WO1996039114A1 - Hair and skin ultramulsion based products - Google Patents
Hair and skin ultramulsion based products Download PDFInfo
- Publication number
- WO1996039114A1 WO1996039114A1 PCT/US1996/009459 US9609459W WO9639114A1 WO 1996039114 A1 WO1996039114 A1 WO 1996039114A1 US 9609459 W US9609459 W US 9609459W WO 9639114 A1 WO9639114 A1 WO 9639114A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ultramulsion
- surfactant
- polydimethylsiloxane
- dispersion
- silicone
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 claims abstract description 149
- -1 cleansers Substances 0.000 claims abstract description 101
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 73
- 239000004094 surface-active agent Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004909 Moisturizer Substances 0.000 claims abstract description 9
- 230000001333 moisturizer Effects 0.000 claims abstract description 9
- 239000006210 lotion Substances 0.000 claims abstract description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 86
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 36
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- 229920001983 poloxamer Polymers 0.000 claims description 14
- 229960000502 poloxamer Drugs 0.000 claims description 12
- 150000002632 lipids Chemical class 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 7
- 230000003020 moisturizing effect Effects 0.000 claims description 7
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims description 6
- 230000006870 function Effects 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 2
- 239000000820 nonprescription drug Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 3
- 239000003814 drug Substances 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 21
- 239000004530 micro-emulsion Substances 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000002453 shampoo Substances 0.000 abstract description 7
- 239000006184 cosolvent Substances 0.000 abstract description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 34
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- 230000002335 preservative effect Effects 0.000 description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 239000003205 fragrance Substances 0.000 description 18
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 18
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
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- 125000000217 alkyl group Chemical group 0.000 description 11
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
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- 229910052708 sodium Inorganic materials 0.000 description 9
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
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- 238000000576 coating method Methods 0.000 description 8
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 150000008051 alkyl sulfates Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
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- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 6
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- BOUCRWJEKAGKKG-UHFFFAOYSA-N n-[3-(diethylaminomethyl)-4-hydroxyphenyl]acetamide Chemical compound CCN(CC)CC1=CC(NC(C)=O)=CC=C1O BOUCRWJEKAGKKG-UHFFFAOYSA-N 0.000 description 6
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- FAGMGMRSURYROS-UHFFFAOYSA-M trihexadecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC FAGMGMRSURYROS-UHFFFAOYSA-M 0.000 description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229940075529 glyceryl stearate Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 229940100460 peg-100 stearate Drugs 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 229940044476 poloxamer 407 Drugs 0.000 description 5
- 230000002633 protecting effect Effects 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 150000003462 sulfoxides Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 239000003599 detergent Substances 0.000 description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 4
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
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- 229960004889 salicylic acid Drugs 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 3
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- 229940096386 coconut alcohol Drugs 0.000 description 3
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- 238000001816 cooling Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229940047642 disodium cocoamphodiacetate Drugs 0.000 description 3
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 3
- 230000001815 facial effect Effects 0.000 description 3
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- ADWNFGORSPBALY-UHFFFAOYSA-M sodium;2-[dodecyl(methyl)amino]acetate Chemical compound [Na+].CCCCCCCCCCCCN(C)CC([O-])=O ADWNFGORSPBALY-UHFFFAOYSA-M 0.000 description 3
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- DYNHRNODLOIZQP-UHFFFAOYSA-N 3-dodecoxy-2-hydroxy-n,n-bis(3-hydroxypropyl)propan-1-amine oxide Chemical compound CCCCCCCCCCCCOCC(O)C[N+]([O-])(CCCO)CCCO DYNHRNODLOIZQP-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
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- 208000002874 Acne Vulgaris Diseases 0.000 description 1
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- 239000004264 Petrolatum Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 238000010923 batch production Methods 0.000 description 1
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- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- 239000004148 curcumin Substances 0.000 description 1
- ZAKOWWREFLAJOT-UHFFFAOYSA-N d-alpha-Tocopheryl acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-UHFFFAOYSA-N 0.000 description 1
- ZRKZFNZPJKEWPC-UHFFFAOYSA-N decylamine-N,N-dimethyl-N-oxide Chemical compound CCCCCCCCCC[N+](C)(C)[O-] ZRKZFNZPJKEWPC-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229960001673 diethyltoluamide Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- ZCTXEAQXZGPWFG-UHFFFAOYSA-N imidurea Chemical compound O=C1NC(=O)N(CO)C1NC(=O)NCNC(=O)NC1C(=O)NC(=O)N1CO ZCTXEAQXZGPWFG-UHFFFAOYSA-N 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 229960004194 lidocaine Drugs 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
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- 102000035118 modified proteins Human genes 0.000 description 1
- 108091005573 modified proteins Proteins 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920006294 polydialkylsiloxane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000009877 rendering Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 208000008742 seborrheic dermatitis Diseases 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000004215 skin function Effects 0.000 description 1
- 229940045998 sodium isethionate Drugs 0.000 description 1
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 1
- IWMMSZLFZZPTJY-UHFFFAOYSA-M sodium;3-(dodecylamino)propane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCNCCCS([O-])(=O)=O IWMMSZLFZZPTJY-UHFFFAOYSA-M 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940042585 tocopherol acetate Drugs 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/007—Preparations for dry skin
-
- 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
- A61K8/062—Oil-in-water 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- 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
- A61Q5/02—Preparations for cleaning the hair
Definitions
- the present invention is directed to hair and skin ULTRAMULSIONTM based products, including, hair care products such as shampoos and rinses; skin care products, such as lotions, moisturizers, cleansers, and the like. All of these products are improved when an ULTRAMULSIONTM dispersion containing silicone and a surfactant is used as taught herein.
- ULTRAMULSIONTM is a trademark of WhiteHill Oral Technologies Inc.
- the ULTRAMULSIONTM dispersions of the present invention combine certain characteristics of emulsions with certain features of microemulsions. Like conventional emulsions, they are two phase systems comprising a silicone dispersed in a continuous, surfactant phase, wherein the silicone is insoluble in the surfactant.
- these dispersions are stable. Unlike microemulsions, but like conventional emulsions, mechanical work is required to form ULTRAMULSIONTM dispersions. Unlike microemulsions, but like conventional emulsions, these ULTRAMULSIONTM dispersions are not formed spontaneously. Like conventional emulsions, the ULTRAMULSIONTM dispersions do not contain a cosolvent commonly found in microemulsions. Of course, the ULTRAMULSIONTM dispersions of the present invention can be easily dispersed in various liquids such as water to obtain stable dispersions.
- ULTRAMULSIONTM dispersions have excellent utility in various hair and skin products.
- a. “Stable” is defined as follows; a dispersion of the ULTRAMULSIONTM dispersion in water when subjected to centrifuging in a 100 G environment for 5 minutes, less than about 10% by weight of the ULTRAMULSIONTM dispersion separates from the continuous water phase and/or a substantial portion (i.e., >50%) of the dispersed phase resists separation. This latter definition is particularly applicable to higher viscosity silicones.
- b. "Water-free" means that the ULTRAMULSIONTM dispersion of silicone and surfactant is substantially free from water.
- solvent free means that the ULTRAMULSIONTM dispersion of silicone and surfactant is substantially free from co-solvents such as ethanol, isopropanol, and the like.
- Oriented means that the polar moieties of the "uncoiled" polydimethylsiloxane in the ULTRAMULSIONTM dispersion are generally aligned in one plane with the hydrophilic oil seeking moieties aligned in a second plane such as illustrated in Fig. 2.
- Monolayer means that the monomolecular film of the ULTRAMULSIONTM dispersion of the present invention when dispersed in water is attracted to hair by secondary bonding force to form a substantive coating thereon.
- one preferred embodiment of the present invention relates to various hair care products containing stable dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on hair with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about 10 microns, with a particle size distribution such that from between about 80 and 95% of the dispersed silicone is within this particle size range. In certain embodiments, between 80-95% of two dispersed silicones is less than 1 - 2 microns ( ⁇ ) in particle size.
- ULTRAMULSIONTM dispersions which, together with their physical properties, when contained in hair care products, provide these hair care products with distinctive conditioning, moisturizing, protecting, etc. properties where the non continuous silicone phase functions as a reservoir for various hair treatment substances.
- Another preferred embodiment of the present invention relates to various skin care products containing stable dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on skin with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about 10 microns, with a particle size distribution such that from between about 80 and 95% of die dispersed silicone is within this particle size range. In certain embodiments, between 80-95% of two dispersed silicones is less than 1 - 2 microns ( ⁇ ) in particle size.
