibly being interrupted with an arylene group or terminated with an aryl group;
- R 2 and R 3 which may be identical or different, in particular R 2 and R 3 are identical, denote a (CrC 6 )alkyl group; preferably, R 2 and R 3 represent a methyl group;
- R 4 denotes a linear or branched, preferably linear, divalent hydrocarbon-based radical, comprising from 1 to 10 and preferably from 1 to 5 carbon atoms, optionally substituted in particular with one or more hydroxyl groups;
- Z denotes a heteroatom or a divalent group chosen from -O- and -N(R)- with R as defined previously,
- n denotes a number equal to 1 or 2;
- m denotes an integer equal to 0 or 1 ;
- the radicals R 1 R 2 R 3 N + -R'-(Z) m - are identical or different, preferably identical; and - the surfactant of formula (B3) being electrically neutral, it may comprise anionic and/or cationic counterions to produce the electrical neutrality of the molecule.
- unsaturated hydrocarbon-based chain means a hydrocarbon-based chain which comprises one or more double bonds and/or one or more triple bonds, the said bonds possibly being conjugated or non-conjugated.
- alkyl radical means a saturated, linear or branched hydrocarbon-based radical, preferably of Ci-C 8 .
- alkenyl radical means a linear or branched, preferably C 2 -C 8 , hydrocarbon- based radical; which is unsaturated, comprising one or more conjugated or non-conjugated double bonds.
- alkoxy radical means an alkyl-oxy radical for which the alkyl radical is a linear or branched C Ci 6 and preferentially Ci-C 8 hydrocarbon-based radical.
- aryP' radical means a fused or non-fused monocyclic or polycyclic carbon- based group comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl.
- arylene radical means a fused or non-fused monocyclic or polycyclic carbon- based group comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially phenylene and more preferentially 1 ,3- or 1 ,4-phenylene;
- radicals chosen from the following radicals: i) hydroxyl, ii) Ci-C 4 alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different C1-C4 alkyl radicals, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom.
- organic or mineral acid salt more particularly means salts chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 S0 4 , iv) alkylsulfonic acids: Alk-S(0) 2 OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(0) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-O- S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xi
- organic or mineral base salt more particularly means salts chosen from a salt derived from basifying agents as defined in “Additional basifying agents” hereinbelow.
- anionic counterion means an anion or an anionic group derived from an organic or mineral acid salt which counterbalances the cationic charge of the dye; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including Ci-C 6 alkylsulfonates: Alk-S(0) 2 0 " such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: Ar-S(0) 2 0 " such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-0-S(0)0 " such as methyl sulfate and ethyl sulfate;
- the cationic counterion(s) are chosen from alkali metals such as Na or K or alkaline-earth metals such as Mg or Ca, or organic cations such as ammonium or mono/di/tri(Ci-C 6 )alkylammonium, and/or the anionic counterion(s) are chosen from halides such as chloride or alkylsulfonates such as mesylates.
- the optional cationic counterion(s) are chosen from alkali metals such as Na or K or alkaline-earth metals such as Mg or Ca, and/or the anionic counterion(s) are chosen from halides such as chloride or alkylsulfonates such as mesylates.
- the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which n is equal to 1 and G " denotes an anionic radical chosen from * -C(0)0- and * -S(0) 2 -0 " .
- the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which R 4 denotes a linear C 1 -C5 divalent alkylene radical optionally substituted with a hydroxyl group, such as -CH 2 -CH 2 -CH 2 -, -CH 2 - CH(OH)-CH 2 - or -CH 2 -CH 2 -.
- the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which m is 1 and Z represents an oxygen atom or a group -N(R)- with R as defined previously. More preferentially, when m is 1 , then Z represents an oxygen atom.
- the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which m is 0.
- the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which R 1 denotes a group chosen from i) C 6 -C 3 o alkyl; ii) C 6 -C 3 o alkenyl; -alkyl(C6-C 3 o)-amido-(Ci-C 4 )alkyl or -alkenyl(C 6 -C 3 o)-amido- (CrC 4 )alkyl, with amido representing a group -C(0)-N(R)- and R being as defined previously.
- R denotes a hydrogen atom. More particularly, R 1 denotes a linear or branched, preferably linear, C 6 -C 3 o alkyi radical.
- amphoteric surfactants use is preferably made of (C 8 - C 2 o)alkylbetaines such as cocoylbetaine, and (C 8 -C2o)alkylamido(C2-C 2 o)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof.
- amphoteric surfactant(s) are chosen from cocoylamidopropylbetaine and cocoylbetaine.
- the ingredient iii) represents one or more anionic surfactants.
- anionic surfactant means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the following groups:
- the anionic parts comprising a cationic counterion such as those of an alkali metal, an alkaline-earth metal or an ammonium.
- anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyi sulfates, alkyi ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkyi sulfosuccinates, alkyi ether sulfosuccinates, alkylamide sulfosuccinates, alkyi sulfoacetates, acylsarcosinates, acylglutamates, alkyi sulfosuccinamates, acylisethionates and N- acyltaurates, polyglycoside polycarboxylic acid and alkyi monoester
- These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
- the salts of C 6 -C 24 alkyi monoesters of polyglycoside-polycarboxylic acids may be chosen from C 6 -C 24 alkyi polyglycoside-citrates, C 6 -C 24 alkyi polyglycoside-tartrates and C 6 - C 24 alkyi polyglycoside-sulfosuccinates.
- anionic surfactant(s) When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as the magnesium salts.
- alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as the magnesium salts.
- amino alcohol salts examples include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2- amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
- Alkali metal or alkaline-earth metal salts, and in particular sodium or magnesium salts, are preferably used.
- anionic surfactants use is preferably made of (C 6 -C 2 4)alkyl sulfates, (C 6 -C 2 4)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
- (Ci 2 -C 2 o)alkyl sulfates (Ci 2 -C 20 )alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
- (Ci 2 -C 2 o)alkyl sulfates (Ci 2 -C 20 )alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
- sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.
- the ingredient(s) iii) represent one or more cationic surfactants.
- the cationic surfactant(s) that may be used in the composition according to the invention comprise, for example, optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
- tertiary fatty amines mention may be made more particularly of oleylamidopropyldimethylamine.
- Quaternary ammonium salts that may especially be mentioned include:
- R 8 to Rii which may be identical or different, represent a linear or branched, saturated or unsaturated aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R 8 to Rn comprises from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms; and
- ⁇ X " represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (CrC 4 )alkyl- sulfates, (CrC 4 )alkyl- or (d- C 4 )alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate;
- the aliphatic groups of R 8 to Rn may also comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens;
- the aliphatic groups of R 8 to Rn are chosen in particular from C 1 -C30 alkyl, C 1 -C30 alkoxy, polyoxy(C 2 -C 6 )alkylene, C 1 -C30 alkylamide, (Ci 2 -C 22 )alkylamido(C 2 -C 6 )alkyl, (Ci 2 -C 22 )alkyl acetate, and C 1 -C30 hydroxyalkyl groups
- X " is an anionic counterion chosen from the group of halides, phosphates, acetates, lactates, (CrC 4 )alkyl sulfates, and (Ci-C 4 )alkyl- or (Ci-C 4 )alkylaryl sulfonates;
- tetraalkylammonium chlorides for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride;
- ⁇ R-I2 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow;
- ⁇ Ri 3 represents a hydrogen atom, a C C 4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;
- ⁇ Ri 4 represents a C C 4 alkyl group
- ⁇ Ri 5 represents a hydrogen atom or a C C 4 alkyl group
- ⁇ X " represents an organic or mineral anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (Ci-C 4 )alkyl- sulfates, (Ci-C 4 )alkyl- or (d- C 4 )alkylaryl sulfonates;
- R-I2 and Ri 3 preferably denote a mixture of alkyl or alkenyl groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids, Ri 4 preferably denotes a methyl group, and Ri 5 preferably denotes a hydrogen atom; such a product is sold, for example, under the name Rewoquat® W75 by the company Rewo;
- ⁇ R-16 denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;
- R-I7 is selected from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH 2 ) 3 -N + (R 16a )(R 17a )(R 18a ), X " ;
- R 16a , Ri7a, Risa, Ri8, Ri9, R20 and R21 which may be identical or different, are selected from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms;
- ⁇ X " which may be identical or different, represent an organic or mineral anionic counterion, such as that selected from halides, acetates, phosphates, nitrates, (C1-C4) alkyl sulfates, (C1-C4) alkyl- or (C1-C4) alkyl aryl sulfonates, more particularly methyl sulfate and ethyl sulfate;
- Such compounds are, for example, Finquat CT-P, available from the company Finetex (Quaternium 89), and Finquat CT, available from the company Finetex (Quaternium 75);
- R 22 is chosen from CrC 6 alkyl groups and CrC 6 hydroxyalkyl or CrC 6 dihydroxyalkyl groups;
- ⁇ R23 is chosen from:
- Ci-C 22 hydrocarbon-based groups R27 - linear or branched, saturated or unsaturated Ci-C 22 hydrocarbon-based groups R27,
- ⁇ R25 is chosen from:
- Ci-C 6 hydrocarbon-based groups R 29 - linear or branched, saturated or unsaturated Ci-C 6 hydrocarbon-based groups R 29 ,
- R24, R26 and R 2 8 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;
- ⁇ y is an integer ranging from 1 to 10,
- ⁇ x and z which may be identical or different, are integers ranging from 0 to 10;
- ⁇ X " represents an organic or mineral anionic counterion
- the alkyl groups R 22 may be linear or branched, and more particularly linear;
- R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group; advantageously, the sum x + y + z is from
- R 23 is a hydrocarbon-based group R 27 , it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
- R 25 is a hydrocarbon-based group R 29 , it preferably contains 1 to 3 carbon atoms.
- R 24 , R 26 and R 28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn-C 2 i hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn-C 2 i alkyl and alkenyl groups.
- x and z which may be identical or different, are equal to 0 or 1 .
- y is equal to 1.
- r, s and t which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
- the anionic counterion X " is preferably a halide, such as chloride, bromide or iodide; a (CrC 4 )alkyl sulfate or a (CrC 4 )alkyl- or (Ci-C 4 )alkylaryl sulfonate.
- a halide such as chloride, bromide or iodide
- a (CrC 4 )alkyl sulfate or a (CrC 4 )alkyl- or (Ci-C 4 )alkylaryl sulfonate it is possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function.
- the anionic counterion X " is even more particularly chloride, methyl sulfate or ethyl sulfate.
- R 22 denotes a methyl or ethyl group
- - R25 is chosen from:
- R 2 4, R26 and R 2 8, which may be identical or different, are selected from linear or branched, saturated or unsaturated C13-C17 hydrocarbon groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
- hydrocarbon-based radicals are linear.
- examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,
- acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil, such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
- This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
- an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
- Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.
- composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
- ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
- Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.
- the ammonium salts containing at least one ester function contain two ester functions.
- the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, dipalmitoylethylhydroxyethylammonium methosulfate and oleylamidopropyldimethylamine, and mixtures thereof.
- the ingredient iii) represents one or more nonionic surfactants.
- nonionic surfactant means a surfactant that does not bear any anionic or cationic charge.
- examples of nonionic surfactants that can be used in the composition used according to the invention are described, for example, in the "Handbook of Surfactants” by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp. 1 16-178.
- They are especially chosen from alcohols, a-diols and (CrC 2 o)alkylphenols, these compounds being polyethoxylated, polypropoxylated and/or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 50, and for the number of glycerol groups to especially range from 2 to 30.
- the nonionic surfactants are chosen more particularly from mono- or polyoxyalkylenated or mono- or polyglycerolated nonionic surfactants.
- the oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
- oxyalkylenated nonionic surfactants of:
- esters of saturated or unsaturated, linear or branched, C 8 -C 3 o acids and of polyethylene glycols • esters of saturated or unsaturated, linear or branched, C 8 -C 3 o acids and of polyethylene glycols;
- the surfactants contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100, preferably between 2 and 50 and preferably between 2 and 30.
- the nonionic surfactants do not comprise any oxypropylene units.
- the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 mol of ethylene oxide; polyoxyethylenated esters of linear or branched, saturated or unsaturated C 8 -C 30 acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.
- monoglycerolated or polyglycerolated nonionic surfactants monoglycerolated or polyglycerolated nonionic surfactants.
- monoglycerolated or polyglycerolated C 8 -C 4 o alcohols are preferably used.
- R 29 represents a linear or branched C 8 -C 40 and preferably C 8 -C 3 o alkyl or alkenyl radical
- ⁇ m represents a number ranging from 1 to 30 and preferably from 1 to 10.
- lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1 .5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.
- the alcohol of formula (B8) may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohols may coexist in the form of a mixture.
- the monoglycerolated or polyglycerolated alcohols it is more particularly preferred to use the C 8 /Ci 0 alcohol containing 1 mol of glycerol, the C1 0 /C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol.
- saturated or unsaturated, linear or branched C 8 -C 3 o acid esters of polyoxyethylenated sorbitol the ones that are preferred are those with a number of moles of ethylene oxide of less than or equal to 20, particularly comprising from 8 to 24 carbon atoms and more particularly from 8 to 18 carbon atoms.
- the fatty acids are especially chosen from lauric acid, palmitic acid, oleic acid and stearic acid, and preferably from lauric acid and stearic acid, and even more particularly lauric acid.
- C 8 -C 24 fatty acid monoesters of oxyethylenated sorbitan are preferably used.
- the number of moles of ethylene oxide is preferably less than 10 and more particularly ranges from 3 to 8 mol of ethylene oxide and in particular is equal to 4.
- the preferred sorbitan esters are sorbitan monolaurate oxyethylenated with 4 mol of ethylene oxide (4 EO) or polysorbate 21 , sorbitan monostearate oxyethylenated with 4 mol of ethylene oxide (4 EO) or polysorbate 61 , and sorbitan monooleate oxyethylenated with 5 mol of ethylene oxide (5 EO) or polysorbate 81 .
- Polysorbate 21 is particularly preferred and is sold especially under the name Tween
- the composition may advantageously comprise mixtures of oxyethylenated sorbitan esters and especially polysorbate 21 with polysorbate 20 (sorbitan monolaurate oxyethylenated with 20 EO).
- the surfactant(s) iii) are chosen from nonionic, cationic and anionic surfactants and are particularly chosen from nonionic and anionic surfactants. More particularly, the surfactant(s) present in the composition are chosen from nonionic surfactants.
- the nonionic surfactant(s) are monooxyalkylenated or polyoxyalkylenated, particularly monooxyethylenated or polyoxyethylenated, or monooxypropylenated or polyoxypropylenated, nonionic surfactant(s), or a combination thereof, more particularly monooxyethylenated or polyoxyethylenated.
- nonionic surfactants are chosen from polyoxyethylenated sorbitol esters and polyoxyethylenated fatty alcohols, and mixtures thereof.
- the composition according to the invention in the event of supplementary addition of water, the predispersion and the process for treating (dyeing) keratin fibres used as ingredient iii) one or more surfactants chosen from nonionic surfactants, in particular mono oxyalkylenated or polyoxyalkylenated surfactants, more particularly chosen from polyoxyethylenated saturated or unsaturated, linear or branched C 8 -C 3 o acid esters of sorbitol as defined previously; and/or one or more anionic surfactants, in particular of alkyl sulfate type as defined previously, in particular an alkali metal or alkaline-earth metal salt of lauryl ether sulfate.