- ULTRAMULSIONTM dispersions which, together with their physical properties, when contained in skin care products, provide these skin care products with distinctive treating, moisturizing, protecting, etc. properties where the non continuous silicone phase functions as a reservoir for various skin treatment substances.
- the ULTRAMULSIONTM dispersions of skin care products of the present invention combine certain characteristics of emulsions wim certain features of microemulsions. That is, like emulsions, they are two phase systems comprising a silicone dispersed in a continuous, surfactant phase, wherein the silicone is insoluble in the surfactant. Unlike emulsions, but like microemulsions, these dispersions are stable.
- ULTRAMULSIONTM dispersions Unlike microemulsions, but like emulsions, mechanical work is required to form ULTRAMULSIONTM dispersions. Unlike microemulsions, but like emulsions, these ULTRAMULSIONTM dispersions are not formed spontaneously. Like emulsions, the ULTRAMULSIONTM dispersions do not contain a cosolvent commonly found in microemulsions. Of course, the ULTRAMULSIONTM dispersions of the present invention can be dispersed in various liquids such as water as stable dispersions.
- Fig. 1 illustrates the "coiled" molecular configuration proposed for polydimethylsiloxanes
- Fig. 2 illustrates the proposed molecular configuration of oriented polydimethylsiloxanes after ULTRAMULSIONTM dispersion processing
- Fig. 3 illustrates schematically an ULTRAMULSIONTM dispersion process of the present invention
- Figs. 4 and 5 illustrate that the ULTRAMULSIONTM dispersions of the present invention produced via various high shear dispersing means having particle size distribution of 80+ % under 10 microns.
- Fig. 1 illustrates the accepted "coiled" configuration advanced for polydimethylsiloxanes, wherein the methyl moieties are oriented outwardly while the oxygen moieties are oriented inwardly toward the axis of the coil or helix.
- This configuration does not readily promote, bonding between the oxygen moieties and compatible surfaces such as hair, skin, etc.
- Fig. 2 illustrates the "uncoiled oriented" configuration proposed for polydimethylsiloxanes that have been dispersed in the stable, ULTRAMULSIONTM dispersions of the present invention, wherein the oxygen moieties are generally oriented in one plane distinct from that of the methyl moieties.
- This proposed uncoiled oriented configuration appears to support the unique and unexpected stability, bonding and enhanced substantivity properties of the ULTRAMULSIONTM dispersions of the present invention, as evidenced by the various coating applications of these ULTRAMULSIONTM dispersions.
- Fig. 2 illustrates the "uncoiled oriented" configuration proposed for polydimethylsiloxanes that have been dispersed in the stable, ULTRAMULSIONTM dispersions of the present invention, wherein the oxygen moieties are generally oriented in one plane distinct from that of the methyl moieties.
- This proposed uncoiled oriented configuration appears to support the unique and unexpected stability, bonding and enhanced substantivity properties of the ULTRAMULSION
- FIG. 3 illustrates the ULTRAMULSIONTM dispersion process of the present invention wherein a nonionic surfactant and a polydimethylsiloxane 1, substantially free from water and co-solvent, are mixed in vessel 2, provided with mixing means 3, heat source 4, and inert head space 5.
- the heated and mixed surfactant-poly- dimethylsiloxane 6, is then subjected to high shear dispersion at an elevated temperature in dispersing means 7, to produce the ULTRAMULSIONTM dispersion 8, of die present invention.
- the high shear dispersion device (7) is typically selected from among devices manufactured by Ross, IKA Works, etc. Other energy sources such as flow-through ultrasonic cells may be used as well.
- Fig. 4 is a chart describing a typical particle size distribution of an ULTRAMULSIONTM dispersion of the present invention containing from about 50 to 95% by weight nonionic surfactant and from about 5 to 50% by weight polydimethylsiloxane (2.5 million cs) produced in a continuous process with an IKA Works dispersing means, (high shear dispersing) with an inlet temperature of 140°C and an outlet temperature of 210°C.
- Fig. 5 is a chart describing a typical particle size distribution of an ULTRAMULSIONTM dispersion of the present invention containing from about 50 to 95% by weight nonionic surfactant and from about 5 to 50% by weight polydimethylsiloxane (2.5 million cs) produced in a batch process with a Ross M/E 100 LC dispersing means fitted with a 20 mesh screen, operated at a temperature from about 120° to 160°C.
- the term "silicone” means a clear, colorless substance containing polydialkylsiloxane polymers with average kinematic viscosities ranging from about 100,000 centistokes (cs) to about 50 million cs, preferably from about 1 million cs to about 25 million cs, more preferably from about 1.5 million cs to about 10 million cs, and most preferably from about 2 million to about 5 million cs.
- This definition intentionally includes the so-called “gum” silicones having viscosities of 30 to 50 million cs.
- Certain high viscosity polydimethylsiloxanes having viscosities from about 2.5 million cs to about 4 million cs are particularly preferred for the hair care products of the present invention.
- polydimethylsiloxanes suitable for the present invention include "substituted" water insoluble silicones and mixtures of polydiorganosiloxanes and substituted water insoluble silicones. Specifically, water soluble silicones are excluded from the ULTRAMULSIONTM dispersions of die present invention.
- the viscosity of some silicones can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
- the silicone may be eiti er a high viscosity polyalkyl siloxane as described in detail below, a polyaryl siloxane, a polyalkylaryl siloxane or a polyedier siloxane copolymer. Mixtures of these silicones may also be used and are preferred in certain embodiments of the present invention.
- the polyalkylaryl siloxanes mat may be used include, for example, polymethylphenylsiloxanes having viscosities above 1 million centistokes at 20°C. Some of these siloxanes are available, for example, from the General Electric Company, from Dow Corning, and/or from Rhone-Poulenc.
- the polyether siloxane copolymer mat may be used is, for example, a polypropylene oxide modified dimethylpolysiloxane although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
- Silicone materials found especially useful in the present compositions to provide good dry combing are silicone gums. Silicone gums described by Petrarch and others including U.S. Patent No. 4,152,416, May 1, 1979 to Spitzer et al., and Noll, Walter, "Chemistry and Technology of Silicones," Academic Press, New York (1968). Also describing silicone gums are various General Electric Silicone Rubber Product Data Sheets. See also, "Silicone gum” materials denote high molecular weight polydiorganosiloxanes having a viscosity up to about 50,000,000 cs.
- polydimethylsiloxane examples include polydimethylsiloxane; polydimethylsiloxane; methylvinylsiloxane copolymer; polydimethylsiloxane; diphenylmethvinylsiloxane copolymer and mixtures thereof.
- polydimethylsiloxanes i.e., those above 100,000 cs are preferred in this invention.
- Particularly preferred are polydimethylsiloxanes having viscosities ranging from between about 2.5 million cs and about 50 million cs.
- the preferred polydimethylsiloxanes useful in the hair care compositions of the present invention are described as polymethylsiloxanes with the chemical composition (CH 3 ) 3 SiO[SiO(CH 3 ) 2 ] n Si(CH 3 ) 3 , wherein n is a whole number.
- These polydimethylsiloxanes have viscosities ranging up to about 50 million cs., and are generally described as having high molecular weight.
- the particle size of the silicone in the ULTRAMULSIONTM dispersions of the present invention can range from between about 0.1 and about 10 microns.
- the particle size of polydimethylsiloxanes in the ULTRAMULSIONTM dispersion ranges from below 1 up to about 5 microns.
- the particle size distribution of the polydimethylsiloxanes in the ULTRAMULSIONTM dispersions of the present invention generally range from between about 80% and about 95% of the particles under 10 microns. See especially Figs. 4 and 5. In a preferred embodiment of the present invention, from between about 80% and about 95% of the particles are under 5 microns.
- An essential component of the ULTRAMULSIONTM dispersion of the present invention is a surfactant.
- the surfactant may be selected from any of a wide variety of synthetic anionic, amphoteric, zwitterionic and nonionic surfactants.
- the surfactants suitable for the purposes of the present invention must function as the continuous phase and contain the discontinuous silicone phase.
- Synthetic anionic surfactants can be exemplified by the alkali metal salts of organic sulfuric reaction products having in eir molecular structure an alkyl radical containing from 8-22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (NOTE: included in the term alkyl is the alkyl portion of higher acyl radicals).
- a higher fatty alcohol e
- Zwitterionic surfactants can be exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxyl, sulfonate, sulfate, phosphate, or phosphonate.
- a general formula for these compounds is:
- R 2 contains an alkyl, alkenyl, or hydroxyl alkyl radical of from about 8 to 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety;
- Y is selected from the group consisting of nitrogen, phosphorous, and sulfur atoms;
- R 3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms;
- x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorous atom;
- R 4 is an alkylene or hydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
- Examples include; 4-[N,N-di(2-hydroxye yl)-N-octadecylammonio]-butane- 1 - carboxylate; 5-(S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l-sulfate;
- betaines useful herein include the higher alkyl betaines such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethylene betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methyl betaine, stearyl bis-(20-hydroxy-propyl)- carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2- hydroxypropyl)alpha-carboxyethyl betaine, etc.
- higher alkyl betaines such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethylene betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methyl betaine, stearyl bis-(20-hydroxy-propyl)- carboxymethyl be
- the sulfobetaines may be represented by cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoemyl betaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine and die like; amido betaines and amidosulfo betaines, wherein the RCONH(CH 2 ) 3 radical is attached to the nitrogen atom of me betaine are also useful in this invention.
- the amido betaines are preferred for use in some of the compositions of mis invention.
- a particularly preferred composition utilizes an amido betaine, a quaternary compound, a silicone, a suspending agent and has a pH of from about 2 to about 4.
- amphoteric surfactants which can be used in the ULTRAMULSIONTM dispersions of the present invention are tiiose which can be broadly described as derivatives of aliphatic secondary and tertiary amine in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
- tiiose which can be broadly described as derivatives of aliphatic secondary and tertiary amine in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or
- Examples of compounds falling within this definition are sodium 3- dodecylamino-propionate, sodium 3-dodecylamino-propane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine wi sodium isethionate according to the teachings of U.S. Patent No. 2,658,072, N-higher alkyl aspartic acids such as tiiose produced according to the teachings of U.S. Patent No. 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Patent No. 2,528,378.
- Nonionic surfactants which are preferably used in combination witii an anionic, amphoteric or zwitterionic surfactant, can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) wi an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of preferred classes of nonionic surfactants are: 1.
- the polyethylene oxide condensates of alkyl phenols, e.g., die condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 60 moles of ethylene oxide per mole of alkyl phenol.
- the alkyl substituent in such compounds may be derived from polymerized propylene, disobutylene, octane, or nonane, for example.
- Those derived from me condensation of emylene oxide with die product resulting from the reaction of propylene oxide and ethylenediamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired.
- compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 15,000 resulting from the reaction of ethylene oxide groups witi a hydrophobic base constituted of me reaction product of e ylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
- ethylene oxide e.g., a coconut alcohol emylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
- R contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms from 0 to about 10 emylene oxide moieties, and from 0 to 1 glyceryl moiety
- R 2 and R 3 contains from 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxy etiryl, or hydroxypropyl radicals.
- the arrow in d e formula is a conventional representation of a semipolar bond.
- Example of amine oxides suitable for use in mis invention include dimethyl-dodecylamine oxide, oleyldi(2-hydroxy-e yl)amine oxide, dimediyloctylamine oxide, dimethyl-decylamine oxide, dimediyltetradecylamine oxide. 3,6,9-trioxaheptadecyldiemylamine oxide, di(2-hydroxye yl)-tetracylamine oxide, 2- dodecoxyed yldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi-(3-hydroxy- propyl)amine oxide, dimethylhexadecylamine oxide. 5. Long chain tertiary phosphine oxides corresponding to the following general formula: R'- P ⁇ O
- R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chain length from 0 to about 10 ethylene oxide moieties and from
- R' and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms.
- the arrow in the formula is again the conventional representation of a semipolar bond.
- suitable phosphine oxides are: dodecyldime ylphosphine oxide, tetradecyl-dimethylphosphine oxide, tetradecyl-me ylethylphosphine oxide.
- Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of 1 to about 3 carbon atoms (usually methyl) and one long hydrophosphinic chain which contain alkyl, alkenyl, hydroxyalkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety.
- Examples include octadecyl menthyl sulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trioxooctadecyl 2- hydroxyemyl sulfoxide, dodecyl menthyl sulfoxide, oleyl 3 -hydroxypropyl sulfoxide, tetradecyl menthyl sulfoxide, 3-mefl ⁇ oxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxy-butyl methyl sulfoxide.
- Many additional nonsoap surfactants are described in McCUTCHEON'S, DETERGENTS AND EMULSIFIERS, 1979 ANNUAL, published by Allured Publishing Corporation.
- nonionic surfactants are nonionic poloxamer surfactants of block copolymers of ethylene oxide and propylene oxide ranging from flowable liquids of varying viscosities, to paste, prills and cast solids with molecular weights from 1,100 to 150,000.
- Suitable nonionic surfactants are manufactured and marketed by BASF Corporation under die trademarks Pluronic.
- Particularly preferred nonionic surfactants are Pluronic F-68, F-88, F-108 and Pluronic F-127. These are described in a BASF brochure entitled "Pluronic and Tetronic Block Copolymer Surfactant.”
- nonionic surfactants suitable for me present invention can be described by me following structure:
- nonionic surfactants of choice for die ULTRAMULSIONTM dispersions of the present invention are reported in die referenced brochure to have marginal detergency, emulsif ⁇ cation and wetting properties.
- the preferred nonionic poloxamer surfactants useful in the coating compositions of e present invention are described as polyoxyethylene- polyoxypropylene block copolymers such as Pluronic F-68, F-88, F-108 and F-127 (BASF) which have molecular weights of at least about 1000 such as those described in U.S. Patent Nos. 4,343,785, 4,465,663, 4,511,563 and 4,476,107.
- Emulsions of various coating substances including polydimethylsiloxanes in various surfactants including nonionic surfactants are disclosed and claimed in U.S. Patents 4,911,927, 4,942,034; 4,950,479; 5,009,881; 5,032,387; 5,057,306; 5,057,307; 5,057,308, 5,057,309; 5,057,310, 5,098,711, 5,165,913 and 5,284,648.
- tiiese references mat tiiese high viscosity silicone emulsions are stable nor that the "coating" substances are oriented as they are in the ULTRAMULSIONTM dispersions of the present invention.
- the ratio of surfactant to silicone in the ULTRAMULSIONTM dispersion coating compositions of die present invention can range from between about 400:1 and about 1 :2. In a preferred embodiment of the invention die ratio of surfactant to silicone is from between about 25:1 and 1:2.
- the ULTRAMULSIONTM dispersions of the present invention may be prepared as follows; generally, if not a liquid, the surfactant is first heated to a temperature at which it becomes a liquid.
- the silicone is men dispersed in the heated surfactant witii various high shear dispersing means.
- me heated surfactant is mechanically stirred along wim the silicone, to form a pre- emulsion mixture in which the silicone is uniformly dispersed in the surfactant in droplets of a larger size tiian desired for me ULTRAMULSIONTM dispersions but small enough to optimize the subsequent high shear dispersions.
- This mixture is subjected to high-shear dispersions witii a means such as the IKA- WORKS DISPAX- Reactor witii at least one superfine generator, alternatively, a Ross Model M.E., 100 LC fitted wim a 20 mesh screen or a ultrasonicator such as MEDSONIC XL2010 fitted with 800-C Flow Cell & 800-2 ICT 3/4 inch flanged horn can be used.
- Various ULTRAMULSIONTM dispersions useful in the present invention are prepared as described in the examples below: Examples 1 - 10 are formed as follows; the Poloxamer is heated to 70-90°C to melt the solid material. Once melted, the Poloxamer is stirred witii an overhead mixing blade.
- Dimediicone is added and the entire mass is mixed to obtain a uniform dispersion while maintaining the melt temperature.
- the material is then transferred to the homogenizer, ROSS homogenizer, model M.E. 100LC, and homogenized for 0.5 to 1.5 hours at 8000-10,000 RPM.
- the material is then cooled by a suitable cooling apparatus. The cooled material is then ready for use.
- Examples 11 - 15 are formed by adding the lipid soluble material to the dimethicone to solubilize; and a clear solution results. This solution is then added to the previously melted Poloxamer held at from about 60° to 80°C and mixed until uniform. The mixture is then homogenized in a ROSS, model ME 100LC mixer for 0.5 to 1.5 hours at 8000-10,000 RPM. The material is then cooled using any suitable cooling apparatus. These examples are:
- poloxamer/polydimethylsiloxane ULTRAMULSIONTM dispersions suitable for use witii various hair care products include die following examples: 16. 33 wt% Dimethicone (100,000 cs) and 67 wt% Poloaxmer-338; having a particle size distribution of ⁇ l ⁇ (44%); ⁇ 2 ⁇ (50%); ⁇ 3 ⁇ (4%); ⁇ 4 ⁇ (1%); ⁇ 5 ⁇ (1%); and >10 ⁇ (0%).