- the predispersion or preemulsion of the invention preferably contains from 1 % to 60% by weight, preferably from 5% to 50% by weight and better still from 10% to 40% by weight of surfactant(s), relative to the total weight of the said pre
- composition of the invention preferably contains from 1 % to 40% by weight, preferably from 2% to 20% by weight and better still from 5% to 20% by weight of surfactant(s), relative to the total weight of the said composition.
- the final composition preferably contains from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1 % to 10% by weight of surfactant(s), relative to the total weight of the said final composition.
- water or the aqueous phase preferably contains from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1 % to 10% by weight of surfactant(s), relative to the total weight of the said final composition.
- composition according to the invention and the final composition in the event of supplementary addition of water, as defined previously, comprise water.
- This water constitutes all or part of an aqueous phase.
- aqueous phase means a phase which comprises essentially water, and also comprises other ingredients that are water-miscible or water-soluble at room temperature and at atmospheric pressure.
- polar or polar protic organic solvents as defined below, salts of mineral or organic acids or bases, or water-soluble cosmetic active agents.
- the predispersion of the invention contains water preferably in an amount ranging from 5% to 50% by weight, better still from 7% to 40% and particularly from 8% to 20% by weight relative to the total weight of the said composition.
- composition of the invention contains water preferably in an amount ranging from 3% to 40% by weight, better still from 5% to 20% and particularly from 7% to 15% by weight relative to the total weight of the said composition.
- the final composition contains water preferably in an amount ranging from 20% to 90% by weight, better still from 30% to 80% and particularly from 50% to 70% by weight relative to the total weight of the said final composition.
- the ready-to-use composition and/or the predispersion and/or, where appropriate, the intermediate composition of the invention may comprise one or more organic solvents.
- organic solvents include Ci-C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
- the organic solvents are present in proportions preferably of between 0.1 % and 20% by weight approximately and even more preferentially between 0.5% and 10% by weight approximately relative to the total weight of the composition under consideration.
- Adjuvants preferably of between 0.1 % and 20% by weight approximately and even more preferentially between 0.5% and 10% by weight approximately relative to the total weight of the composition under consideration.
- composition according to the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents other than the fatty substances of the invention, for instance ceramides, film-forming agents, preserving agents, opacifiers and mineral or organic thickeners such as clays.
- adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispers
- the above adjuvants are generally present in an amount for each of them of between 0.01 % and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition under consideration.
- composition according to the invention may also contain one or more additional direct dyes other than ingredient i) as defined previously.
- direct dyes are chosen, for example, from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than henna or indigo, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine and methine cyanine direct dyes, and fluorescent dyes.
- aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than henna or indigo, neutral, acidic or cationic quinone and in particular anthraquinone
- the composition according to the invention may comprise one or more natural dyes other than i) as defined previously.
- natural direct dyes mention may be made of juglone, isatin, curcumin, spinulosin, apigenidin and orceins, in defined compound form.
- These natural dyes may be added in the form of extracts or of plant parts.
- the said defined compounds from extracts or from plant parts are preferably in the form of powders, in particular fine powders whose particles have sizes identical to that of the red henna and/or indigo powder i) as defined previously.
- the natural or non-natural direct dye(s) different from i) particularly represent from 0.001 % to 10% by weight and even more preferentially from 0.05% to 5% by weight relative to the total weight of the composition of the invention or, where appropriate, of the final composition.
- the compositions of the invention do not contain any synthetic direct dyes, i.e. dyes that do not occur in nature.
- composition according to the invention may also comprise one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibres.
- oxidation bases mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
- couplers mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
- the oxidation base(s) present in the composition of the invention are each generally present in an amount of between 0.001 % and 10% by weight relative to the total weight of the dye composition(s).
- the composition according to the invention the final composition in the event of supplementary addition of water and the predispersion do not contain any oxidation dyes. pH of the compositions and of the predispersion
- the pH of the composition of the invention and/or, where appropriate, of the final composition is neutral, i.e. it has a pH of about 7.
- the composition of the invention and/or, where appropriate, the final composition of the invention are acidic and preferably have a pH ranging from 3 to 6.5.
- the pH of the composition may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres or alternatively with the aid of standard buffer systems, or of clays present in the composition, in the preemulsion or in the aqueous phase is added to make the poultice as defined previously.
- acidifying agents for the compositions used in the invention examples include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids; the acid is preferably an organic acid such as citric acid.
- this alkaline agent is chosen from aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine or triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (II) below:
- W is a CrC 6 alkylene group such as propylene, optionally substituted with a hydroxyl group or a C1-C4 alkyl radical;
- R a , R b , R c and R d which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.
- the ready-to-use composition of the invention does not contain any "mordants”, i.e. metal salts conventionally used in "mordanting” (see for example Ullmann's Encyclopedia of Industrial Chemistry ("Textile Dyeing", Herbert Leube et al., DOI: 10.1002/14356007. a26_351 , and in particular point 4.8.2, p. 72; ibid, "Metal-complex dyes", Klaus Gryschtol et al., DOI: 10.1002/14356007.a16_299).
- the composition of the invention contains at least one "mordant", i.e. metal salts conventionally used in "mordanting” as defined above.
- the metal salt(s) are chosen from iron, copper, zinc, manganese, etc.
- the metal salt(s) are preferably in the predispersion as defined previously.
- composition according to the invention is characterized by its preparation method, which consists in mixing the ingredient(s) as defined previously in a dispersion that is being prepared beforehand, also known as a "predispersion”, preferably a “preemulsion”, as defined previously, and which comprises the ingredients i) to iv) as defined previously.
- Supplementary water may be added to the composition of the invention especially to make the composition of the invention more creamy or more easy to apply.
- the mixing of the predispersion with the ingredient(s) i) may be performed at time of use without addition of water to give the composition of the invention.
- This composition may optionally be stored and used at the time of use with addition of water, preferably hot water (temperature between 30°C and 80°C).
- the mixing of the predispersion with the ingredient i) may be performed at the time of use with addition of water, preferably hot water (temperature between 30°C and 80°C) to give the final composition.
- the henna and/or indigo powder, ingredient i) of the invention is mixed sparsely with or dispersed in the predispersion in a ratio of ingredient i) and of predispersion ranging from 0.015 part to 0.5 part of ingredient i) by weight per 1 part by weight of predispersion.
- the ratio of ingredient i) and the predispersion is greater than 0.5 part by weight of ingredient i) per 1 part by weight of predispersion, and preferably the ratio is inclusively between 0.6 and 3 parts by weight of ingredient i) per 1 part by weight of predispersion, more preferentially 2 parts by weight of i) per 1 part by weight of predispersion.
- the composition obtained is pasty and the ingredient i) is coated with the predispersion.
- the weight ratio of the mixture of the predispersion/ingredient i) and of the additional water preferably ranges from 0.1 to 2 parts and better still from 0.5 to 1 part of mixture per 1 part of additional water.
- compositions of the invention are cosmetic, i.e. they are cosmetically acceptable and are therefore suitable for use for application to keratin fibres.
- the composition of the invention or, where appropriate, the final composition are in non-compact galenical forms, such as a lotion, a mousse, a cream or a gel, or in any other form that is suitable for dyeing keratin fibres.
- these compositions are in the form of a poultice with a pleasant, creamy consistency.
- one or more identical or different clays may be added.
- the predispersion is a preemulsion and is preferably in the form of a microemulsion or nanoemulsion and/or contains the following ingredients:
- the predispersion is a preemulsion which is in the form of a microemulsion or nanoemulsion and/or which contains the following ingredients: Ingredients Commercial name
- Behenyltrimethylammonium chloride (cationic Behentrimonium chloride surfactant)
- the predispersion is a preemulsion which is in the form of a microemulsion or nanoemulsion and/or which contains the following ingredients:
- the predispersion is a preemulsion which is in the form of a microemulsion or nanoemulsion and/or which contains the following ingredients:
- the dyeing process is performed in several steps:
- the first step consists in preparing composition (la) of the invention, i.e. the composition obtained by mixing at the time of use the ingredient i) as defined previously with the predispersion as defined previously optionally with supplementary addition of water to give the final composition (lla);
- composition (la) or (lla) is applied to the keratin fibres and is left on the said fibres preferably for a minimum time of 30 minutes, preferentially a time ranging from 30 minutes to 24 hours and better still ranging from 1 hour to 12 hours;
- the keratin fibres are rinsed with water until the poultice has disappeared, preferably without shampooing;
- the keratin fibres may then be dried or left to dry naturally, without a hairdryer.
- the dyeing process is performed in several steps:
- the first step consists in preparing composition (la) or (lla) of the invention as described previously;
- composition (la) or (lla) is left to stand for several hours, preferably 24 hours, and is then applied preferably in the form of a poultice and left on the said fibres preferably for a minimum time of 30 minutes (preferably ranging from 30 minutes to 24 hours and better still from 1 hour to 12 hours);
- the keratin fibres are rinsed with water until composition (la) or (lla) has disappeared, preferably without shampooing;
- the keratin fibres may then be dried or left to dry naturally, without a hairdryer.
- the keratin fibres are:
- heat sources include a hairdryer, hairdrying hoods, a hair-straightening iron, an infrared ray dispenser and other standard heating appliances.
- the application temperature for composition (la) or (lla) ranges from room temperature (15 to 25°C) to 80°C and more particularly from 15 to 45°C.
- the head of hair may advantageously be subjected to a heat treatment by heating to a temperature ranging from 30 to 60°C.
- this operation may be performed using a styling hood, a hairdryer, an infrared ray dispenser or other standard heating appliances.
- Use may be made, both as means for heating and straightening the hair, of a heating iron at a temperature ranging from 60 to 220°C and preferably from 120 to 200°C.
- a specific form of the invention relates to a dyeing process which is performed at room temperature (25° C).
- each of these processes may be followed by another dyeing process P1 or P2 comprising as ingredient i) indigo; and vice versa, i.e. irrespective of the dyeing process P1 or P2 as defined previously, if ingredient i) used is indigo, each of these processes may be followed by another dyeing process P1 or P2 comprising as ingredient i) henna powder.
- the dyeing process may take place, for example, in three different ways.
- Henna and/or indigo powder (1 part) is mixed with the predispersion (0.5 part) and with water at a temperature of between 40 and 98°C (2.5 parts) in a bowl, and the whole is then mixed for the time required to obtain a creamy poultice.
- the poultice is then applied to the head for a minimum time of 30 minutes (preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours) before rinsing without shampooing, and the hair is then dried.
- Henna and/or indigo powder (1 part) is mixed with the predispersion (0.5 part) and with water at a temperature of between 10 and 40°C (2.5 parts) in a bowl, and the whole is then mixed for the time required to obtain a creamy poultice.
- the poultice is then applied to the head for a minimum time of 30 minutes (preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours) before rinsing without shampooing, and the hair is then dried.
- the cream cationic preemulsion as a nanoemulsion or microemulsion or emulsion, i.e. comprising at least one cationic surfactant as defined previously
- henna and/or indigo powder is applied to the head for a minimum time of 30 minutes (preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours) before rinsing without shampooing, and the hair is then dried.
- the application temperature of the composition comprising i) to iv) to the keratin fibres ranges from room temperature (15 to 25°C) to 80°C and more particularly from 15 to 45°C.
- the head of hair may advantageously be subjected to a heat treatment by heating to a temperature ranging from 30 to 60°C.
- this operation may be performed using a styling hood, a hairdryer, an infrared ray dispenser or other standard heating appliances.
- process of the invention is performed according to the following two processes:
- a composition preferably in the form of a poultice containing henna and/or indigo- producing plant(s) in an amount of 1 part by weight and water at a temperature inclusively between 40 and 98°C for an amount of 2-3 parts by weight i) is applied to the head for a minimum time of 30 minutes, preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours, followed by ii) rinsing preferably without shampooing, and then iii) the hair is dried; next, iv) a heating iron at a temperature inclusively between 100 and 230°C and preferably between 130 and 180°C is used along the length of the head of hair;
- a composition preferably in the form of a poultice containing henna and/or indigo- producing plant(s) in an amount of 1 part by weight and water at a temperature inclusively between 10 and 40°C for an amount of 2-3 parts by weight i) is applied to the head for a minimum time of 30 minutes, preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours, followed by ii) rinsing preferably without shampooing, and then iii) the hair is dried; next, iv) a heating iron at a temperature between 100 and 230°C and preferably between 130 and 180°C is used along the length of the head of hair.
- a specific form of the invention relates to a dyeing process which is performed at room temperature (25° C).
- all the ingredients used in the process are of natural origin, and preferably of plant origin.
- the evaluation of the coloration can be done visually or read on a spectrocolorimeter (such as Minolta CM3600d, illuminant D65, angle 10°, SCI values) for the L * , a * , b * colorimetric measurements.
- L * represents the intensity of the color
- a * indicates the green/red color axis
- b * indicates the blue/yellow color axis.
- the lower the value of L the darker or more intense the color.
- the higher the value of a * the redder the shade; the higher the value of b * , the yellower the shade.
- ⁇ * corresponding to the colour uptake on keratin fibers, according to the following equation:
- L * , a * and b * represent the values measured after dyeing the natural hair comprising 90% of white hairs and L 0 * , a 0 * and b 0 * represent the values measured for the untreated natural hair comprising 90% of white hairs.
- L * , a * and b * represent the values measured after dyeing the natural hair comprising 90% of white hairs and L 0 * , a 0 * and b 0 * represent the values measured after dyeing the permed or sensibilised hair.
- the lowest ⁇ * the best homogeneity of the hair color.
- ⁇ * is also calculated for the L 0 * , a 0 * , b 0 * and L * , a * , b * measured of the locks before and after exposure to the light, respectively.
- compositions were prepared as follows:
- the percentages are indicated on a weight basis relative to 100 g of composition.
- composition A Active material 1 part of composition A is mixed with 0.5 part of composition B or C and 2.5 parts of warm water at 37°C in a bowl, or in cold water ( 0°C), and .5 parts of composition D were mixed with 2.5 parts of warm water at 37°C, or in cold water at 10°C. The mixing takes place easily even in cold water.
- the poultices obtained are very creamy and are easy to apply to keratin fibres, totally impregnating the keratin fibres from the root to the end.
- the poultice is applied to 90% grey hair, with a leave-on time of 30 minutes.
- the hair is rinsed thoroughly.
- the hair is dried.
- compositions B and C A strong coppery aesthetic coloration is obtained with compositions B and C, and a blue- green coloration with composition D.
- the hair is smooth and soft, and the coloration is very uniform from one fibre to another and from the root to the end.