- the discontinuous silicone phase of the ULTRAMULSIONTM dispersion can also contain a wide range of lipid soluble and/or lipid dispersible hair care ingredients ranging from proteins, to essential oils, to fragrance to protectants such as U.V. absorbers, to pesticides such as pyrethrums, to repellents such as N,N-diethyl-m- toluamide (DEET).
- lipid soluble and/or lipid dispersible hair care ingredients ranging from proteins, to essential oils, to fragrance to protectants such as U.V. absorbers, to pesticides such as pyrethrums, to repellents such as N,N-diethyl-m- toluamide (DEET).
- the hair care products containing the ULTRAMULSIONTM dispersions of the present invention will contain a variety of essential components ranging from surfactants for cleaning, to various conditioning substances such as various proteins and modified proteins, to styling materials such as resins etc. These are detailed in various Examples described below.
- Water is an essential component of most shampoo/conditioners and conditioners of die present invention which contain one or more of the various ULTRAMULSIONSTM dispersions described above.
- the water in these products is generally present at a level of from about 20% to about 95%, preferably from between about 60% and about 90%.
- Such conventional optional ingredients are well known to tiiose skilled in die art, e.g., preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)- dimethylammonium chloride; tiiickeners and viscosity modifiers such as diemanolamide of a long chain fatty acid (e.g., PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and etiiyl alcohol; pH adjusting agents such as citric acid, succinic acid
- the pH of the present hair care compositions is not critical and may be in the range of from 2 to about 10. However, as set forth earlier, certain zwitterionic/quaternary compositions preferably have pH's of from about 2 to about 4.
- the shampoo/conditioners and conditioners and various styling and hair treatment products of the present invention can be made by mixing the materials together and heating from about 70°C to about 90°C.
- the mixture is mixed thoroughly for about 10 minutes at from about 70°C to about 90°C before being pumped flirough a heat exchanger to cool it to ambient temperature.
- the shampoo/conditioners, conditioners and various hair treatment products of the present invention are used in a conventional manner for cleaning conditioning and/or treating hair. From about O.lg to about 10 g of a composition is applied to hair tiiat has been wetted, generally witii water, worked through die hair and dien rinsed out.
- compositions are stable and deliver good conditioning to hair that is washed with die compositions.
- compositions are also stable and deliver good hair conditioning.
- Additional shampoo-conditioner examples of the present invention include the following:
- Examples 38 - 59 are directed to ULTRAMULSIONTM based skin care compositions. Like the hair care compositions of die preceding examples, these examples are formed as follows; the Poloxamer is heated to 70-90°C to melt the solid material. Once melted, die Poloxamer is stirred with an overhead mixing blade. Dimethicone is added and die entire mass is mixed to obtain a uniform dispersion while maintaining the melt temperature. The material is then transferred to the homogenizer (a ROSS Homogenizer, Model M.E. 100LC), and homogenized for 1/2 hour at 5000-10,000 RPM. The material is then cooled by a suitable cooling apparatus. The cooled material is men ready for use.
- the homogenizer a ROSS Homogenizer, Model M.E. 100LC
- the cooled material is men ready for use.
- the following additional examples of such dispersions have been found to be especially useful in skin care composition:
- the discontinuous silicone phase of die ULTRAMULSIONTM dispersion can also contain a wide range of lipid soluble and/or lipid dispersible skin care ingredients ranging from colorants to essential fragrances such as menthol and camphor to protectants such as U.V.
- absorbers to repellents such as N,N.-diethyl-toluamide (DEET) to moisturizers, such as petrolatum, glycerin, etc; to medicinals such as Vitamin E, aloe, etc., to deodorants/antiperspirants such as triclosan, aluminum zirconium trichlorohydrex gly, etc.; to antimicrobials such as triclosan; to antiseptics such as benzalkonium chloride, etc.; to antihistamines such as diphenylhydramine hydrochloride; to seborrheic dermatitis as psoriasis actives such as coal tar and steroids to analgesics such as benzocaine, lidocaine, etc.
- DEET N,N.-diethyl-toluamide
- the various ingredients are contained at least to some extent in the silicone phase of the ULTRAMULSIONTM dispersion to perform various skin functions as though they are contained in a "reservoir" as they continue to be available at the ULTRAMULSIONTM skin care interface, as long as the ULTRAMULSIONTM dispersion coating remains substantive to the skin.
- the sustained moisturizing, protecting, healing, etc. effects on skin obtained witii tiiese improved skin care products are discussed in various examples below.
- the skin care products containing die ULTRAMULSIONTM dispersions of the present invention will contain a variety of essential components ranging from surfactants for cleaning, to various moisturizing substances. These are detailed in various Examples described below.
- Water is an essential component of most skin care products of die present invention which contain one or more of the various ULTRAMULSIONTM dispersions described above.
- the water in these products is generally present at a level of from about 20% to about 95%, preferably from between about 60% and about 90%.
- tiiese skin care products can contain a variety of nonessential optional components suitable for rendering such compositions more cosmetically acceptable.
- Such conventional optional ingredients are well known to tiiose skilled in die art, e.g., preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidizolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)- dimethylammonium chloride; thickeners and viscosity modifiers such as dieflianolamide of a long chain fatty acid (e.g., PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate,
- the pH of the skin care compositions is not critical and may be in the range of from 2 to about 10. However, as set forth earlier certain zwitterionic/quaternary compositions preferably have pH's of from about 2 to about 4.
- the skin treatment products of die present invention can be made by mixing the materials together and heating to about 72°C. The mixture is mixed thoroughly for about 10 minutes at the 72°C temperature before being pumped through a heat exchanger to cool it to about 27°C.
- the skin treatment ULTRAMULSIONTM dispersions of the present invention are used in a conventional manner in various cosmetic, OTC Drug and R* drug products for cleaning, moisturizing, coloring, protecting, treating, healing etc. the skin, as shown in the Examples below:
- Skin Moisturizer Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSIONTM dispersion of Example 2; Phase D - 0.5 wt% triedianolamine; Phase E - preservative and fragrance (qv to 100%)
- Skin Moisturizer Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSIONTM dispersion of Example 3; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%)
- Skin Moisturizer Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSIONTM dispersion of Example 5; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%)
- Skin Moisturizer Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSIONTM dispersion of Example 8; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%) 52.
- Skin Moisturizer Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSIONTM dispersion of Example 15; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%) 53.
- Facial Cleanser 12 wt% disodium cocoamphodiacetate, 10 wt% sodium lauryl sarcosinate, 7 wt% cocoamido beatine, 4 wt% laurylamide DEA, 62.5 wt% water, 0.5 wt% citric acid, 4 wt% of the ULTRAMULSIONTM dispersion of Example 6, preservative and fragrance (qv).
- Facial Cleanser 12 wt% disodium cocoamphodiacetate, 10 wt% sodium lauryl sarcosinate, 7 wt% cocoamido beatine, 4 wt% laurylamide DEA, 63.5 wt% water, 0.5 wt% citric acid, 3 wt% of the ULTRAMULSIONTM dispersion of Example 4, preservative and fragrance (qv).
- Facial Cleanser 12 wt% disodium cocoamphodiacetate, 10 wt% sodium lauryl sarcosinate, 7 wt% cocoamido beatine, 4 wt% laurylamide DEA, 63.5 wt% water, 0.5 wt% citric acid, 3 wt% of the ULTRAMULSIONTM dispersion of Example 10, preservative and fragrance (qv).
- Hand and Face Liquid Detergent 62.9 wt% water, 25 wt% sodium lauryl sulfate, 6 wt% sodium laureth sulfate, 3 wt% cocoamidopropyl beatine, 2 wt% glyceryl cocoate, 0.5 wt% EDTA, 0.6 wt% NaCl, 3 wt% of the ULTRAMULSIONTM dispersion of Example 1, preservative and fragrance (qv).
- Hand and Face Liquid Detergent 62.9 wt% water, 25 wt% sodium lauryl sulfate, 6 wt% sodium laureth sulfate, 3 wt% cocoamidopropyl beatine, 2 wt% glyceryl cocoate, 0.5 wt% EDTA, 0.6 wt% NaCl, 3 wt% of the ULTRAMULSIONTM dispersion of Example 4, preservative and fragrance (qv). 59.