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Abstract
The invention relates to a composition for dyeing keratin fibres, comprising i) at least % and preferably at least 5% of red henna (Lawsonia inermis, alba) powder and/or of powder of indigo-producing plant(s), ii) at least one oil, iii) optionally at least one surfactant, and iv) water or an aqueous phase, preferably water, it being understood that the ingredients 10 ii), iii) and iv) are predispersed together to form a predispersion and the ingredient(s) i) are then mixed into the said predispersion or the said predispersion is mixed with the ingredient(s) i); the invention also relates to a composition comprising the said composition and a supplement of water or of aqueousphase, the process for dyeing keratin fibres using the said compositions, and to the use of the said compositions for dyeing keratin fibres.1 The compositions and the poultice according to the invention make it possible to dye keratin fibres with strong, chromatic dyeing results that are resistant to washing, perspiration, sebum and light, and that are moreover long-lasting, without impairing the said fibres. Furthermore, the use of the compositions or of the poultice does not give off any raw material 20 dust (dust-free). These compositions are easy to use, in total safety and with no risk of staining. In addition, the composition and the dyeing active agent(s) remain stable on storage. The treated keratin fibres have a very pleasant cosmetic aspect, their integrity is respected.
Description
COMPOSITION BASED ON HENNA OR INDIGO POWDER WITH A PREDISPERSION OF OIL, AND HAIR DYEING PROCESS USING THIS COMPOSITION
The invention relates to a composition for dyeing keratin fibres, comprising i) at least 1 % and preferably at least 5% of red henna (Lawsonia inermis, alba) powder and/or of powder of indigo-producing plant(s), ii) at least one oil, iii) optionally at least one surfactant, and iv) water or an aqueous phase, preferably water, it being understood that the ingredients ii), iii) and iv) are predispersed together and the ingredient(s) i) and the said predispersion are then mixed together; the invention also relates to a composition comprising the said composition and a supplement of water or of aqueous phase, the process for dyeing keratin fibres using the said compositions, and to the use of the said compositions for dyeing keratin fibres.
Two major methods for dyeing human keratin fibers, and in particular the hair, are known.
The first, known as oxidation dyeing or permanent dyeing, consists in using one or more oxidation dye precursors, more particularly one or more oxidation bases optionally combined with one or more couplers.
Oxidation bases are usually selected from ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, can give rise via a process of oxidative condensation to coloured species, which remain trapped within the fibre.
The shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen especially from aromatic meta- diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.
The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.
The second dyeing method, known as direct dyeing or semipermanent dyeing, comprises the application of direct dyes, which are coloured and colouring molecules that have affinity for fibres. Given the nature of the molecules used, they tend rather to remain on the surface of the fibre and penetrate relatively little into the fibre, when compared with the small molecules of oxidation dye precursors. The main advantages of this type of dyeing are that it does not require any oxidizing agent, which limits the degradation of the fibres, and that it does not use any dyes that have particular reactivity, resulting in limitation of the intolerance risks.
The first hair dyes were semi-permanent. One of the most well known natural dyes is that derived from the henna plant. Henna is still be used in feminine beauty enhancement for colouring the hair or the nails, or for dyeing leather, silk and wool, etc. It is also be used traditionally for various important events, celebrations and beliefs.
Red henna consists of leaves of shrubs of the genus Lawsonia from the family of Lythraceae, which is based on the principle of dyeing with the active agent lawsone: 2- hydroxy-1 ,4-naphthoquinone. Lawsone [83-72-7] (CI Natural Orange 6; CI 75420), also known as isojuglone, may be found in henna shrubs (Lawsonia alba, Lawsonia inermis) ("Dyes, Natural", Kirk-Othmer Encyclopedia of Chemical Technology, "Henna" Encyclopedia Britannica).
This dye affords an orange-red coloration on grey hair, and a "warm" i.e. coppery to red colour on chestnut-brown hair. The dyeing process using henna is difficult to perform. A kind of "paste" (often referred to as a "poultice") is first made from ground or powdered henna leaves, which is then diluted at the time of use with warm water, and the said paste is then applied to the keratin fibres.
However, this process using the said paste has drawbacks. During the preparation and application of the composition to keratin fibres, it is not always possible to obtain satisfactory impregnation due to the poor consistency of the composition obtained from the coarsely ground powder. Furthermore, it is very difficult to hope to reproduce shades exactly, since the lawsone content very often varies from one batch to another and between different ground materials.
Another very well-known natural dye is indigo (see Ullmann's Encyclopedia of Industrial Chemistry, Hair preparation, point 5.2.3, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; 10.1002/14356007.a12 571.pub2). Indigo continues to be used for feminine beauty by dyeing the hair or the nails, or for dyeing fabrics (jeans), leather, silk, wool, etc. Indigo [482-89-3] is a natural dye, originating especially from the indigo plant, and having the empirical formula: Ci6H10N2O2; and having the structure:
Indigo is derived from indican and may be prepared from various plants known as indigo-producing plants such as Indigofera tinctoria, Indigo suffruticosa, Isatis tinctoria, etc. (see Kirk-Othmer Encyclopedia of Chemical Technology, updated on 17/04/2009, DOI: 10.1002/0471238961.0425051903150618.a01.pub2). The indigo-producing plants are generally chopped and soaked in hot water, heated, fermented and oxidized in the open air to liberate the purple-blue coloured indigo (see Chem. Rev. 201 1 , 111 , 2537-2561 , pp. 2537-2561 ). Indigo is the result of the fermentation and then oxidization of indican (glycosyl precursor). The indigo molecule is insoluble in water.
The problem is that dyeing using the indigo plant is difficult because the uptake of the colour into the keratin fibres is very poor. This dye affords a blue coloration on grey hair, and a "cold" colour of ash to violet colour on chestnut-brown hair. The dyeing process using
indigo leaves is difficult to perform. A kind of "paste" (often referred so as a poultice) is first made from ground or powdered leaves of indigo plant (or Indian indigo or dyer's indigo) or dyer's pastel (Isatis tinctoria), which needs to have been fermented, and which is then diluted at the time of use with warm water, and the said paste is then applied to the keratin fibres. However, this process using the said paste has drawbacks. During the preparation and application of the composition to keratin fibres, it is not always possible to obtain satisfactory impregnation due to the poor consistency of the composition obtained from the coarsely ground powder. Furthermore, it is very difficult to hope to reproduce shades exactly, since the indigo content very often varies from one batch to another and between different ground materials.
As much as the colour obtained on chestnut-brown hair has a natural look, grey hair is dyed an unaesthetic and unnatural orange colour with henna or blue colour with indigo ("Hair preparations", Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, Inc.). Furthermore, the colorations obtained are not uniform between the root and the end or from one fibre to another (The Science of Hair Care, C. Bouillon, J. Wilkinson, 2d Ed., CRC Press, Taylor & Francis Group; Boca Raton, London, pp. 236-241 (2005)).
Added to this are the risks of staining of clothing and the skin with henna or indigo during the preparation of the "paste" and also during its application to the keratin fibres, since the consistency is very irregular.
In addition, the leave-on time is very long with henna or indigo. It may vary from several tens of minutes to several hours (overnight) depending on the desired intensity, with no ability to control the result. The result varies as a function of the fibres to be dyed and of the indigo or henna raw material used.
It is known practice to use metal salts as mordants for improving the coloration of henna {Ullmann's Encyclopedia, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a12 571 .pub2 and US 2010/03133362). It is also known practice to use metal salts to improve the dyeing of indigo (vat dyes - see Chem. Rev. 201 1 , 111 , 2537- 2561 , pp. 2537-2561 ). The use of these agents requires great know-how, multiplies the steps of the process, is not always friendly towards the integrity of the fibre (cosmetically unfriendly) and may disrupt subsequent cosmetic treatments.
Another solution is to use dye powder, optionally in the presence of excipients in fine powder form (DE 195 48 291 ). Generally, these powders are conditioned in sachets or blister packs (DE 101 31 385). If the packaging of the said powder happens to become broken, a large amount of raw material is lost into the air and cannot be recovered. Added to the problem of the loss of raw material is that linked to the fineness of the particles for users. Specifically, in the form of a suspension, the particles in the atmosphere can cause respiratory problems or allergies such as rhinitis for the users, sellers of extracts or natural
dyeing professionals (Allergy, J. Scibilia, E. Galdi, G. Biscaldi, G. Moscato, 52, 231 -232, (1997)).
Another solution for improving the coloration using these natural dyes is to use very finely ground henna leaf powder, for example, optionally in the presence of excipients in powder form (DE 299 02 432). Generally, these powders are conditioned in sachets or blister packs. If the packaging of the dye powder happens to become broken, a large amount of raw material is lost into the air and cannot be recovered. Added to the problem of the loss of raw material is that linked to the pulverulence for users as indicated previously. Specifically, in the form of fine particles, henna or indigo becomes suspended in the atmosphere and can cause respiratory problems or allergies such as rhinitis for the users, sellers of extracts or natural dyeing professionals (Allergy, J. Scibilia, E. Galdi, G. Biscaldi, G. Moscato, 52, 231 - 232, (1997)).
To overcome the problem of the poor dyeing efficacy of natural dyes, it is known practice to "dope" coloration by adding direct dyes that are generally used in direct dyeing, such as nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, a pyridine, azine or triarylmethane direct dyes (DE 199 05 707, EP 0 806 199, JP 2010- 0001278). This option has the drawback for natural product users, or for partisans of "natural/bio" products, in that the coloration is partly performed using synthetic dyes. International patent application WO 97/39724 describes hair treatment compositions in solid form and compounds whose viscosity does not exceed 500 mPa.s. The proposed compositions cannot produce rapid or satisfactory colorations. Furthermore, the solid compositions do not always readily break down in water. In addition, the poultices derived from the compositions of the prior art are not always creamy and/or easy to apply.
There is thus a real need to develop dyeing processes that can produce powerful colorations using henna and/or indigo, while at the same time being friendly to the cosmetics of keratin fibres. In particular, there is a need to provide a henna- or indigo-based dyeing product that does not have the drawbacks mentioned above, especially a dust-free product that is easy to store, readily miscible (rapid breakdown) in water, and that can especially produce colorations that are less aggressive to the hair and at the same time that are resistant to external agents (light, bad weather or shampooing), and that are fast and homogeneous, while at the same time remaining powerful and chromatic. This aim is achieved with the present invention, a first subject of which is a composition comprising:
i) at least 1 % by weight and preferably at least 5% by weight of red henna powder and/or of powder of indigo-producing plant(s), relative to the total weight of the composition; ii) at least one oil, preferably of plant origin;
iii) optionally at least one surfactant, preferably a nonionic and/or anionic surfactant; and iv) water or an aqueous phase, preferably water;
it being understood that the ingredients ii), iii) and iv) are predispersed together to form a predispersion, and the ingredient(s) (i) are then dispersed in the said predispersion or the said predispersion is dispersed in the said ingredient(s) i).
Preferably, the predispersion comprising the ingredients ii), iii) and iv) is an emulsion of water-in-oil type. More particularly, the predispersion is a microemulsion or even a nanoemulsion, preferably of water-in-oil type.
According to a particular embodiment of the invention, the above composition is a ready-to-use composition, i.e. it may be used as such at the time of use, without requiring supplementary addition of water. It may advantageously be in the form of a poultice.
According to a particular embodiment, the composition of the invention may be used subsequently, optionally after storage with or without subsequent addition of water.
A subject of the invention is also a process for preparing the preceding composition, which consists in preparing a predispersion comprising ingredients ii), iii) and iv) of the composition and then in mixing the ingredient(s) i) with the said predispersion.
A subject of the invention is also a process for dyeing keratin fibres, especially the hair, using the composition as defined previously.
The compositions and the process using the composition according to the invention have the advantage of dyeing keratin fibres, especially human keratin fibres, with strong, chromatic colorations that are resistant to washing, perspiration, sebum and light, and that are moreover long-lasting, without impairing the said fibres. Furthermore, the colorations obtained using the composition and the process give uniform colours from the root to the end of a fibre (little coloration selectivity). Furthermore, the application of the composition does not give off any raw material dust (dust-free). The composition is easy to use, in total safety and with no risk of staining. In addition, the composition and the active agent(s) (henna and/or indigo natural dyes) remain stable on storage. The treated keratin fibres have a very pleasant cosmetic aspect, their integrity is respected.
In addition, the composition or the poultice derived from the composition as defined below of the invention is particularly creamy and/or shows excellent adhesion to the hair.
Unless otherwise mentioned in the invention, the term "at least one..." means "one or more...";
the ranges of values of the invention inclusively comprise the indicated limits in the said ranges. i) red henna powder and/or indigo
According to a particular embodiment of the invention, the composition comprises as first ingredient i) red henna in powder form, preferably as fine particles.
The henna powder may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US).
According to one particular mode of the invention, the size of the henna powder particles is fine. According to the invention, a particle size of less than or equal to 500 μηη is more particularly intended. Preferentially, the powder consists of fine particles with sizes inclusively between 50 and 300 μηη and more particularly between 10 and 200 μηη.
It is understood that the said henna particles preferentially have a moisture content of between 0 and 10% by weight relative to the total weight of the powders.
Where appropriate, the composition according to the invention comprises red hen a powder in an amount ranging from 1 % to 85% by weight, relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and more particularly from 10% to 75% relative to the total weight of the composition.
In the event of supplementary addition of water, the final composition comprises red hen a powder in an amount ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition. According to another particular embodiment of the invention, the composition comprises as first ingredient i) a powder of indigo-producing plant(s), preferably as fine particles.
As indigo-producing plants, mention may be made of numerous species derived from the following genera:
- Indigofera such as Indigofera tinctoria, Indigo suffraticosa, Indigofera articulata
Indigofera arrecta, Indigofera gerardiana, Indigofera argenta, Indigofera indica, Indigofera longiracemosa;
- Isatis such as Isatis tinctoria;
- Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria);
- Wrightia such as Wrightia tinctoria;
- Calanthe such as Calanthe veratrifolia; and
- Baphicacanthus such as Baphicacanthus cusia.
Preferably, the indigo-producing plant is of the genus Indigofera and more particularly is Indigofera tinctoria.
Use may be made of all or part (in particular the leaves especially for Indigofera tinctoria) of the indigo-producing plant.
The indigo-producing plant powder may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US).
According to a particular mode of the invention, the size of the indigo-producing plant powder particles is fine. According to the invention, a particle size of less than or equal to 500 μηη is more particularly intended. Preferentially, the powder consists of fine particles with sizes inclusively between 50 and 300 μηη and more particularly between 10 and 200 μηη.
It is understood that the said indigo-producing plant particles preferentially have a moisture content of between 0 and 10% by weight relative to the total weight of the powders.
Where appropriate, the composition according to the invention comprises indigo- producing plant powder in an amount ranging from 1 % to 85% by weight, relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and preferentially from 10% to 75% relative to the total weight of the composition.
In the event of supplementary addition of water, the final composition comprises indigo- producing plant powder in an amount ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition.
According to another advantageous embodiment of the invention, the composition comprises as first ingredient i) a mixture of red henna powder as defined previously and of indigo-producing plant powder, preferably as fine particles, as defined previously.
Where appropriate, the composition according to the invention comprises the mixture of powders in an amount ranging from 1 % to 85% by weight, relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and preferentially from 10% to 75% relative to the total weight of the composition.
In the event of supplementary addition of water, the final composition comprises the mixture of powders in an amount ranging from 1 % to 80% by weight, relative to the total weight of the composition, more particularly ranging from 1 % to 75% by weight, preferentially ranging from 2% to 70% by weight and better still from 10% to 70% relative to the total weight of the final composition. Predispersion, emulsion, microemulsion and nanoemulsion
The predispersion of the invention uses the ingredients ii) and iv), and optionally iii), as defined below, which are thus predispersed.