- Hand and Face Liquid Detergent 62.9 wt% water, 25 wt% sodium lauryl sulfate, 6 wt% sodium laureth sulfate, 3 wt% cocoamidopropyl beatine, 2 wt% glyceryl cocoate, 0.5 wt% EDTA, 0.6 wt% NaCl, 3 wt% of the ULTRAMULSIONTM dispersion of Example 17, preservative and fragrance
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Abstract
The present invention is directed to hair and skin ULTRAMULSIONTM based products, including hair care products such as shampoos and rinses; and skin care products, such as lotions, cleansers, moisturizers, and the like. All of these products are improved when an ULTRAMULSIONTM dispersion containing silicone and a surfactant is used as taught herein. The ULTRAMULSIONTM dispersions of the present invention combine certain characteristics of emulsions with certain features of microemulsions. Like conventional emulsions, they are two-phase systems comprising a silicone dispersed in a continuous, surfactant phase, wherein the silicone is insoluble in the surfactant. Unlike conventional emulsions, but like microemulsions, these dispersions are stable. Unlike microemulsions, but like conventional emulsions, mechanical work is required to form ULTRAMULSIONTM dispersions. Unlike microemulsions, but like conventional emulsions, these ULTRAMULSIONTM dispersions are not formed spontaneously. Like conventional emulsions, the ULTRAMULSIONTM dispersions do not contain a cosolvent commonly found in microemulsions. Of course, the ULTRAMULSIONTM dispersions of the present invention can be easily dispersed in various liquids such as water to obtain stable dispersions. These dispersions of ULTRAMULSIONTM dispersions in water have excellent utility in various hair and skin products.
Description
HAIR AND SKIN ULTRAMULSION BASED PRODUCTS
SUMMARY OF THE INVENTION
The present invention is directed to hair and skin ULTRAMULSION™ based products, including, hair care products such as shampoos and rinses; skin care products, such as lotions, moisturizers, cleansers, and the like. All of these products are improved when an ULTRAMULSION™ dispersion containing silicone and a surfactant is used as taught herein. ULTRAMULSION™ is a trademark of WhiteHill Oral Technologies Inc.
The ULTRAMULSION™ dispersions of the present invention combine certain characteristics of emulsions with certain features of microemulsions. Like conventional emulsions, they are two phase systems comprising a silicone dispersed in a continuous, surfactant phase, wherein the silicone is insoluble in the surfactant.
Unlike conventional emulsions, but like microemulsions, these dispersions are stable. Unlike microemulsions, but like conventional emulsions, mechanical work is required to form ULTRAMULSION™ dispersions. Unlike microemulsions, but like conventional emulsions, these ULTRAMULSION™ dispersions are not formed spontaneously. Like conventional emulsions, the ULTRAMULSION™ dispersions do not contain a cosolvent commonly found in microemulsions. Of course, the ULTRAMULSION™ dispersions of the present invention can be easily dispersed in various liquids such as water to obtain stable dispersions. These dispersions of ULTRAMULSION™ dispersions in water have excellent utility in various hair and skin products. For the purposes of the present invention: a. "Stable" is defined as follows; a dispersion of the ULTRAMULSION™ dispersion in water when subjected to centrifuging in a 100 G environment for 5 minutes, less than about 10% by weight of the ULTRAMULSION™ dispersion separates from the continuous water phase and/or a substantial portion (i.e., >50%) of the dispersed phase resists separation. This latter definition is particularly applicable to higher viscosity silicones. b. "Water-free" means that the ULTRAMULSION™ dispersion of
silicone and surfactant is substantially free from water. c. "Solvent free" means that the ULTRAMULSION™ dispersion of silicone and surfactant is substantially free from co-solvents such as ethanol, isopropanol, and the like. d. "Oriented" means that the polar moieties of the "uncoiled" polydimethylsiloxane in the ULTRAMULSION™ dispersion are generally aligned in one plane with the hydrophilic oil seeking moieties aligned in a second plane such as illustrated in Fig. 2. e. "Monolayer" means that the monomolecular film of the ULTRAMULSION™ dispersion of the present invention when dispersed in water is attracted to hair by secondary bonding force to form a substantive coating thereon.
As described above, one preferred embodiment of the present invention relates to various hair care products containing stable dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on hair with enhanced substantivity, and b. the particle size of the dispersed silicone is from between about 0.1 and about 10 microns, with a particle size distribution such that from between about 80 and 95% of the dispersed silicone is within this particle size range. In certain embodiments, between 80-95% of two dispersed silicones is less than 1 - 2 microns (μ) in particle size. These stable dispersions are described as ULTRAMULSION™ dispersions, which, together with their physical properties, when contained in hair care products, provide these hair care products with distinctive conditioning, moisturizing, protecting, etc. properties where the non continuous silicone phase functions as a reservoir for various hair treatment substances.
Another preferred embodiment of the present invention relates to various skin care products containing stable dispersions of certain high viscosity silicones in certain surfactants; wherein: a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on skin with enhanced substantivity, and
b. the particle size of the dispersed silicone is from between about 0.1 and about 10 microns, with a particle size distribution such that from between about 80 and 95% of die dispersed silicone is within this particle size range. In certain embodiments, between 80-95% of two dispersed silicones is less than 1 - 2 microns (μ) in particle size. These stable dispersions are described as ULTRAMULSION™ dispersions, which, together with their physical properties, when contained in skin care products, provide these skin care products with distinctive treating, moisturizing, protecting, etc. properties where the non continuous silicone phase functions as a reservoir for various skin treatment substances. The ULTRAMULSION™ dispersions of skin care products of the present invention combine certain characteristics of emulsions wim certain features of microemulsions. That is, like emulsions, they are two phase systems comprising a silicone dispersed in a continuous, surfactant phase, wherein the silicone is insoluble in the surfactant. Unlike emulsions, but like microemulsions, these dispersions are stable. Unlike microemulsions, but like emulsions, mechanical work is required to form ULTRAMULSION™ dispersions. Unlike microemulsions, but like emulsions, these ULTRAMULSION™ dispersions are not formed spontaneously. Like emulsions, the ULTRAMULSION™ dispersions do not contain a cosolvent commonly found in microemulsions. Of course, the ULTRAMULSION™ dispersions of the present invention can be dispersed in various liquids such as water as stable dispersions.
These dispersions of ULTRAMULSION™ dispersions in water have excellent utility in various skin care products. See various examples below.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 illustrates the "coiled" molecular configuration proposed for polydimethylsiloxanes;
Fig. 2 illustrates the proposed molecular configuration of oriented polydimethylsiloxanes after ULTRAMULSION™ dispersion processing;
Fig. 3 illustrates schematically an ULTRAMULSION™ dispersion process of the present invention; and
Figs. 4 and 5 illustrate that the ULTRAMULSION™ dispersions of the present invention produced via various high shear dispersing means having particle size distribution of 80+ % under 10 microns.
DETAILED DESCRD7TION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, Fig. 1 illustrates the accepted "coiled" configuration advanced for polydimethylsiloxanes, wherein the methyl moieties are oriented outwardly while the oxygen moieties are oriented inwardly toward the axis of the coil or helix. This configuration does not readily promote, bonding between the oxygen moieties and compatible surfaces such as hair, skin, etc.
Fig. 2 illustrates the "uncoiled oriented" configuration proposed for polydimethylsiloxanes that have been dispersed in the stable, ULTRAMULSION™ dispersions of the present invention, wherein the oxygen moieties are generally oriented in one plane distinct from that of the methyl moieties. This proposed uncoiled oriented configuration appears to support the unique and unexpected stability, bonding and enhanced substantivity properties of the ULTRAMULSION™ dispersions of the present invention, as evidenced by the various coating applications of these ULTRAMULSION™ dispersions. Fig. 3 illustrates the ULTRAMULSION™ dispersion process of the present invention wherein a nonionic surfactant and a polydimethylsiloxane 1, substantially free from water and co-solvent, are mixed in vessel 2, provided with mixing means 3, heat source 4, and inert head space 5. The heated and mixed surfactant-poly- dimethylsiloxane 6, is then subjected to high shear dispersion at an elevated temperature in dispersing means 7, to produce the ULTRAMULSION™ dispersion 8, of die present invention. The high shear dispersion device (7) is typically selected from among devices manufactured by Ross, IKA Works, etc. Other energy sources such as flow-through ultrasonic cells may be used as well.
Fig. 4 is a chart describing a typical particle size distribution of an ULTRAMULSION™ dispersion of the present invention containing from about 50 to 95% by weight nonionic surfactant and from about 5 to 50% by weight polydimethylsiloxane (2.5 million cs) produced in a continuous process with an IKA
Works dispersing means, (high shear dispersing) with an inlet temperature of 140°C and an outlet temperature of 210°C.