The term "predispersed" means that the ingredients ii), iv) and optionally iii) are mixed with iv) water or the aqueous phase of the composition of the invention so as to obtain a "dispersion", which is preferably stable at room temperature and at atmospheric pressure, before being mixed with the ingredient i), and with the optional remainder of water, the said predispersion possibly containing the optional ingredients as described below.
When the predispersion comprises at least one surfactant, it will be referred to as a preemulsion.
For the purposes of the present invention, the term "dispersed" means that the solid ingredient (such as the ingredient i)) is distributed in the mixture of ingredients ii), iv) and optionally iii) without being dissolved. For the purposes of the invention, the term "emulsion" means the mixture of a liquid
(such as the oils: ingredient ii)) with another immiscible liquid (such as water: ingredient iv) or an aqueous phase) preferably in the presence of an emulsifier (such as the surfactants, ingredient iii)), one of which is finely distributed in the other as droplets (see "Emulsions", Kirk-Othmer Encyclopedia of Chemical Technology, Edward Kostansek, published Online on 13/07/2012, DOI: 10.1002/0471238961 .051321 1206180902.a01.pub3).
The mean size of the droplets of the emulsion according to the invention is preferably between 10 nm and 100 μηη and preferably between 20 nm and 50 μηη. This is the mean diameter D(3.2), which may be measured especially using a laser particle sizer.
When the emulsion droplets size is less than or equal to 200 nm, these emulsions will be referred to as nanoemulsions or microemulsions, the first being thermodynamically unstable and the second being thermodynamically stable.
The emulsion may be direct, i.e. of oil-in-water (O/W) type, and the emulsion is then in the form of an aqueous continuous phase (or outer phase) in which is distributed a discontinuous fatty phase (or inner phase: oil + optionally solid fatty substances).
According to another preferred embodiment of the invention, the emulsion has a mean size of greater than 200 nm, and is an inverse emulsion, i.e. of water-in-oil (W/O) type, the emulsion then being in the form of a continuous fatty phase (or outer phase: oil + optionally solid fatty substances) in which is distributed a discontinuous aqueous phase (or inner phase).
The emulsion of the invention is prepared via standard processes for preparing emulsions or dispersions, which are well known to those skilled in the art (see, for example, 'Emulsions", Kirk-Othmer Encyclopedia of Chemical Technology, Edward Kostansek, published Online on 13/07/2012, DOI: 10.1002/0471238961.051321 1206180902.a01.pub3, point 3 "Preparation").
The microemulsions may be obtained by simple hot or cold mixing of the water, oils and surfactants, provided that the mixing lies within the correct zone of the phase diagrams.
The nanoemulsions are obtained via standard methods known to those skilled in the art
(see, for example, J. Phys.: Condens. Matter, "Nanoemulsions: formation, structure, and physical properties", T.G. Mason et al., 18, 635-666 (2006)).
The production of the nanoemulsions may take place by lying within adequate zones of the phase diagrams and using powerful stirring devices such as high-pressure homogenizers.
It may also be performed via phase inversion techniques that are well known to those skilled in the art.
Preferably, the preemulsion according to the invention is a preemulsion of water or of aqueous phase in oil, i.e. of W/O type.
According to a particular embodiment, the predispersion of the invention is free of any surfactant. For the purposes of the present invention, the term "free of surfactants" means free of any non-polymeric compound with an HLB value of greater than or equal to 1 .
According to another advantageous embodiment of the invention, the predispersion comprises at least one surfactant, i.e. the ingredient iii) as defined previously. It is then referred to as a preemulsion as indicated above.
According to another variant, the predispersion comprises at least one stabilizing polymer compound, which is preferably silylated, such as those based on polydimethylsiloxane PDMS and/or on SMDI and polyalkylene glycol, especially polyethylene glycol and polypropylene glycol. This or these stabilizing polymer compound(s) may represent from 0.1 % to 20%, preferably from 0.5% to 15% by weight and better still from 1 % to 10% by weight, relative to the total weight of the said predispersion.
Preferably, the ready-to-use composition applied to the keratin fibres is not a compact solid.
//) the oil(s)
The composition of the invention, the final composition in the event of supplementary addition of water or the predispersion comprise one or more oils preferably of plant origin.
The term "o/7" means a "fatty substance" that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg). The viscosity at 25°C is preferably less than 1200 cps and better still less than 500 cps (defined, for example, from the Newtonian plateau determined using an ARG2 rheometer from TA Instruments equipped with a spindle with cone-plate geometry 60 mm in diameter and with an angle of 2 degrees over a shear stress range of from 0.1 Pa to 100 Pa).
The term "fatty substance" means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They have in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
More particularly, the oils are chosen from non-silicone oils and in particular C6-Ci6 hydrocarbons or hydrocarbons containing more than 16 carbon atoms and in particular alkanes; oils of animal origin; triglyceride oils of plant origin; essential oils; fluoro oils or glycerides of synthetic origin, fatty alcohols; fatty acid and/or fatty alcohol esters other than triglycerides, and silicone oils.
Preferably, the oils do not comprise any C2-C3 oxyalkylene units or any glycerolated units.
Preferably, the oils are not fatty acids which, in salified form, give water-soluble soaps. The oils that may be used as second ingredient ii) in the composition in accordance with the invention may be silicones.
The silicones may be volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified with organic groups, having a viscosity from 5x10"6 to 2.5 m2/s at
25°C, and preferably 1 *10"5 to 1 m2/s.
Preferably, the silicone is chosen from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMSs), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amino groups and alkoxy groups.
Organopolysiloxanes are defined in greater detail in Walter Noll's "Chemistry and
Technology of Silicones" (1968), Academic Press. They may be volatile or non-volatile.
When they are volatile, the silicones are more particularly chosen from those with a boiling point of between 60°C and 260°C, and even more particularly from:
(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
These are, for example, octamethylcyclotetrasiloxane sold in particular under the name
Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union
Carbide, and Silbione® 70045 V5 by Rhodia, and mixtures thereof.
Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone® FZ 3109 sold by the company Union Carbide, of formula:
I— D"— D' D" - D' -
CH CH, with D": — Si - O— with D': - Si - O—
I I
CH, C8H17
Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 ,1 '-(hexa-2,2,2',2',3,3'-trimethylsilyloxy)neopentane;
(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10-6 m2/s at 25°C. An example is
decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers, "Volatile Silicone Fluids for Cosmetics".
Use is preferably made of non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the organofunctional groups above, and mixtures thereof.
These silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups. The viscosity of the silicones is measured at 25°C according to ASTM
Standard 445 Appendix C.
Among these polydialkylsiloxanes, mention may be made, in a nonlimiting manner, of the following commercial products:
- the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000;
- the oils of the Mirasil® series sold by the company Rhodia;
- the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm2/s;
- the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
Mention may also be made of polydimethylsiloxanes possessing dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as oils of the 48 series from Rhodia.
The fatty alcohols, acids, amides and esters that may be used as second ingredient ii) in the composition in accordance with the invention are in the form of oils.
It is recalled that, for the purposes of the invention, fatty alcohols, amides, esters and acids, which are liquid (oils), more particularly have at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising 6 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
More precisely, the ingredient ii) may represent an ester of a C-I-C-IO alcohol and of a C6-C3o fatty acid such as R-C(0)-0-R' with R representing a linear or branched C6-C3o alkyl or linear or branched C6-C30 alkenyl group, comprising one or two unsaturations, and R representing a linear or branched C1-C10 alkyl group.
Preferentially, R represents a linear C10-C20 alkyl group and R' represents a Ci-C6 alkyl group that is preferably branched, such as isopropyl myristate.
According to another advantageous variant, the ingredient ii) represents one or more amides of a C6-C3o fatty acid and of a primary or secondary, preferably primary, C1-C10 amine, such as those of formula R"-C(0)-N(Ra)-R"' with R" representing a linear or branched C6-C30 alkyl or linear or branched C6-C30 alkenyl group, comprising one or two unsaturations,
which may be substituted with one or more hydroxyl groups, or (di)(Ci-C6)(alkyl)amino, and '" representing a linear or branched C1-C10 alkyl group, Ra representing a hydrogen atom or an alkyl group as defined for R'". Preferably, R" represents a C14-C20 alkenyl group, Ra represents a hydrogen atom and R'" represents a Ci-C6 alkyl group optionally substituted with (di)(Ci-C4)(alkyl)amino such as oleylamidopropyldimethylamine.
As regards the C6-Ci6 alkanes, they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane. The linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam®.
Among the animal oils, mention may be made of perhydrosqualene.
Among the triglycerides of plant or synthetic origin, mention may be made of liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
Among the fluoro oils, mention may be made of perfluoromethylcyclopentane and perfluoro-1 ,3-dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-(trifluoromethyl)perfluoromorpholine sold under the name PF 5052® by the company 3M.
Among the essential oils contained in the composition of the invention, mention may be made of those mentioned in Ullmann's Encyclopedia of Industrial Chemistry ("Flavors and Fragrances", Karl-Georg Fahlbusch et al., Published Online: 15 JAN 2003, DOI: 10.1002/14356007. a1 1_141 ). According to a preferred embodiment, the ingredient(s) ii) are other than essential oils.
According to a preferred variant of the invention, the oil(s) are chosen from C6-Ci6 alkanes, polydecenes, liquid esters of a fatty acid and/or of a fatty alcohol, and liquid fatty alcohols, or mixtures thereof. Better still, the fatty substance is chosen from liquid petroleum jelly, C6-Ci6 alkanes and polydecenes.
In this preferred variant, the oil(s) are chosen from mineral oils such as liquid petroleum jelly.
According to another most particularly advantageous mode of the invention, the oils, ingredient ii), are chosen from oils of natural origin and particularly oils of plant origin, such as jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, corn oil,
argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil and rapeseed oil.
Preferentially, the oil(s), ingredient ii), of the invention are chosen from sunflower oil, avocado oil, olive oil, sesame oil and jojoba oil, and are more preferentially chosen from avocado oil and sunflower oil.
According to a preferred mode of the invention, the above plant oils in are in a mixture with one or more esters of a C1-C10 alcohol and of a C6-C3o fatty acid such as R-C(0)-0-R' with R representing a linear or branched C6-C30 alkyl or linear or branched C6-C30 alkenyl group, comprising one or two unsaturations, and R representing a linear or branched C-I-C-IO alkyl group; preferentially, R represents a linear Ci0-C2o alkyl group and R' represents a preferably branched Ci-C6 alkyl group, such as isopropyl myristate.
According to another preferred mode of the invention, the above oils of plant origin are in a mixture with one or more amides of a C6-C30 fatty acid and of a primary or secondary, preferably primary, C-I-C-IO amine, such as those of formula R"-C(0)-N(Ra)-R"' with R" representing a linear or branched C6-C30 alkyl or linear or branched C6-C30 alkenyl group, comprising one or two unsaturations, which may be substituted with one or more hydroxyl groups, or (di)(Ci-C6)(alkyl)amino, and R'" representing a linear or branched C1-C10 alkyl group, Ra representing a hydrogen atom or an alkyl group as defined for R'". Preferably, R" represents a C14-C20 alkenyl group, Ra represents a hydrogen atom and R'" represents a Ci-C6 alkyl group optionally substituted with (di)(Ci-C4)(alkyl)amino such as oleylamidopropyldimethylamine.
Preferably, the oil(s) of the invention are non-silicone oils. The term "non-silicone o/V means an oil not containing any silicon atoms (Si) and the term "silicone o/V means an oil containing at least one silicon atom.
Preferably, the predispersion of the invention before addition of the ingredient(s) i) comprises from 30% to 90% by weight and preferably 40% to 75% by weight of one or more oils relative to the total weight of the said predispersion.
The composition according to the invention comprises from 1 0% to 85% by weight, preferably from 1 5% to 80% by weight and better still from 20% to 75% by weight of one or more oils relative to the total weight of the said composition.
In the event of supplementary addition of water, the composition comprises from 1 0% to 60% by weight, preferably from 1 5% to 50% by weight and better still from 20% to 40% by weight of one or more oils relative to the total weight of the said final composition.
Fatty substance other than oils: butters, waxes or resins
According to a particular embodiment of the invention, the composition of the invention, the final composition in the event of supplementary addition of water or the predispersion also comprise one or more fatty substances other than the oil(s) ii) as defined previously.
According to a particular embodiment of the invention, the composition comprises one or more butters, preferably of plant origin.
For the purposes of the present invention, the term "butter" (also known as a "pasty fatty substance") means a lipophilic fatty compound which undergoes a reversible solid/liquid change of state and which comprises, at a temperature of 25°C and at atmospheric pressure (760 mmHg), a liquid fraction and a solid fraction. In other words, the starting melting point of the pasty compound may be less than 25°C. The liquid fraction of the pasty compound, measured at 25°C, may represent 9% to 97% by weight of the compound. This liquid fraction at 25°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
Preferably, the butter(s) have an end melting point of less than 60°C.
Preferably, the butter(s) have a hardness of less than or equal to 6 MPa.
Preferably, the pasty fatty substances have, in the solid state, an anisotropic crystal organization, which is visible by X-ray observation.
For the purpose of the invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in Standard
ISO 1 1357-3; 1999. The melting point of a pasty substance or of a wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.
As regards the measurement of the melting point and the determination of the end melting point, the sample preparation and measurement protocols are as follows:
A sample of 5 mg of pasty fatty substance, preheated to 80°C and withdrawn with magnetic stirring using a spatula that is also heated, is placed in a hermetic aluminium capsule, or a crucible. Two tests are performed to ensure the reproducibility of the results.
The measurements are performed on the abovementioned calorimeter. The oven is flushed with nitrogen. Cooling is performed by an RCS 90 heat exchanger. The sample is then subjected to the following protocol: it is first placed at a temperature of 20°C, and then subjected to a first temperature rise passing from 20°C to 80°C, at a heating rate of 5°C/minute, then is cooled from 80°C to -80°C at a cooling rate of 5°C/minute and finally subjected to a second temperature rise passing from -80°C to 80°C at a heating rate of 5°C/minute. During the second temperature increase, the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of butter is measured as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
The end melting point corresponds to the temperature at which 95% of the sample has melted.
The liquid fraction by weight of the butter at 25°C is equal to the ratio of the heat of fusion consumed at 25°C to the enthalpy of fusion of the butter.
The heat of fusion of the pasty compound is the heat consumed by the compound in order to pass from the solid state to the liquid state. The butter is said to be in the solid state when all of its mass is in crystalline solid form. The butter is said to be in the liquid state when all of its mass is in liquid form.
The heat of fusion of the butter is equal to the integral of the entire melting curve obtained using the abovementioned colorimeter, with a temperature rise of 5 or 10°C/minute, according to Standard ISO 1 1357-3:1999. The heat of fusion of the butter is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
The heat of fusion consumed at 25°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 25°C, constituted of a liquid fraction and a solid fraction.
The liquid fraction of the butter measured at 32°C preferably represents from 30% to 100% by weight of the compound, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the compound. When the liquid fraction of the butter measured at 32°C is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
The liquid fraction of the butter measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound. The heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.
As regards the measurement of the hardness, the sample preparation and measurement protocols are as follows:
The composition according to the invention or the butter is placed in a mould 75 mm in diameter, which is filled to about 75% of its height. In order to overcome the thermal history and to control the crystallization, the mould is placed in a Votsch VC0018 programmable oven, where it is first placed at a temperature of 80°C for 60 minutes, then cooled from 80°C to 0°C at a cooling rate of 5°C/minute, and then left at the stabilized temperature of 0°C for 60 minutes, and then subjected to a temperature rise ranging from 0°C to 20°C, at a heating rate of 5°C/minute, and then left at the stabilized temperature of 20°C for 180 minutes.
The compression force measurement is taken using a TA TX2i texturometer from Swantech. The spindle used is chosen according to the texture:
- cylindrical steel spindle 2 mm in diameter for very rigid starting materials;
- cylindrical steel spindle 12 mm in diameter for sparingly rigid starting materials.
The measurement comprises three steps:
- a first step after automatic detection of the surface of the sample, where the spindle moves at a measuring speed of 0.1 mm/second, and penetrates into the composition according to the invention or the butter to a penetration depth of 0.3 mm, and the software notes the maximum force value reached;
- a second step, known as relaxation, where the spindle remains in this position for one second and the force is noted after 1 second of relaxation; and finally
- a third step, known as withdrawal, where the spindle returns to its original position at a speed of 1 mm/second, and the withdrawal energy of the spindle (negative force) is noted.
The hardness value measured during the first step corresponds to the maximum compression force measured in newtons divided by the area of the texturometer cylinder expressed in mm2 in contact with the butter or the composition according to the invention. The hardness value obtained is expressed in megapascals or MPa.
According to one preferred mode of the invention, the particular butter(s) are of plant origin, such as those described in Ullmann's Encyclopedia of Industrial Chemistry ("Fats and Fatty Oils", A. Thomas, published online: 15/06/2000, DOI: 10.1002/14356007.a10_173, point 13.2.2.2. Shea Butter, Borneo Tallow, and Related Fats (Vegetable Butters)).
Mention may be made more particularly of shea butter, Karite Nilotica butter (Butyrospermum parkii), galam butter, (Butyrospermum parkii), Borneo butter or fat or tengkawang tallow (Shorea stenoptera), shorea butter, illipe butter, madhuca butter or Bassia madhuca longifolia butter, mowrah butter (Madhuca latifolia), katiau butter (Madhuca mottleyana), phulwara butter (M. butyracea), mango butter (Mangifera indica), murumuru butter (Astrocaryum murumuru), kokum butter (Garcinia indica), ucuuba butter (Virola sebifera), tucuma butter, painya butter (Kpangnan) (Pentadesma butyracea), coffee butter (Coffea arabica), apricot butter (Prunus armeniaca), macadamia butter (Macadamia ternifolia), grapeseed butter (Vitis vinifera), avocado butter (Persea gratissima), olive butter (Olea europaea), sweet almond butter (Prunus amygdalus dulcis), cocoa butter (Theobroma cacao) and sunflower butter.
According to one preferred mode of the invention, the weight content of Ci6 fatty acid triglycerides, expressed relative to the total amount of fatty acid triglycerides in the butter(s) according to the invention, is less than 23%.
In one preferred variant of the invention, the weight content of Ci6 fatty acid triglycerides, expressed relative to the total amount of fatty acid triglycerides, ranges from 0 to 22%, better still from 0 to 15% and even better still from 2% to 12%.
Preferentially, the butter(s) according to the invention are chosen from murumuru butter, ucuuba butter, shorea butter, illipe butter, shea butter and cupuagu butter, and even more preferentially from murumuru butter and ucuuba butter. The waxes may be fatty alcohols or fatty esters that are solid at room temperature and at atmospheric pressure.
According to one particular embodiment of the invention, the composition comprises as third constituent one or more solid fatty alcohols.
The fatty alcohols that are suitable for use in the invention are more particularly chosen from linear saturated alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and a mixture thereof (cetearyl alcohol). As regards the solid fatty acid esters and/or fatty alcohols, mention may preferably be made of esters of saturated linear fatty acids and of saturated linear fatty alcohols, such as cetyl palmitate, stearyl stearate or cetyl stearate.
According to another particular embodiment of the invention, the composition comprises as third constituent one or more waxes, other than the fatty alcohols and fatty esters mentioned above, preferably of plant origin.
The non-silicone wax(es) are chosen in particular from carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite, plant waxes, such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute flower waxes, such as the blackcurrant blossom essential wax sold by Bertin (France), or animal waxes, such as beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy raw materials that can be used according to the invention are in particular marine waxes, such as that sold by the company Sophim under the reference M82, polyethylene waxes or polyolefin waxes in general. According to another particular embodiment of the invention, the composition comprises one or more silicone waxes, resins or gums.
In the category of polydialkylsiloxanes, mention may be made of the waxes sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are polydi(Cr C2o)alkylsiloxanes.
The silicone gums that may be used in accordance with the invention are especially polydialkylsiloxanes and preferably polydimethylsiloxanes with high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent. This solvent can be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane or tridecane, or mixtures thereof.
Products that can be used more particularly in accordance with the invention are mixtures such as:
- the mixtures formed from a hydroxy-terminated polydimethylsiloxane or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2 1401 sold by Dow Corning;
- mixtures of a polydimethylsiloxane gum and a cyclic silicone, such as the product SF 1214 Silicone Fluid from the company General Electric; this product is an SF 30 gum corresponding to a dimethicone, having a number-average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;
- mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is a mixture of a gum SE 30 defined above, with a viscosity of 20 m2/s and of an oil SF 96 with a viscosity of 5x10"6 m2/s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.
The organopolysiloxane resins that may be used in accordance with the invention are crosslinked siloxane systems containing the following units:
R2Si02/2, R3S1O1/2, RS1O3/2 and Si04/2,
in which R represents an alkyl containing 1 to 16 carbon atoms. Among these products, the ones that are particularly preferred are those in which R denotes a C C4 lower alkyl group, more particularly methyl.
Among these resins, mention may be made of the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid SS 4230 and SS 4267 by the company General Electric, which are silicones of dimethyl/trimethylsiloxane structure.
Mention may also be made of the trimethyl siloxysilicate type resins sold especially under the names X22-4914, X21 -5034 and X21 -5037 by the company Shin-Etsu.
Preferably, the fatty substance(s) other than the oil(s) ii) do not comprise any C2-C3 oxyalkylene units or any glycerolated units and are other than fatty acids.
Preferably, the fatty substance(s) other than the oil(s) ii) are chosen from butters.
The predispersion of the invention before addition of the ingredient(s) i) may comprise one or more fatty substances other than the oil(s) ii) in an amount ranging from 0.1 % to 50% by weight, more particularly from 1 % to 40% by weight, preferentially from 2% to 30% by weight and more preferentially from 3% to 20% by weight relative to the weight of the said predispersion.
The composition according to the invention may comprise one or more fatty substances other than the oil(s) ii) in an amount ranging from 0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and preferentially from 1 % to 10% by weight relative to the weight of the said composition.
In the event of supplementary addition of water, the final composition may comprise one or more fatty substances other than the oil(s) ii) in an amount ranging from 0.1 % to 20%
by weight, more particularly from 0.5% to 10% by weight and preferentially from 1 % to 5% by weight relative to the weight of the said final composition.
///') the surfactant(s)
According to a preferred embodiment, the composition of the invention, the final composition in the event of supplementary addition of water or the predispersion comprise one or more surfactants, i.e. ingredient(s) iii).
This or these surfactant(s) may be chosen from nonionic, anionic, cationic and amphoteric surfactants.
According to a particular embodiment of the invention, the ingredient iii) represents one or more amphoteric surfactants.
The amphoteric surfactant(s) that may be used in the present invention may be chosen especially from optionally quaternized secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
According to a particular embodiment of the invention, the ingredient(s) iii) are in the predispersion and/or the compositions of the invention and are chosen from the compounds of respective structures (B1) and (B2) below:
Ra-C(0)-N(Z)-CH2-(CH2)m-N+(Rb)(Rc)-CH2-C(0)-0-, M+, X (B1) (to be transferred into PR231 )
in which formula (B1):
· Ra represents a Ci0-C3o alkyl or alkenyl group derived from a carboxylic acid RaC(0)OH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
• Rb represents a β-hydroxyethyl group; and
• Rc represents a carboxymethyl group;
· M+ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine, and
• X" represents an organic or mineral anionic counterion, preferably chosen from halides, acetates, phosphates, nitrates, (CrC4)alkyl sulfates, (Ci-C4)alkyl- or (d- C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate;
• m is equal to 0, 1 or 2;
• Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group;
or alternatively M+ and X" are absent; Ra'-CiOJ-NiZJ-CHHCHz -NiBXB') (B2)
in which formula (B2):
• B represents the group -CH2-CH2-0-X';
• B' represents the group -(CH2)ZY\ with z = 1 or 2;
• X' represents the group -CH2-C(0)OH, -CH2-C(0)OZ\ -CH2-CH2-C(0)OH, -CH2-CH2- C(0)OZ', or a hydrogen atom;
· Y' represents the group -C(0)OH, -C(0)OZ\ -CH2-CH(OH)-S03H or the group -CH2-
CH(OH)-S03-Z';
• Z' represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• Ra' represents a Ci0-C3o alkyl or alkenyl group of an acid Ra C(0)OH preferably present in hydrolysed linseed oil or coconut oil, an alkyl group, in particular of Ci7 and its iso form, or an unsaturated Ci7 group.
• m' is equal to 0, 1 or 2;
• Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group.
The compounds of this type are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.
Examples that may be mentioned include the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate or under the trade name Miranol Ultra C 32 and the product sold by the company Chimex under the trade name Chimexane HA (to be transferred into PR231 ).
According to another particular embodiment of the invention, the ingredient(s) iii) are in the predispersion and/or the compositions of the invention and are chosen from the compounds of respective structure (B'2) below: Ra"-N(H)-CH(Y")-(CH2)n-C(0)-N(H)-(CH2)n -N(Rd)(Re) (B'2) in which formula (B'2):
• Y" represents the group -C(0)OH, -C(0)OZ", -CH2-CH(OH)-S03H or the group -CH2- CH(OH)-S03-Z";
• Rd and Re represent, independently of each other, a Ci-C4 alkyl or hydroxyalkyl radical;
• Z" represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• Ra" represents a Ci0-C30 alkyl or alkenyl group of an acid Ra"C(0)OH preferably present in coconut oil or in hydrolysed linseed oil;
· n and n' denote, independently of each other, an integer ranging from 1 to 3.
Among the compounds of formula (B'2), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.
According to a particular embodiment of the invention, the ingredient iii) represents one or more surfactants chosen from the compounds of formula (B3) and also the optional salts thereof with organic or mineral acids or bases, and solvates thereof such as hydrates:
· R1 denotes a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising from 6 to 100 carbon atoms and in particular from 6 to 50 carbon atoms, which may be interrupted with one or more heteroatoms, divalent groups, or combinations thereof chosen from -0-, -C(O)- and -N(R)-; with R denoting a hydrogen atom or a CrC4 alkyl radical, and R1 also possibly being interrupted with an arylene group or terminated with an aryl group;
• R2 and R3, which may be identical or different, in particular R2 and R3 are identical, denote a (CrC6)alkyl group; preferably, R2 and R3 represent a methyl group;
• R4 denotes a linear or branched, preferably linear, divalent hydrocarbon-based radical, comprising from 1 to 10 and preferably from 1 to 5 carbon atoms, optionally substituted in particular with one or more hydroxyl groups;
• Z denotes a heteroatom or a divalent group chosen from -O- and -N(R)- with R as defined previously,
• n denotes a number equal to 1 or 2;
• m denotes an integer equal to 0 or 1 ; · G- denotes an anionic radical chosen from carboxylates, sulfates, sulfonates, phosphates and phosphonates (*-C(0)-0", *-S(0)2-0", *-0-S(0)2-0", *-P(0)2-0", *- P(0)-02", *-P(OH)-0", **=P(0)-0" and **=P-0"; with "*-" denoting the point of attachment of the anionic radical to the rest of the molecule via Z or R4 when n is 1 , and "**=" representing the two points of attachment of the anionic radical via Z or R4 when n is 2); it being understood that:
- when n is 2, the radicals R1R2R3N+-R'-(Z)m- are identical or different, preferably identical; and
- the surfactant of formula (B3) being electrically neutral, it may comprise anionic and/or cationic counterions to produce the electrical neutrality of the molecule.
The term "unsaturated" hydrocarbon-based chain means a hydrocarbon-based chain which comprises one or more double bonds and/or one or more triple bonds, the said bonds possibly being conjugated or non-conjugated.
The term "alkyl radical' means a saturated, linear or branched hydrocarbon-based radical, preferably of Ci-C8.
The term "alkenyl radical means a linear or branched, preferably C2-C8, hydrocarbon- based radical; which is unsaturated, comprising one or more conjugated or non-conjugated double bonds.
The term "alkoxy radical means an alkyl-oxy radical for which the alkyl radical is a linear or branched C Ci6 and preferentially Ci-C8 hydrocarbon-based radical.
The term "aryP' radical means a fused or non-fused monocyclic or polycyclic carbon- based group comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl.
The term "arylene" radical means a fused or non-fused monocyclic or polycyclic carbon- based group comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially phenylene and more preferentially 1 ,3- or 1 ,4-phenylene;
The term "optionally substituted" attributed to the radical in question means that the said alkyl radical may be substituted with one or more radicals chosen from the following radicals: i) hydroxyl, ii) Ci-C4 alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different C1-C4 alkyl radicals, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom.
The term "organic or mineral acid salt" more particularly means salts chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H2S04, iv) alkylsulfonic acids: Alk-S(0)2OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(0)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-O- S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3P04; xiii) acetic acid CH3C(0)OH; xiv) triflic acid CF3S03H; and xv) tetrafluoroboric acid HBF4.
The term "organic or mineral base salt" more particularly means salts chosen from a salt derived from basifying agents as defined in "Additional basifying agents" hereinbelow.
The term "anionic counterion" means an anion or an anionic group derived from an organic or mineral acid salt which counterbalances the cationic charge of the dye; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii)
nitrates; iii) sulfonates, including Ci-C6 alkylsulfonates: Alk-S(0)20" such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: Ar-S(0)20" such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-0-S(0)0" such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-0-S(0)0" such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-O- S(0)20" such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-0-S(0)20", xiii) phosphates 0=P(OH)2-0" , 0=P(0")2-OH, 0=P(0")3, HO-[P(0)(0")]w-P(0)(0")2with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate (0=)2S(0")2 or S04 2" and monosulfate HS04 "; the anionic counterion, derived from an organic or mineral acid salt, ensures the electrical neutrality of the molecule; thus, it is understood that when the anion comprises several anionic charges, then the same anion can serve for the electrical neutrality of several cationic groups in the same molecule or else may serve for the electrical neutrality of several molecules; for example, a betaine surfactant which contains two positive charges either may contain two "singly charged" anionic counterions or may contain a "doubly charged" anionic counterion such as (0=)2S(0)2 or 0=P(0")2-OH.