Fig. 5 is a chart describing a typical particle size distribution of an ULTRAMULSION™ dispersion of the present invention containing from about 50 to 95% by weight nonionic surfactant and from about 5 to 50% by weight polydimethylsiloxane (2.5 million cs) produced in a batch process with a Ross M/E 100 LC dispersing means fitted with a 20 mesh screen, operated at a temperature from about 120° to 160°C.
For purposes of the present invention, the term "silicone" means a clear, colorless substance containing polydialkylsiloxane polymers with average kinematic viscosities ranging from about 100,000 centistokes (cs) to about 50 million cs, preferably from about 1 million cs to about 25 million cs, more preferably from about 1.5 million cs to about 10 million cs, and most preferably from about 2 million to about 5 million cs. This definition intentionally includes the so-called "gum" silicones having viscosities of 30 to 50 million cs. Certain high viscosity polydimethylsiloxanes having viscosities from about 2.5 million cs to about 4 million cs are particularly preferred for the hair care products of the present invention. Other polydimethylsiloxanes suitable for the present invention include "substituted" water insoluble silicones and mixtures of polydiorganosiloxanes and substituted water insoluble silicones. Specifically, water soluble silicones are excluded from the ULTRAMULSION™ dispersions of die present invention.
The viscosity of some silicones can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970. The silicone may be eiti er a high viscosity polyalkyl siloxane as described in detail below, a polyaryl siloxane, a polyalkylaryl siloxane or a polyedier siloxane copolymer. Mixtures of these silicones may also be used and are preferred in certain embodiments of the present invention.
The polyalkylaryl siloxanes mat may be used include, for example, polymethylphenylsiloxanes having viscosities above 1 million centistokes at 20°C. Some of these siloxanes are available, for example, from the General Electric Company, from Dow Corning, and/or from Rhone-Poulenc.
The polyether siloxane copolymer mat may be used is, for example, a polypropylene oxide modified dimethylpolysiloxane although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
References disclosing suitable silicone fluids include U.S. Patent No. 2,826,551 to Green; U.S. Patent No. 3,964,500 to Drakoff; U.S. Patent No. 4,364,837 to Padner and British Patent No. 849,433 to Woolston. See also, Silicon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides a very good listing of suitable silicone materials.
Silicone materials found especially useful in the present compositions to provide good dry combing are silicone gums. Silicone gums described by Petrarch and others including U.S. Patent No. 4,152,416, May 1, 1979 to Spitzer et al., and Noll, Walter, "Chemistry and Technology of Silicones," Academic Press, New York (1968). Also describing silicone gums are various General Electric Silicone Rubber Product Data Sheets. See also, "Silicone gum" materials denote high molecular weight polydiorganosiloxanes having a viscosity up to about 50,000,000 cs. Specific examples include polydimethylsiloxane; polydimethylsiloxane; methylvinylsiloxane copolymer; polydimethylsiloxane; diphenylmethvinylsiloxane copolymer and mixtures thereof.
As noted above high viscosity polydimethylsiloxanes i.e., those above 100,000 cs are preferred in this invention. Particularly preferred are polydimethylsiloxanes having viscosities ranging from between about 2.5 million cs and about 50 million cs.
The safety of polydimethylsiloxanes for use in these various products is well documented. See Rowe et al., Journal of Industrial Hygiene, 30(6): 332-352 (1948). See also Calandra et al., ACS Polymer Preprints, 17: 1-4 (1976) and Kennedy et al., J. Toxicol. & Environmental Health, 1: 909-920 (1976).
As noted above, the preferred polydimethylsiloxanes useful in the hair care compositions of the present invention are described as polymethylsiloxanes with the chemical composition (CH3)3SiO[SiO(CH3)2]nSi(CH3)3, wherein n is a whole number. These polydimethylsiloxanes have viscosities ranging up to about 50 million cs., and are generally described as having high molecular weight.
The particle size of the silicone in the ULTRAMULSION™ dispersions of the present invention can range from between about 0.1 and about 10 microns. In a
preferred embodiment of the present invention the particle size of polydimethylsiloxanes in the ULTRAMULSION™ dispersion ranges from below 1 up to about 5 microns. The particle size distribution of the polydimethylsiloxanes in the ULTRAMULSION™ dispersions of the present invention generally range from between about 80% and about 95% of the particles under 10 microns. See especially Figs. 4 and 5. In a preferred embodiment of the present invention, from between about 80% and about 95% of the particles are under 5 microns.
An essential component of the ULTRAMULSION™ dispersion of the present invention is a surfactant. The surfactant, may be selected from any of a wide variety of synthetic anionic, amphoteric, zwitterionic and nonionic surfactants. The surfactants suitable for the purposes of the present invention must function as the continuous phase and contain the discontinuous silicone phase.
Synthetic anionic surfactants can be exemplified by the alkali metal salts of organic sulfuric reaction products having in eir molecular structure an alkyl radical containing from 8-22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (NOTE: included in the term alkyl is the alkyl portion of higher acyl radicals). Preferred are the sodium, ammonium, potassium or triethanolamine alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms), sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and 1 to 12 moles of ethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms, sodium alkyl glyceryl ether sulfonates; d e reaction product of fatty acids having from 10 to 22 carbon atoms esterified with isethionic acid and neutralized with sodium hydroxide; water soluble salts of condensation products of fatty acids wid sarcosine; and others known in the art.
Zwitterionic surfactants can be exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxyl, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds
is:
wherein R2 contains an alkyl, alkenyl, or hydroxyl alkyl radical of from about 8 to 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorous, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorous atom; R4 is an alkylene or hydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Examples include; 4-[N,N-di(2-hydroxye yl)-N-octadecylammonio]-butane- 1 - carboxylate; 5-(S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l-sulfate;
3-[P,P-diemyl-P-3,6,9-trioxatetradecocylphosphonio]-2-hydroxypropane-l-phosphate;
3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-l-phosphate;
3-[N,N-dimethyl-N-hexadecylammonio-propane- 1 -sulfonate;
4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-l-carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane- 1 -phosphate;
3-[P,P-dimethyl-P-dodecylphosphonio]-propane-l -phosphonate; and
5-(N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypentane-l-sulfate.
Other zwitterionics such as betaines are also useful in the present invention.
Examples of betaines useful herein include the higher alkyl betaines such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethylene betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methyl betaine, stearyl bis-(20-hydroxy-propyl)- carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2- hydroxypropyl)alpha-carboxyethyl betaine, etc. The sulfobetaines may be represented by cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl
dimethyl sulfoemyl betaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine and die like; amido betaines and amidosulfo betaines, wherein the RCONH(CH2)3 radical is attached to the nitrogen atom of me betaine are also useful in this invention. The amido betaines are preferred for use in some of the compositions of mis invention. A particularly preferred composition utilizes an amido betaine, a quaternary compound, a silicone, a suspending agent and has a pH of from about 2 to about 4.
Examples of amphoteric surfactants which can be used in the ULTRAMULSION™ dispersions of the present invention are tiiose which can be broadly described as derivatives of aliphatic secondary and tertiary amine in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3- dodecylamino-propionate, sodium 3-dodecylamino-propane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine wi sodium isethionate according to the teachings of U.S. Patent No. 2,658,072, N-higher alkyl aspartic acids such as tiiose produced according to the teachings of U.S. Patent No. 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Patent No. 2,528,378. Nonionic surfactants, which are preferably used in combination witii an anionic, amphoteric or zwitterionic surfactant, can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) wi an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of preferred classes of nonionic surfactants are: 1. The polyethylene oxide condensates of alkyl phenols, e.g., die condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, disobutylene, octane, or nonane, for example.
2. Those derived from me condensation of emylene oxide with die
product resulting from the reaction of propylene oxide and ethylenediamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 15,000 resulting from the reaction of ethylene oxide groups witi a hydrophobic base constituted of me reaction product of e ylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
3. The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol emylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
4. Long chain tertiary amine oxides corresponding to the following general formula:
wherein R, contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms from 0 to about 10 emylene oxide moieties, and from 0 to 1 glyceryl moiety, and R2 and R3 contains from 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxy etiryl, or hydroxypropyl radicals. The arrow in d e formula is a conventional representation of a semipolar bond. Example of amine oxides suitable for use in mis invention include dimethyl-dodecylamine oxide, oleyldi(2-hydroxy-e yl)amine oxide, dimediyloctylamine oxide, dimethyl-decylamine oxide, dimediyltetradecylamine oxide. 3,6,9-trioxaheptadecyldiemylamine oxide, di(2-hydroxye yl)-tetracylamine oxide, 2- dodecoxyed yldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi-(3-hydroxy- propyl)amine oxide, dimethylhexadecylamine oxide. 5. Long chain tertiary phosphine oxides corresponding to the following general formula:
R'- P → O
/ R" wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chain length from 0 to about 10 ethylene oxide moieties and from
0 to 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is again the conventional representation of a semipolar bond. Examples of suitable phosphine oxides are: dodecyldime ylphosphine oxide, tetradecyl-dimethylphosphine oxide, tetradecyl-me ylethylphosphine oxide. 3,6,9-trioxaocta-decyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyl-di(2-hydroxyl)- phosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, cetyldiemylphosphine oxide, dodecyl-died ylphosphine oxide, tetradecyl- diethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(2- hydroxye yl)phosphine oxide, tetradecyl-medιyl-2-hydroxydodecyldimedιylphosphine oxide.
6. Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of 1 to about 3 carbon atoms (usually methyl) and one long hydrophosphinic chain which contain alkyl, alkenyl, hydroxyalkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety. Examples include octadecyl menthyl sulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trioxooctadecyl 2- hydroxyemyl sulfoxide, dodecyl menthyl sulfoxide, oleyl 3 -hydroxypropyl sulfoxide, tetradecyl menthyl sulfoxide, 3-meflιoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxy-butyl methyl sulfoxide. Many additional nonsoap surfactants are described in McCUTCHEON'S, DETERGENTS AND EMULSIFIERS, 1979 ANNUAL, published by Allured Publishing Corporation.
Particularly preferred nonionic surfactants are nonionic poloxamer surfactants of block copolymers of ethylene oxide and propylene oxide ranging from flowable liquids of varying viscosities, to paste, prills and cast solids with molecular weights from 1,100 to 150,000. Suitable nonionic surfactants are manufactured and marketed by BASF Corporation under die trademarks Pluronic. Particularly preferred nonionic
surfactants are Pluronic F-68, F-88, F-108 and Pluronic F-127. These are described in a BASF brochure entitled "Pluronic and Tetronic Block Copolymer Surfactant."
These nonionic surfactants suitable for me present invention can be described by me following structure:
CH3
I
OH-(CH2CH2))x - (CH2CHO)y - (CH2CH2O)x. - H
where x, y and x' are whole numbers. Surprisingly, the nonionic surfactants of choice for die ULTRAMULSION™ dispersions of the present invention are reported in die referenced brochure to have marginal detergency, emulsifϊcation and wetting properties. As noted above, the preferred nonionic poloxamer surfactants useful in the coating compositions of e present invention are described as polyoxyethylene- polyoxypropylene block copolymers such as Pluronic F-68, F-88, F-108 and F-127 (BASF) which have molecular weights of at least about 1000 such as those described in U.S. Patent Nos. 4,343,785, 4,465,663, 4,511,563 and 4,476,107. Emulsions of various coating substances including polydimethylsiloxanes in various surfactants including nonionic surfactants are disclosed and claimed in U.S. Patents 4,911,927, 4,942,034; 4,950,479; 5,009,881; 5,032,387; 5,057,306; 5,057,307; 5,057,308, 5,057,309; 5,057,310, 5,098,711, 5,165,913 and 5,284,648. There is however, no teaching or suggestion in tiiese references mat tiiese high viscosity silicone emulsions are stable nor that the "coating" substances are oriented as they are in the ULTRAMULSION™ dispersions of the present invention.
The ratio of surfactant to silicone in the ULTRAMULSION™ dispersion coating compositions of die present invention can range from between about 400:1 and about 1 :2. In a preferred embodiment of the invention die ratio of surfactant to silicone is from between about 25:1 and 1:2.
The ULTRAMULSION™ dispersions of the present invention may be prepared as follows; generally, if not a liquid, the surfactant is first heated to a temperature at which it becomes a liquid. The silicone is men dispersed in the heated surfactant witii various high shear dispersing means. In one preferred method, me heated surfactant is mechanically stirred along wim the silicone, to form a pre-
emulsion mixture in which the silicone is uniformly dispersed in the surfactant in droplets of a larger size tiian desired for me ULTRAMULSION™ dispersions but small enough to optimize the subsequent high shear dispersions. This mixture is subjected to high-shear dispersions witii a means such as the IKA- WORKS DISPAX- Reactor witii at least one superfine generator, alternatively, a Ross Model M.E., 100 LC fitted wim a 20 mesh screen or a ultrasonicator such as MEDSONIC XL2010 fitted with 800-C Flow Cell & 800-2 ICT 3/4 inch flanged horn can be used. Various ULTRAMULSION™ dispersions useful in the present invention are prepared as described in the examples below: Examples 1 - 10 are formed as follows; the Poloxamer is heated to 70-90°C to melt the solid material. Once melted, the Poloxamer is stirred witii an overhead mixing blade. Dimediicone is added and the entire mass is mixed to obtain a uniform dispersion while maintaining the melt temperature. The material is then transferred to the homogenizer, ROSS homogenizer, model M.E. 100LC, and homogenized for 0.5 to 1.5 hours at 8000-10,000 RPM. The material is then cooled by a suitable cooling apparatus. The cooled material is then ready for use. These ULTRAMULSION™ dispersion examples are:
1. 10 wt% Dimethicone (100,000 cs) and 90 wt% Poloaxmer-338
2. 10 wt% Dimethicone (600,000 cs) and 90 wt% Poloxamer-338 3. 10 wt% Dimethicone (2,500,000 cs) and 90 wt% Poloxamer-338
4. 10 wt% Dimethicone (4,000,000 cs) and 90 wt% Poloxamer-338
5. 33 wt% Dimethicone (100,000 cs) and 67 wt% Poloaxmer-407
6. 33 wt% Dimethicone (600,000 cs) and 67 wt% Poloxamer-407
7. 33 wt% Dimethicone (2,500,000 cs) and 67 wt% Poloxamer-407 8. 33 wt% Dimethicone (4,000,000 cs) and 67 wt% Poloxamer-407
9. 20 wt% Dimethicone (2,500,000 cs) and 80 wt% Poloxamer-188
10. 20 wt% Dimethicone (4,000,000 cs) and 67 wt% Poloxamer-388 Examples 11 - 15 are formed by adding the lipid soluble material to the dimethicone to solubilize; and a clear solution results. This solution is then added to the previously melted Poloxamer held at from about 60° to 80°C and mixed until uniform. The mixture is then homogenized in a ROSS, model ME 100LC mixer for 0.5 to 1.5 hours at 8000-10,000 RPM. The material is then cooled using any suitable
cooling apparatus. These examples are:
11. 10 wt% Dimethicone (2,500,000 cs), 1 wt% octyldimethyl PABA, and 89 wt% Poloxamer-338
12. 10 wt% Dimethicone (2,500,000 cs), 2 wt% Vitamin E Acetate, and 88 wt% Poloxamer-338
13. 10 wt% Dimethicone (2,500,000 cs), 1 wt% Isopropyl Palmitate, and 89 wt% Poloxamer-338
14. 10 wt% Dimethicone (2,500,000 cs), 1.5 wt% Fragrance IFF No. 17.92.3415, and 88.5 wt% Poloxamer-338 15. 10 wt% Dimethicone (4,000,000 cs), 1 wt% Fragrance IFF No. 17.92.3415, and 89 wt% Poloxamer-338
Specific examples of poloxamer/polydimethylsiloxane ULTRAMULSION™ dispersions suitable for use witii various hair care products include die following examples: 16. 33 wt% Dimethicone (100,000 cs) and 67 wt% Poloaxmer-338; having a particle size distribution of <lμ (44%); <2μ (50%); <3μ (4%); <4μ (1%); <5μ (1%); and >10μ (0%).
17. 10 wt% Dimethicone (600,000 cs) and 90 wt% Poloxamer-338; having a particle size distribution of <lμ (24%); <2μ (40%); <3μ (5%); <4μ (2%); <5μ (1%); and >10μ (0%).
18. 10 wt% Dimethicone (2,500,000 cs) and 90 wt% Poloxamer-407; having a particle size distribution of <lμ (2%); <2μ (3%); <3μ (63%); <4μ (24%); <5μ (8%); and >10μ (0%).
19. 10 wt% Dimethicone (4,000,000 cs) and 90 wt% Poloxamer-407; having a particle size distribution of <lμ (1.5%); <2μ (6%); <3μ (51%); <4μ (43.5%);
<5μ (14%); and >10μ (0%).