In particular, the cationic counterion(s) are chosen from alkali metals such as Na or K or alkaline-earth metals such as Mg or Ca, or organic cations such as ammonium or mono/di/tri(Ci-C6)alkylammonium, and/or the anionic counterion(s) are chosen from halides such as chloride or alkylsulfonates such as mesylates.
More preferentially, the optional cationic counterion(s) are chosen from alkali metals such as Na or K or alkaline-earth metals such as Mg or Ca, and/or the anionic counterion(s) are chosen from halides such as chloride or alkylsulfonates such as mesylates.
According to a preferred embodiment of the invention, the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which n is equal to 1 and G" denotes an anionic radical chosen from *-C(0)0- and *-S(0)2-0".
According to an advantageous embodiment of the invention, the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which R4 denotes a linear C1-C5 divalent alkylene radical optionally substituted with a hydroxyl group, such as -CH2-CH2-CH2-, -CH2- CH(OH)-CH2- or -CH2-CH2-.
According to a preferred embodiment of the invention, the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which m is 1 and Z represents an oxygen atom or a group -N(R)- with R as defined previously. More preferentially, when m is 1 , then Z represents an oxygen atom.
According to another preferred embodiment of the invention, the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which m is 0.
According to another preferred embodiment of the invention, the betaine surfactant(s) are chosen from the surfactants of formula (B3) in which R1 denotes a group chosen from i) C6-C3o alkyl; ii) C6-C3o alkenyl; -alkyl(C6-C3o)-amido-(Ci-C4)alkyl or -alkenyl(C6-C3o)-amido- (CrC4)alkyl, with amido representing a group -C(0)-N(R)- and R being as defined previously. Particularly, R denotes a hydrogen atom.
More particularly, R1 denotes a linear or branched, preferably linear, C6-C3o alkyi radical.
Among the amphoteric surfactants mentioned above, use is preferably made of (C8- C2o)alkylbetaines such as cocoylbetaine, and (C8-C2o)alkylamido(C2-C2o)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof.
More preferentially, the amphoteric surfactant(s) are chosen from cocoylamidopropylbetaine and cocoylbetaine.
According to a particular embodiment of the invention, the ingredient iii) represents one or more anionic surfactants.
The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the following groups:
-C(0)OH, -C(0)0", -SO3H, -S(0)20", -OS(0)2OH, -OS(0)20", -P(0)OH2, -P(0)20", -P(0)02 ", -P(OH)2, =P(0)OH, -P(OH)0", =P(0)0", =POH, =PO", the anionic parts comprising a cationic counterion such as those of an alkali metal, an alkaline-earth metal or an ammonium.
As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyi sulfates, alkyi ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkyi sulfosuccinates, alkyi ether sulfosuccinates, alkylamide sulfosuccinates, alkyi sulfoacetates, acylsarcosinates, acylglutamates, alkyi sulfosuccinamates, acylisethionates and N- acyltaurates, polyglycoside polycarboxylic acid and alkyi monoester salts, acyl lactylates, salts of D-galactoside uronic acids, salts of alkyi ether carboxylic acids, salts of alkylaryl ether carboxylic acids, salts of alkylamido ether carboxylic acids; and the corresponding non- salified forms of all these compounds; the alkyi and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.
These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
The salts of C6-C24 alkyi monoesters of polyglycoside-polycarboxylic acids may be chosen from C6-C24 alkyi polyglycoside-citrates, C6-C24 alkyi polyglycoside-tartrates and C6- C24 alkyi polyglycoside-sulfosuccinates.
When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as the magnesium salts.
Examples of amino alcohol salts that may especially be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2- amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
Alkali metal or alkaline-earth metal salts, and in particular sodium or magnesium salts, are preferably used.
Among the anionic surfactants mentioned, use is preferably made of (C6-C24)alkyl sulfates, (C6-C24)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
In particular, it is preferred to use (Ci2-C2o)alkyl sulfates, (Ci2-C20)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.
According to another particular embodiment of the invention, the ingredient(s) iii) represent one or more cationic surfactants.
The cationic surfactant(s) that may be used in the composition according to the invention comprise, for example, optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
Among the tertiary fatty amines, mention may be made more particularly of oleylamidopropyldimethylamine.
Quaternary ammonium salts that may especially be mentioned include:
- a) quaternary ammonium salts of general formula (B4) below:
in which formula (B4):
■ R8 to Rii, which may be identical or different, represent a linear or branched, saturated or unsaturated aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R8 to Rn comprises from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms; and
■ X" represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (CrC4)alkyl- sulfates, (CrC4)alkyl- or (d- C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate;
the aliphatic groups of R8 to Rn may also comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens;
the aliphatic groups of R8 to Rn are chosen in particular from C1-C30 alkyl, C1-C30 alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (Ci2-C22)alkylamido(C2-C6)alkyl, (Ci2-C22)alkyl acetate, and C1-C30 hydroxyalkyl groups, X" is an anionic counterion
chosen from the group of halides, phosphates, acetates, lactates, (CrC4)alkyl sulfates, and (Ci-C4)alkyl- or (Ci-C4)alkylaryl sulfonates;
among the quaternary ammonium salts of formula (B4), preference is given firstly to tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride;
b) quaternary ammonium salts of imidazoline, for instance those of formula (B5) below:
in which formula (B5):
■ R-I2 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow;
■ Ri3 represents a hydrogen atom, a C C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;
■ Ri4 represents a C C4 alkyl group;
■ Ri5 represents a hydrogen atom or a C C4 alkyl group;
■ X" represents an organic or mineral anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (Ci-C4)alkyl- sulfates, (Ci-C4)alkyl- or (d- C4)alkylaryl sulfonates;
R-I2 and Ri3 preferably denote a mixture of alkyl or alkenyl groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids, Ri4 preferably denotes a methyl group, and Ri5 preferably denotes a hydrogen atom; such a product is sold, for example, under the name Rewoquat® W75 by the company Rewo;
c) quaternary diammonium or triammonium salts, in particular of formula (B6) below:
■ R-16 denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;
■ R-I7 is selected from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH2)3-N+(R16a)(R17a)(R18a), X";
■ R16a, Ri7a, Risa, Ri8, Ri9, R20 and R21 , which may be identical or different, are selected from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and
■ X", which may be identical or different, represent an organic or mineral anionic counterion, such as that selected from halides, acetates, phosphates, nitrates, (C1-C4) alkyl sulfates, (C1-C4) alkyl- or (C1-C4) alkyl aryl sulfonates, more particularly methyl sulfate and ethyl sulfate;
such compounds are, for example, Finquat CT-P, available from the company Finetex (Quaternium 89), and Finquat CT, available from the company Finetex (Quaternium 75);
- d) quaternary ammonium salts containing one or more ester functions, such as those of formula (B7) below:
in which formula (B7):
■ R22 is chosen from CrC6 alkyl groups and CrC6 hydroxyalkyl or CrC6 dihydroxyalkyl groups;
■ R23 is chosen from:
O
- the group Ra6 C ,
- linear or branched, saturated or unsaturated Ci-C22 hydrocarbon-based groups R27,
- a hydrogen atom,
■ R25 is chosen from:
O
- the group R28 ^
- linear or branched, saturated or unsaturated Ci-C6 hydrocarbon-based groups R29,
- a hydrogen atom,
■ R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;
■ r, s and t, which may be identical or different, are integers ranging from 2 to 6,
■ r1 and t1 , which may be identical or different, are equal to 0 or 1 , with r2+r1 =2r and t1 +t2=2t,
■ y is an integer ranging from 1 to 10,
■ x and z, which may be identical or different, are integers ranging from 0 to 10;
■ X" represents an organic or mineral anionic counterion,
with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R23 denotes R27, and that when z is 0 then R25 denotes R29; the alkyl groups R22 may be linear or branched, and more particularly linear;
preferably, R22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group; advantageously, the sum x + y + z is from
1 to 10;
When R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
When R25 is a hydrocarbon-based group R29, it preferably contains 1 to 3 carbon atoms.
Advantageously, R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn-C2i hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn-C2i alkyl and alkenyl groups.
Preferably, x and z, which may be identical or different, are equal to 0 or 1 .
Advantageously, y is equal to 1.
Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
The anionic counterion X" is preferably a halide, such as chloride, bromide or iodide; a (CrC4)alkyl sulfate or a (CrC4)alkyl- or (Ci-C4)alkylaryl sulfonate. However, it is possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function.
The anionic counterion X" is even more particularly chloride, methyl sulfate or ethyl sulfate.
Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (B7) in which:
- R22 denotes a methyl or ethyl group,
- x and y are equal to 1 ,
- z is equal to 0 or 1 ,
- r, s and t are equal to 2,
- R23 is chosen from:
O
• the group Ra6 C
• methyl, ethyl or Ci4-C22 hydrocarbon-based groups,
• a hydrogen atom,
- R25 is chosen from:
O
• the group R28 ^
• a hydrogen atom,
- R24, R26 and R28, which may be identical or different, are selected from linear or branched, saturated or unsaturated C13-C17 hydrocarbon groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
Advantageously, the hydrocarbon-based radicals are linear.
Among the compounds of formula (B7), examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,
monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil, such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of vegetable or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.
The composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.
Preferably, the ammonium salts containing at least one ester function contain two ester functions.
Among the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, dipalmitoylethylhydroxyethylammonium methosulfate and oleylamidopropyldimethylamine, and mixtures thereof.
According to another particular embodiment of the invention, the ingredient iii) represents one or more nonionic surfactants.
The term "nonionic" surfactant means a surfactant that does not bear any anionic or cationic charge. Examples of nonionic surfactants that can be used in the composition used according to the invention are described, for example, in the "Handbook of Surfactants" by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp. 1 16-178. They are especially chosen from alcohols, a-diols and (CrC2o)alkylphenols, these compounds being polyethoxylated, polypropoxylated and/or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 50, and for the number of glycerol groups to especially range from 2 to 30.
Mention may also be made of copolymers of ethylene oxide and propylene oxide, optionally oxyethylenated sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyalkylenated fatty acid esters, optionally oxyalkylenated alkyl polyglycosides, alkyl glucoside esters, derivatives of N-alkyl glucamine and of N-acyl methylglucamine, aldobionamides and amine oxides.
The nonionic surfactants are chosen more particularly from mono- or polyoxyalkylenated or mono- or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
Mention may be made, as examples of oxyalkylenated nonionic surfactants, of:
• oxyalkylenated (C8-C24)alkylphenols;
• saturated or unsaturated, linear or branched, oxyalkylenated C8-C3o alcohols;
• saturated or unsaturated, linear or branched, oxyalkylenated C8-C3o amides;
• esters of saturated or unsaturated, linear or branched, C8-C3o acids and of polyethylene glycols;
• polyoxyethylenated esters of saturated or unsaturated, linear or branched, C8-C3o acids and of sorbitol;
• saturated or unsaturated, oxyethylenated plant oils;
• condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures;
• oxyethylenated and/or oxypropylenated silicones.
The surfactants contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100, preferably between 2 and 50 and preferably between 2 and 30. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.
In accordance with one preferred embodiment of the invention, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C8-C30 alcohols comprising from 1 to 100 mol of ethylene oxide; polyoxyethylenated esters of linear or branched, saturated or unsaturated C8-C30 acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.
As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C8-C4o alcohols are preferably used.
In particular, the monoglycerolated or polyglycerolated C8-C40 alcohols correspond to formula (B8) below:
R290-[CH2-CH(CH2OH)-0]m-H (B8)
in which formula (B8):
■ R29 represents a linear or branched C8-C40 and preferably C8-C3o alkyl or alkenyl radical; and
■ m represents a number ranging from 1 to 30 and preferably from 1 to 10.
As examples of compounds of formula (B8) that are suitable within the context of the invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1 .5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.
The alcohol of formula (B8) may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohols may coexist in the form of a mixture.
Among the monoglycerolated or polyglycerolated alcohols, it is more particularly preferred to use the C8/Ci0 alcohol containing 1 mol of glycerol, the C10/C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol.
Among the saturated or unsaturated, linear or branched C8-C3o acid esters of polyoxyethylenated sorbitol, the ones that are preferred are those with a number of moles of ethylene oxide of less than or equal to 20, particularly comprising from 8 to 24 carbon atoms and more particularly from 8 to 18 carbon atoms. The fatty acids are especially chosen from lauric acid, palmitic acid, oleic acid and stearic acid, and preferably from lauric acid and stearic acid, and even more particularly lauric acid.
C8-C24 fatty acid monoesters of oxyethylenated sorbitan are preferably used. The number of moles of ethylene oxide is preferably less than 10 and more particularly ranges from 3 to 8 mol of ethylene oxide and in particular is equal to 4.
The preferred sorbitan esters are sorbitan monolaurate oxyethylenated with 4 mol of ethylene oxide (4 EO) or polysorbate 21 , sorbitan monostearate oxyethylenated with 4 mol of ethylene oxide (4 EO) or polysorbate 61 , and sorbitan monooleate oxyethylenated with 5 mol of ethylene oxide (5 EO) or polysorbate 81 .
Polysorbate 21 is particularly preferred and is sold especially under the name Tween
21 by the company Uniqema.
According to the invention, the composition may advantageously comprise mixtures of oxyethylenated sorbitan esters and especially polysorbate 21 with polysorbate 20 (sorbitan monolaurate oxyethylenated with 20 EO).
Preferably, the surfactant(s) iii) are chosen from nonionic, cationic and anionic surfactants and are particularly chosen from nonionic and anionic surfactants. More particularly, the surfactant(s) present in the composition are chosen from nonionic surfactants. Preferably, the nonionic surfactant(s) are monooxyalkylenated or polyoxyalkylenated, particularly monooxyethylenated or polyoxyethylenated, or monooxypropylenated or polyoxypropylenated, nonionic surfactant(s), or a combination thereof, more particularly monooxyethylenated or polyoxyethylenated.
More preferentially, the nonionic surfactants are chosen from polyoxyethylenated sorbitol esters and polyoxyethylenated fatty alcohols, and mixtures thereof.
According to a variant of the invention, the composition according to the invention, the final composition in the event of supplementary addition of water, the predispersion and the process for treating (dyeing) keratin fibres used as ingredient iii) one or more surfactants chosen from nonionic surfactants, in particular mono oxyalkylenated or polyoxyalkylenated surfactants, more particularly chosen from polyoxyethylenated saturated or unsaturated, linear or branched C8-C3o acid esters of sorbitol as defined previously; and/or one or more anionic surfactants, in particular of alkyl sulfate type as defined previously, in particular an alkali metal or alkaline-earth metal salt of lauryl ether sulfate. The predispersion or preemulsion of the invention preferably contains from 1 % to 60% by weight, preferably from 5% to 50% by weight and better still from 10% to 40% by weight of surfactant(s), relative to the total weight of the said predispersion.
The composition of the invention preferably contains from 1 % to 40% by weight, preferably from 2% to 20% by weight and better still from 5% to 20% by weight of surfactant(s), relative to the total weight of the said composition.
In the event of supplementary addition of water to the composition of the invention, the final composition preferably contains from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1 % to 10% by weight of surfactant(s), relative to the total weight of the said final composition.
iv) water or the aqueous phase
The composition according to the invention, and the final composition in the event of supplementary addition of water, as defined previously, comprise water. This water constitutes all or part of an aqueous phase.
The term "aqueous phase" means a phase which comprises essentially water, and also comprises other ingredients that are water-miscible or water-soluble at room temperature and at atmospheric pressure. As liquids or solids that may be present in the aqueous phase, mention may be made of: polar or polar protic organic solvents as defined below, salts of mineral or organic acids or bases, or water-soluble cosmetic active agents.
The predispersion of the invention contains water preferably in an amount ranging from 5% to 50% by weight, better still from 7% to 40% and particularly from 8% to 20% by weight relative to the total weight of the said composition.
The composition of the invention contains water preferably in an amount ranging from 3% to 40% by weight, better still from 5% to 20% and particularly from 7% to 15% by weight relative to the total weight of the said composition.
In the event of supplementary addition of water to the composition of the invention, the final composition contains water preferably in an amount ranging from 20% to 90% by weight, better still from 30% to 80% and particularly from 50% to 70% by weight relative to the total weight of the said final composition.
Organic solvents:
The ready-to-use composition and/or the predispersion and/or, where appropriate, the intermediate composition of the invention may comprise one or more organic solvents. Examples of organic solvents that may be mentioned include Ci-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
The organic solvents are present in proportions preferably of between 0.1 % and 20% by weight approximately and even more preferentially between 0.5% and 10% by weight approximately relative to the total weight of the composition under consideration. Adjuvants:
The composition according to the invention, the final composition in the event of supplementary addition of water and the predispersion may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants,
penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents other than the fatty substances of the invention, for instance ceramides, film-forming agents, preserving agents, opacifiers and mineral or organic thickeners such as clays.
The above adjuvants are generally present in an amount for each of them of between 0.01 % and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition under consideration.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the composition, preemulsion or poultice that are useful in the dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
Additional dyes:
The composition according to the invention, the final composition in the event of supplementary addition of water and the predispersion may also contain one or more additional direct dyes other than ingredient i) as defined previously.
These direct dyes are chosen, for example, from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than henna or indigo, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine and methine cyanine direct dyes, and fluorescent dyes.
Preferentially, the composition according to the invention, the final composition in the event of supplementary addition of water and the predispersion of the invention may comprise one or more natural dyes other than i) as defined previously. Among the natural direct dyes, mention may be made of juglone, isatin, curcumin, spinulosin, apigenidin and orceins, in defined compound form.
These natural dyes, besides their defined compound form, may be added in the form of extracts or of plant parts. The said defined compounds from extracts or from plant parts are preferably in the form of powders, in particular fine powders whose particles have sizes identical to that of the red henna and/or indigo powder i) as defined previously.
The natural or non-natural direct dye(s) different from i) particularly represent from 0.001 % to 10% by weight and even more preferentially from 0.05% to 5% by weight relative to the total weight of the composition of the invention or, where appropriate, of the final composition.
Preferably, the compositions of the invention do not contain any synthetic direct dyes, i.e. dyes that do not occur in nature.
The composition according to the invention, the final composition in the event of supplementary addition of water and the predispersion may also comprise one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibres.
Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
Among these couplers, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
The oxidation base(s) present in the composition of the invention are each generally present in an amount of between 0.001 % and 10% by weight relative to the total weight of the dye composition(s).
Preferably, the composition according to the invention, the final composition in the event of supplementary addition of water and the predispersion do not contain any oxidation dyes. pH of the compositions and of the predispersion
According to a particular mode of the invention, the pH of the composition of the invention and/or, where appropriate, of the final composition is neutral, i.e. it has a pH of about 7.
According to a particular mode of the invention, the composition of the invention and/or, where appropriate, the final composition of the invention are acidic and preferably have a pH ranging from 3 to 6.5.
The pH of the composition may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres or alternatively with the aid of standard buffer systems, or of clays present in the composition, in the preemulsion or in the aqueous phase is added to make the poultice as defined previously.
Among the acidifying agents for the compositions used in the invention, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids; the acid is preferably an organic acid such as citric acid.
One advantageous variant involves adding a basifying agent to the composition or the poultice according to the invention. More particularly, this alkaline agent is chosen from aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine,
diethanolamine or triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (II) below:
N - W - N
c d (II)
in which formula (II) W is a CrC6 alkylene group such as propylene, optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.
According to a particular mode of the invention, the ready-to-use composition of the invention does not contain any "mordants", i.e. metal salts conventionally used in "mordanting" (see for example Ullmann's Encyclopedia of Industrial Chemistry ("Textile Dyeing", Herbert Leube et al., DOI: 10.1002/14356007. a26_351 , and in particular point 4.8.2, p. 72; ibid, "Metal-complex dyes", Klaus Gryschtol et al., DOI: 10.1002/14356007.a16_299).
According to another particular mode of the invention, the composition of the invention contains at least one "mordant", i.e. metal salts conventionally used in "mordanting" as defined above. Preferably, the metal salt(s) are chosen from iron, copper, zinc, manganese, etc. In addition, the metal salt(s) are preferably in the predispersion as defined previously.
Composition after mixing ofi) + predispersion
The composition according to the invention is characterized by its preparation method, which consists in mixing the ingredient(s) as defined previously in a dispersion that is being prepared beforehand, also known as a "predispersion", preferably a "preemulsion", as defined previously, and which comprises the ingredients i) to iv) as defined previously.
Supplementary water may be added to the composition of the invention especially to make the composition of the invention more creamy or more easy to apply.
The mixing of the predispersion with the ingredient(s) i) may be performed at time of use without addition of water to give the composition of the invention. This composition may optionally be stored and used at the time of use with addition of water, preferably hot water (temperature between 30°C and 80°C).
The mixing of the predispersion with the ingredient i) may be performed at the time of use with addition of water, preferably hot water (temperature between 30°C and 80°C) to give the final composition.
According to a preferred embodiment of the invention, the henna and/or indigo powder, ingredient i) of the invention, is mixed sparsely with or dispersed in the predispersion in a ratio of ingredient i) and of predispersion ranging from 0.015 part to 0.5 part of ingredient i) by weight per 1 part by weight of predispersion.
According to another particular embodiment of the invention, the ratio of ingredient i) and the predispersion is greater than 0.5 part by weight of ingredient i) per 1 part by weight of predispersion, and preferably the ratio is inclusively between 0.6 and 3 parts by weight of ingredient i) per 1 part by weight of predispersion, more preferentially 2 parts by weight of i) per 1 part by weight of predispersion. In this second advantageous option, the composition obtained is pasty and the ingredient i) is coated with the predispersion.
In the case of supplementary addition of water to the composition according to the invention, the weight ratio of the mixture of the predispersion/ingredient i) and of the additional water preferably ranges from 0.1 to 2 parts and better still from 0.5 to 1 part of mixture per 1 part of additional water.
More preferentially, 1.5 parts of mixture per 2.5 parts of additional water will be used.
The compositions of the invention are cosmetic, i.e. they are cosmetically acceptable and are therefore suitable for use for application to keratin fibres.
According to a preferred embodiment of the invention, the composition of the invention or, where appropriate, the final composition are in non-compact galenical forms, such as a lotion, a mousse, a cream or a gel, or in any other form that is suitable for dyeing keratin fibres.
Preferably, these compositions are in the form of a poultice with a pleasant, creamy consistency.
During the preparation of the composition of the invention, one or more identical or different clays may be added.
According to a particular embodiment of the invention, the predispersion is a preemulsion and is preferably in the form of a microemulsion or nanoemulsion and/or contains the following ingredients:
According to a particular embodiment of the invention, the predispersion is a preemulsion which is in the form of a microemulsion or nanoemulsion and/or which contains the following ingredients:
Ingredients Commercial name
Polyethylene glycol monoisostearate PEG 8 isostearate
Behenyltrimethylammonium chloride (cationic Behentrimonium chloride surfactant)
Protected avocado oil Persea gratissima oil
Jojoba oil Simmondsia chinensis seed oil
Cyclopentadimethylsiloxane Cyclopentasiloxane
Glycerol Glycerin
Ethyl alcohol Alcohol
SMDI/polyethylene glycol copolymer bearing alkyl end PEG-150/stearyl alcohol/SMDI groups (methyl/C18) at 15% in a maltodextrin/water copolymer
matrix
1 ,3-Butylene glycol Butylene glycol
Water
According to a particular embodiment of the invention, the predispersion is a preemulsion which is in the form of a microemulsion or nanoemulsion and/or which contains the following ingredients:
According to a particular embodiment of the invention, the predispersion is a preemulsion which is in the form of a microemulsion or nanoemulsion and/or which contains the following ingredients:
Ingredients Commercial name
Protected avocado oil Persea gratissima oil
Sesame oil Sesamum indicum seed oil
Texapon N62 Sodium lauryl ether sulfate
Oleylamidopropyldimethylamine Mackine 501 V
Water
Dveinp process using the composition of the invention
According to a particular embodiment P1 of the invention, the dyeing process is performed in several steps:
- the first step consists in preparing composition (la) of the invention, i.e. the composition obtained by mixing at the time of use the ingredient i) as defined previously with the predispersion as defined previously optionally with supplementary addition of water to give the final composition (lla);
- in the second step, composition (la) or (lla) is applied to the keratin fibres and is left on the said fibres preferably for a minimum time of 30 minutes, preferentially a time ranging from 30 minutes to 24 hours and better still ranging from 1 hour to 12 hours;
- in the third step, the keratin fibres are rinsed with water until the poultice has disappeared, preferably without shampooing;
- the keratin fibres may then be dried or left to dry naturally, without a hairdryer.
According to another particular embodiment P2 of the invention, the dyeing process is performed in several steps:
- the first step consists in preparing composition (la) or (lla) of the invention as described previously;
- in the second step, composition (la) or (lla) is left to stand for several hours, preferably 24 hours, and is then applied preferably in the form of a poultice and left on the said fibres preferably for a minimum time of 30 minutes (preferably ranging from 30 minutes to 24 hours and better still from 1 hour to 12 hours);
- in the third step, the keratin fibres are rinsed with water until composition (la) or (lla) has disappeared, preferably without shampooing;
- the keratin fibres may then be dried or left to dry naturally, without a hairdryer.
According to a particularly advantageous process, after the third step of P1 or P2, the keratin fibres are:
a) either mechanically wiped with a towel or absorbent paper,
b) or dried by heat with a heat source (confection, convention or radiation) by passing over, for example, a stream of a warm gas such as air necessary to evaporate off the solvent(s); heat sources that may be mentioned include a hairdryer, hairdrying
hoods, a hair-straightening iron, an infrared ray dispenser and other standard heating appliances.
Irrespective of the application method, the application temperature for composition (la) or (lla) ranges from room temperature (15 to 25°C) to 80°C and more particularly from 15 to 45°C. Thus, after application of the ready-to-use composition according to the invention, the head of hair may advantageously be subjected to a heat treatment by heating to a temperature ranging from 30 to 60°C. In practice, this operation may be performed using a styling hood, a hairdryer, an infrared ray dispenser or other standard heating appliances.
Use may be made, both as means for heating and straightening the hair, of a heating iron at a temperature ranging from 60 to 220°C and preferably from 120 to 200°C.
A specific form of the invention relates to a dyeing process which is performed at room temperature (25° C).
Irrespective of the dyeing process, in particular of P1 and P2 as defined previously, if ingredient i) used is henna powder, each of these processes may be followed by another dyeing process P1 or P2 comprising as ingredient i) indigo; and vice versa, i.e. irrespective of the dyeing process P1 or P2 as defined previously, if ingredient i) used is indigo, each of these processes may be followed by another dyeing process P1 or P2 comprising as ingredient i) henna powder.
More specifically, the dyeing process may take place, for example, in three different ways.
Process 1 :
Henna and/or indigo powder (1 part) is mixed with the predispersion (0.5 part) and with water at a temperature of between 40 and 98°C (2.5 parts) in a bowl, and the whole is then mixed for the time required to obtain a creamy poultice. The poultice is then applied to the head for a minimum time of 30 minutes (preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours) before rinsing without shampooing, and the hair is then dried. Process 2:
Henna and/or indigo powder (1 part) is mixed with the predispersion (0.5 part) and with water at a temperature of between 10 and 40°C (2.5 parts) in a bowl, and the whole is then mixed for the time required to obtain a creamy poultice. The poultice is then applied to the head for a minimum time of 30 minutes (preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours) before rinsing without shampooing, and the hair is then dried. Process 3:
The cream (cationic preemulsion as a nanoemulsion or microemulsion or emulsion, i.e. comprising at least one cationic surfactant as defined previously) mixed with henna and/or indigo powder is applied to the head for a minimum time of 30 minutes (preferably between
30 minutes and 24 hours and better still between 1 hour and 12 hours) before rinsing without shampooing, and the hair is then dried.
Irrespective of the application method, the application temperature of the composition comprising i) to iv) to the keratin fibres ranges from room temperature (15 to 25°C) to 80°C and more particularly from 15 to 45°C. Thus, after application of the poultice according to the invention, the head of hair may advantageously be subjected to a heat treatment by heating to a temperature ranging from 30 to 60°C. In practice, this operation may be performed using a styling hood, a hairdryer, an infrared ray dispenser or other standard heating appliances.
More particularly, the process of the invention is performed according to the following two processes:
- Process 4:
A composition preferably in the form of a poultice containing henna and/or indigo- producing plant(s) in an amount of 1 part by weight and water at a temperature inclusively between 40 and 98°C for an amount of 2-3 parts by weight i) is applied to the head for a minimum time of 30 minutes, preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours, followed by ii) rinsing preferably without shampooing, and then iii) the hair is dried; next, iv) a heating iron at a temperature inclusively between 100 and 230°C and preferably between 130 and 180°C is used along the length of the head of hair;
- Process 5:
A composition preferably in the form of a poultice containing henna and/or indigo- producing plant(s) in an amount of 1 part by weight and water at a temperature inclusively between 10 and 40°C for an amount of 2-3 parts by weight i) is applied to the head for a minimum time of 30 minutes, preferably between 30 minutes and 24 hours and better still between 1 hour and 12 hours, followed by ii) rinsing preferably without shampooing, and then iii) the hair is dried; next, iv) a heating iron at a temperature between 100 and 230°C and preferably between 130 and 180°C is used along the length of the head of hair.
A specific form of the invention relates to a dyeing process which is performed at room temperature (25° C).
According to a particularly advantageous embodiment of the invention, all the ingredients used in the process are of natural origin, and preferably of plant origin.
The evaluation of the coloration can be done visually or read on a spectrocolorimeter (such as Minolta CM3600d, illuminant D65, angle 10°, SCI values) for the L*, a*, b* colorimetric measurements. In this L*, a*, b* system, L* represents the intensity of the color,
a* indicates the green/red color axis and b* indicates the blue/yellow color axis. The lower the value of L, the darker or more intense the color. The higher the value of a*, the redder the shade; the higher the value of b*, the yellower the shade. The variation in coloring between the colored locks of natural white hair (NW) which is untreated (control) and after treatment or coloration are defined by ΔΕ*, corresponding to the colour uptake on keratin fibers, according to the following equation:
ΔΕ* = -(L*— Lo *)2 +(a*— ao * f + (b* - b0 *)2
In this equation, L*, a* and b* represent the values measured after dyeing the natural hair comprising 90% of white hairs and L0 *, a0 * and b0 * represent the values measured for the untreated natural hair comprising 90% of white hairs.
The greater the value of ΔΕ, the greater the difference in color between the control locks and the dyed locks and the greater colour uptake is.
On the other hand for evaluating the selectivity of the color between the root and tip of the keratin fiber, measurement can be done on permed or sensibilised white hair (PW) and natural white hair, wherein the variation in coloring between the colored locks PW and the colored natural white hair are defined by ΔΕ*, corresponding to the selectivity of the colour, is calculated according to the following equation:
ΔΕ* = -(L*— Lo *)2 +(a*— ao * f + (b* - b0 *)2
In this equation, L*, a* and b* represent the values measured after dyeing the natural hair comprising 90% of white hairs and L0 *, a0 * and b0 * represent the values measured after dyeing the permed or sensibilised hair. The lowest ΔΕ*, the best homogeneity of the hair color.
If the light fastness is investigated, ΔΕ* is also calculated for the L0 *, a0 *, b0 * and L*, a*, b* measured of the locks before and after exposure to the light, respectively.
Chromaticity in the CIE L*, a*, b* colorimetric system is calculated according to the following equation :
The greater the value of C*, the greater the chromaticity is.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
DYEING EXAMPLES
The following compositions were prepared as follows:
The percentages are indicated on a weight basis relative to 100 g of composition.
Com osition A:
AM: Active material 1 part of composition A is mixed with 0.5 part of composition B or C and 2.5 parts of warm water at 37°C in a bowl, or in cold water ( 0°C), and .5 parts of composition D were mixed
with 2.5 parts of warm water at 37°C, or in cold water at 10°C. The mixing takes place easily even in cold water. The poultices obtained are very creamy and are easy to apply to keratin fibres, totally impregnating the keratin fibres from the root to the end.
The poultice is applied to 90% grey hair, with a leave-on time of 30 minutes.
The hair is rinsed thoroughly.
The hair is dried.
A strong coppery aesthetic coloration is obtained with compositions B and C, and a blue- green coloration with composition D. The hair is smooth and soft, and the coloration is very uniform from one fibre to another and from the root to the end.
Claims
1 . Composition comprising:
i) at least 5% by weight of red henna powder and/or of powder of indigo-producing plant(s);
ii) at least one oil selected from oils of natural origin ;
iii) at least one surfactant selected from monooxyalkylenated nonionic surfactants, polyoxyalkylenated nonionic surfactants, mono- or polyglycerolated nonionic surfactants, and anionic surfactants ; and
iv) water;
it being understood that the ingredients ii), iii) and iv) are predispersed together to form a predispersion, and the ingredient(s) are then dispersed in the said predispersion or the said predispersion is dispersed in the said ingredient(s) i).
2. Ready-to-use composition according to the preceding claim, which is preferably a poultice.
3. Composition according to either of the preceding claims, in which ingredient i) in powder form consists of fine particles with a size of less than or equal to 500 μηη; preferentially, the powder consists of fine particles with sizes inclusively between 50 and 300 μηη and more particularly between 10 and 200 μηη.
4. Composition according to any one of the preceding claims, in which ingredient i) represents red henna powder.
5. Composition according to any one of the preceding claims, in which ingredient i) represents powder of indigo-producing plant(s).
6. Composition according to any one of the preceding claims, in which ingredient i) is in an amount ranging from 1 % to 85% by weight relative to the total weight of the composition, more particularly ranging from 5% to 80% by weight and more particularly from 10% to 75% by weight relative to the total weight of the composition.
7. Composition according to any one of the preceding claims, in which the predispersion contains at least one surfactant iii) and is a preemulsion preferably with a mean droplet size of greater than 200 nm of the water-in-oil W/O type, the ingredients ii), iii) and iv) particularly being in microemulsion and more particularly in nanoemulsion.
8. Composition according to any one of the preceding claims, in which the oil(s) are chosen from non-silicone oils and in particular C6-Ci6 hydrocarbons or
hydrocarbons containing more than 16 carbon atoms and in particular alkanes; oils of animal origin; triglyceride oils of plant origin; essential oils; fluoro oils or glycerides of synthetic origin, fatty alcohols; fatty acid and/or fatty alcohol esters other than triglycerides, and silicone oils.
9. Composition according to any one of the preceding claims, in which the oil(s) ii) are chosen from oils of plant origin and essential oils, preferentially oils of plant origin such as jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, corn oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, almond oil, castor oil, avocado oil, shea butter oil, rapeseed oil, borage oil, evening primrose oil, pomegranate oil, mango oil, palm oil, cotton seed oil and copra oil; more preferentially, the oil(s), ingredient ii) of the invention, are chosen from sunflower oil, avocado oil, sesame oil and jojoba oil, and even more preferentially are chosen from avocado oil and sunflower oil.
10. Composition according to any one of the preceding claims, in which the content of oil(s) ranges from 10% to 85% by weight, preferably from 15% to 80% by weight and better still from 20% to 75% by weight relative to the total weight of the said composition.
11. Composition according to any one of the preceding claims, in which the predispersion of the invention before addition of the ingredient(s) i) comprises from 30% to 90% by weight and preferably 40% to 75% by weight of one or more oils relative to the total weight of the said predispersion.
12. Composition according to any one of the preceding claims, in which the ratio of ingredient i) and the predispersion is greater than 0.5 part by weight of ingredient i) per 1 part by weight of predispersion, and preferably the ratio is inclusively between 0.6 and 3 parts by weight of ingredient i) per 1 part by weight of predispersion, more preferentially 2 parts by weight of i) per 1 part by weight of predispersion.
13. Composition according to any one of the preceding claims, which also comprises one or more fatty substances other than i), the said additional fatty substance(s) being chosen from butters, preferably of plant origin, and are particularly chosen from shea butter, Karite Nilotica butter (Butyrospermum parkii), galam butter, (Butyrospermum parkii), Borneo butter or fat or tengkawang tallow (Shorea stenoptera), shorea butter, illipe butter, madhuca butter or Bassia madhuca longifolia butter, mowrah butter (Madhuca latifolia), katiau butter (Madhuca mottleyana), phulwara butter (M. butyracea), mango butter (Mangifera indica), murumuru butter (Astrocaryum murumuru), kokum butter (Garcinia indica), ucuuba butter (Virola sebifera), tucuma butter, painya butter (Kpangnan) (Pentadesma butyracea), coffee butter (Coffea arabica), apricot butter (Prunus armeniaca), macadamia butter (Macadamia ternifolia), grapeseed butter (Vitis vinifera), avocado butter
(Persea gratissima), olive butter (O/ea europaea), sweet almond butter (Prunus amygdalus dulcis), cocoa butter (Theobroma cacao) and sunflower butter.
14. Composition according to any one of the preceding claims, which comprises at least one surfactant iii), in particular which is chosen from nonionic, cationic and anionic surfactants and more particularly chosen from nonionic and anionic surfactants.
15. Composition according to any one of the preceding claims, which comprises at least one iii) monooxyalkylenated or polyoxyalkylenated nonionic surfactants, chosen from polyoxyethylenated saturated or unsaturated, linear or branched C8-C30 acid esters of sorbitol, and anionic surfactants of alkyl sulfate type, in particular an alkali metal or alkaline-earth metal salt of lauryl ether sulfate.
16. Composition according to any one of the preceding claims, which comprises at least one surfactant iii) selected from nonionic surfactants, and (B8), and also the optional organic or mineral acid or base salts thereof, and solvates thereof such as hydrates, below:
the nonionic surfactants are chosen from mono- or polyoxyalkylenated, mono- or polyglycerolated nonionic surfactants :
· oxyalkylenated (C8-C24)alkylphenols;
• saturated or unsaturated, linear or branched, oxyalkylenated C8-C3o alcohols;
• saturated or unsaturated, linear or branched, oxyalkylenated C8-C3o amides;
• esters of saturated or unsaturated, linear or branched, C8-C3o acids and of polyethylene glycols,
· polyoxyethylenated esters of saturated or unsaturated, linear or branched, C8-C30 acids and of sorbitol,
• saturated or unsaturated, oxyethylenated plant oils;
• condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures;
· oxyethylenated and/or oxypropylenated silicones;
• the surfactants containing a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100, preferably between 2 and 50 and preferably between 2 and 30; and
R290-[CH2-CH(CH2OH)-0]m-H (B8)
in which formula (B8):
■ R29 represents a linear or branched C8-C4o and preferably C8-C30 alkyl or alkenyl radical; and
■ m represents a number ranging from 1 to 30 and preferably from 1 to 10.
17. Composition according to any one of Claims 1 , 7 and 14 to 16, which contains from 1 % to 40% by weight, preferably from 2% to 20% by weight and in particular from 5% to 20% by weight of surfactant(s) relative to the total weight of the said composition.
18. Composition according to any one of Claims 1 , 7 and 14 to 17, in which the predispersion is a preemulsion and contains from 1 % to 60% by weight, preferably from 5% to 50% by weight and better still from 10% to 40% by weight of surfactant(s) iii) relative to the total weight of the said preemulsion.
19. Composition according to any one of the preceding claims, in which water or the ingredient iv) in the predispersion is in an amount ranging from 5% to 50% by weight relative to the total weight of the said predispersion, more particularly from 7% to 40% by weight and better still from 8% to 20% by weight relative to the total weight of the said predispersion.
20. Composition according to any one of the preceding claims, which contains water in an amount ranging from 3% to 40% by weight, better still from 5% to 20% by weight and particularly from 7% to 15% by weight relative to the total weight of the said composition.
21. Composition according to any one of the preceding claims, in which the ingredient(s) i) are mixed sparsely with or dispersed in the predispersion in a ratio of ingredient(s) i) and of predispersion ranging from 0.015 part to 0.5 part of ingredient(s) i) by weight per 1 part by weight of predispersion.
22. Composition according to any one of Claims 1 to 20, in which the ratio of ingredient(s) i) and the predispersion is greater than 0.5 part by weight of ingredient(s) i) per 1 part by weight of predispersion, and preferably the ratio is inclusively between 0.6 and 3 parts by weight of ingredient(s) i) per 1 part by weight of predispersion, more preferentially 2 parts by weight of ingredient(s) i) per 1 part by weight of predispersion.
23. Composition according to any one of Claims 1 to 21 , which is mixed with additional water to give a final composition whose weight ratio of the mixture of the predispersion/ingredient i) and of the additional water ranges from 0.1 to 2 parts and preferably from 0.5 to 1 part of mixture per 1 part of additional water.
24. Process for dyeing keratin fibres, chosen from processes P1 and P2 in which:
• process P1 consists in:
- in the first step, preparing the composition according to any one of the preceding claims; - in the second step, the said composition is:
a) either immediately applied to the keratin fibres, and left on the fibres for a minimum time of 30 minutes, preferentially ranging from 30 minutes to 24 hours and particularly from 1 hour to 12 hours,
b) or left to stand for several hours, preferably 24 hours, and then applied and left on the fibres for a minimum time of 30 minutes, preferably ranging from 30 minutes to 24 hours and particularly from 1 hour to 12 hours;
- in the third step, the keratin fibres are rinsed with water until the composition has disappeared, preferably without shampooing;
- the keratin fibres may then be dried with a source of heat or left to dry naturally at room temperature;
• and process P2 consists in:
- in the first step, preparing the composition as described previously;
- in the second step, the said composition is left to stand for several hours, preferably 24 hours, and the said composition is then applied and left on the said fibres preferably for a minimum time of 30 minutes, preferably ranging from 30 minutes to 24 hours and particularly from 1 hour to 12 hours;
- in the third step, the keratin fibres are rinsed with water until the composition has disappeared, preferably without shampooing;
- the keratin fibres may then be dried with a source of heat or left to dry naturally at room temperature;
preferably, after the third step of P1 or P2, the keratin fibres are:
a) either mechanically wiped with a towel or absorbent paper,
b) or dried by heat with a heat source by passing over, for example, a stream of a warm gas such as air necessary to evaporate off the solvent(s); heat sources that may be mentioned include a hairdryer, hairdrying hoods, a hair-straightening iron, an infrared ray dispenser and other standard heating appliances;
it being understood that irrespective of the dyeing process P1 or P2 as defined previously, if ingredient i) used is henna powder, each of these processes may be followed by another dyeing process P1 or P2 comprising as ingredient i) indigo; and vice versa, i.e. irrespective of the dyeing process P1 or P2 as defined previously, if ingredient i) used is indigo, each of these processes may be followed by another dyeing process P1 or P2 comprising as ingredient i) henna powder.
25. Use of the composition according to any one of Claims 1 to 23, for dyeing keratin fibres such as the hair.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1353847A FR3004941B1 (en) | 2013-04-26 | 2013-04-26 | COMPOSITION BASED ON HENNE OR INDIGO POWDER WITH OIL PRE-DISPERSION, HAIR COLORING METHOD USING THE SAME |
FR1353847 | 2013-04-26 |
Publications (2)
Publication Number | Publication Date |
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WO2014174116A2 true WO2014174116A2 (en) | 2014-10-30 |
WO2014174116A3 WO2014174116A3 (en) | 2015-04-02 |
Family
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Family Applications (1)
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PCT/EP2014/058603 WO2014174116A2 (en) | 2013-04-26 | 2014-04-28 | Composition based on henna or indigo powder with a predispersion of oil, and hair dyeing process using this composition |
Country Status (2)
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FR (1) | FR3004941B1 (en) |
WO (1) | WO2014174116A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109771339A (en) * | 2019-03-13 | 2019-05-21 | 中国热带农业科学院椰子研究所 | A kind of preparation method of coconut oil nanoemulsion with whitening and moisturizing effect |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3075643B1 (en) * | 2017-12-22 | 2019-11-15 | L'oreal | PROCESS FOR COLORING MULTI-STAGE KERATIN FIBERS FROM INDIGOFERE (S) PLANT POWDER AND ACID PROCESSING COMPRISING A PARTICULATE COLOR |
FR3104997B1 (en) * | 2019-12-20 | 2021-11-26 | Oreal | Process for Preparing a Composition for Coloring the Hair from a Composition In the Form of a Powder and an Aqueous Composition |
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CN1103214C (en) * | 1998-12-10 | 2003-03-19 | 中国科学院新疆化学研究所 | Natural medicine as hair restorer |
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DE29902432U1 (en) | 1999-02-11 | 2000-06-29 | Goldwell GmbH, 64297 Darmstadt | Means for coloring human hair |
DE19905707A1 (en) | 1999-02-11 | 2000-08-24 | Goldwell Gmbh | Powdered composition containing solid direct dye, useful for dyeing human hair, contains a fatty acid or its ester to provide a non-dusting product |
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CN109771339A (en) * | 2019-03-13 | 2019-05-21 | 中国热带农业科学院椰子研究所 | A kind of preparation method of coconut oil nanoemulsion with whitening and moisturizing effect |
Also Published As
Publication number | Publication date |
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FR3004941A1 (en) | 2014-10-31 |
WO2014174116A3 (en) | 2015-04-02 |
FR3004941B1 (en) | 2015-05-22 |
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