The discontinuous silicone phase of the ULTRAMULSION™ dispersion can also contain a wide range of lipid soluble and/or lipid dispersible hair care ingredients ranging from proteins, to essential oils, to fragrance to protectants such as U.V. absorbers, to pesticides such as pyrethrums, to repellents such as N,N-diethyl-m- toluamide (DEET). These various ingredients in the silicone phase of the ULTRAMULSION™ dispersion perform tiieir intended function in various hair
conditioners, shampoo/conditioners, styling products etc. as ti ough they are contained in a "reservoir" as they continue to be available at die ULTRAMULSION™ dispersion containing-hair interface, as long as the ULTRAMULSION™ dispersion coating remains substantive to the hair. The sustained conditioning moisturizing, protecting, repairing, and like effects on hair obtained with these improved hair care products are discussed in various examples below.
The hair care products containing the ULTRAMULSION™ dispersions of the present invention will contain a variety of essential components ranging from surfactants for cleaning, to various conditioning substances such as various proteins and modified proteins, to styling materials such as resins etc. These are detailed in various Examples described below.
Water is an essential component of most shampoo/conditioners and conditioners of die present invention which contain one or more of the various ULTRAMULSIONS™ dispersions described above. The water in these products is generally present at a level of from about 20% to about 95%, preferably from between about 60% and about 90%.
Such conventional optional ingredients are well known to tiiose skilled in die art, e.g., preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)- dimethylammonium chloride; tiiickeners and viscosity modifiers such as diemanolamide of a long chain fatty acid (e.g., PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and etiiyl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc., perfumes; dyes; and, sequestering agents such as disodium efliylenediamine tetraacetate. Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about 0.5% to about 5.0% by weight of the composition.
The pH of the present hair care compositions is not critical and may be in the range of from 2 to about 10. However, as set forth earlier, certain
zwitterionic/quaternary compositions preferably have pH's of from about 2 to about 4.
The shampoo/conditioners and conditioners and various styling and hair treatment products of the present invention can be made by mixing the materials together and heating from about 70°C to about 90°C. The mixture is mixed thoroughly for about 10 minutes at from about 70°C to about 90°C before being pumped flirough a heat exchanger to cool it to ambient temperature.
The shampoo/conditioners, conditioners and various hair treatment products of the present invention are used in a conventional manner for cleaning conditioning and/or treating hair. From about O.lg to about 10 g of a composition is applied to hair tiiat has been wetted, generally witii water, worked through die hair and dien rinsed out.
The following additional examples are illustrative of die shampoo-conditioners of die present invention:
20. 7.5 wt% Sodium lauryl sulfate, 5.0 wt% sodium lauryl ether sulfate; 5.0 wt% Lauramide DEA, 1.0 wt% Cocoamidopropyl Beatine, 1.3 wt% of die Example
2 ULTRAMULSION™ dispersion, preservative (qv), 0.4 wt% citric acid, 0.3 wt% NaCl, deionized water (qv to 100%); pH 6.0
21. 7.5 wt% Sodium lauryl sulfate, 5.0 wt% sodium lauryl ether sulfate; 5.0 wt% Lauramide DEA, 1.0 wt% Cocoamidopropyl Beatine, 1.3 wt% of die Example 3 ULTRAMULSION™ dispersion, preservative (qv), 0.4 wt% citric acid, 0.3 wt% NaCl, deionized water (qv to 100%); pH 6.0
22. 7.5 wt% Sodium lauryl sulfate, 5.0 wt% sodium lauryl e er sulfate; 5.0 wt% Lauramide DEA, 1.0 wt% Cocoamidopropyl Beatine, 1.3 wt% of the Example
4 ULTRAMULSION™ dispersion, preservative (qv), 0.4 wt% citric acid, 0.3 wt% NaCl, deionized water (qv to 100%); pH 6.0
23. 7.5 wt% Sodium lauryl sulfate, 5.0 wt% sodium lauryl eflier sulfate; 5.0 wt% Lauramide DEA, 1.0 wt% Cocoamidopropyl Beatine, 1.3 wt% of die Example 9 ULTRAMULSION™ dispersion, preservative (qv), 0.4 wt% citric acid, 0.3 wt% NaCl, deionized water (qv to 100%); pH 6.0 24. 7.5 wt% Sodium lauryl sulfate, 5.0 wt% sodium lauryl ether sulfate; 5.0 wt% Lauramide DEA, 1.0 wt% Cocoamidopropyl Beatine, 1.3 wt% of the Example
5 ULTRAMULSION™ dispersion, preservative (qv), 0.4 wt% citric acid, 0.3
wt% NaCl, deionized water (qv to 100%); pH 6.0
These compositions are stable and deliver good conditioning to hair that is washed with die compositions.
The following examples are two anionic shampoo compositions illustrative of the present invention.
25. 15 wt% TEA C12-C14 alkyl sulfate, 3 wt% Cocamide MEA, 1.5 wt% cocoamidopropyl betaine, 3 wt% Example 3 ULTRAMULSION™ dispersion, 0.6 wt% citric acid, 0.4 wt% NaCl, color, preservative, fragrance (qv)
26. NH4 CI2-C,4 alkyl ether sulfate, 1.9 wt% Sodium C12-C14 alkyl sulfate, 1.5 wt% Cocamide MEA, 1.5 wt% cocoamidopropyl betaine, 3 wt% Example 4
ULTRAMULSION™ dispersion, 0.6 wt% citric acid, color, preservative, fragrance (qv)
These compositions are also stable and deliver good hair conditioning. Additional shampoo-conditioner examples of the present invention include the following:
27. 12 wt% ammonium lauryl sulfate, 4 wt% ammonium laureth sulfate, 2.2 wt% ammonium xylene sulfonate, 1 wt% cetearyl alcohol, .75 wt% glycol distearate, 1 wt% cocamide MEA, 3 wt% of the ULTRAMULSION™ dispersion of Example 11, 1 wt% tricetyl methyl ammonium chloride, color, perfume, preservative and water (qv to 100%)
28. 12 wt% ammonium lauryl sulfate, 4 wt% ammonium laureth sulfate, 2.2 wt% ammonium xylene sulfonate, 1 wt% cetearyl alcohol, 2.5 wt% glycol distearate, 1.5 wt% cocamide MEA, 3 wt% of the ULTRAMULSION™ dispersion of Example 11, 0.5 wt% tricetyl methyl ammonium chloride, color, perfume, preservative and water (qv to 100%)
29. 12 wt% ammonium lauryl sulfate, 4 wt% ammonium laureth sulfate, 3.0 wt% ammonium xylene sulfonate, 1 wt% cetearyl alcohol, 0.75 wt% glycol distearate, 1 wt% cocamide MEA, 3 wt% of the ULTRAMULSION™ dispersion of Example 14, 0.75 wt% lauryl trimethyl ammonium chloride, 0.5 wt% tricetyl methyl ammonium chloride, color, perfume, preservative and water (qv to 100%)
30. 15 wt% ammonium lauryl sulfate, 4 wt% ammonium laureth sulfate, 0.5 wt%
cetearyl alcohol, 0.75 wt% glycol distearate, 1 wt% cocamide MEA, 3 wt% of the ULTRAMULSION™ dispersion of Example 12, 0.75 wt% lauryl trimethyl ammonium chloride, 0.5 wt% tricetyl methyl ammonium chloride, color, perfume, preservative and water (qv to 100%) 31. 8 wt% ammonium lauryl sulfate, 8 wt% ammonium laureth sulfate, 1 wt% cetearyl alcohol, 0.75 wt% glycol distearate, 1 wt% cocamide MEA, 3 wt% of the ULTRAMULSION™ dispersion of Example 12, 2 wt% tri C8.I0 methyl ammonium chloride, color, perfume, preservative and water (qv to 100%)
32. 8 wt% ammonium lauryl sulfate, 8 wt% ammonium laureth sulfate, 1 wt% cetearyl alcohol, 0.75 wt% glycol distearate, 1 wt% cocamide MEA, 3 wt% of the ULTRAMULSION™ dispersion of Example 15, 2 wt% tri C13 amine, color, perfume, preservative and water (qv to 100%)
33. 18.2 wt% TEA C12.14 alkyl sulfate, 3 wt% cocamide MEA, 0.6 wt% NaOH (50%), 2 wt% of the ULTRAMULSION™ dispersion of Example 3, water, perfume, preservative, color (qs to 100%)
34. 16 wt% NH4 C-2.14 alkyl sulfate, 1 wt% cocamide MEA, 1 wt% cetearyl alcohol, 0.75 wt% ethylene glycol distearate, 0.1 wt% NaOH (50%), 3.5 wt% of the ULTRAMULSION™ dispersion of Example 4, water, perfume, preservative, color (qs to 100%) 35. 8 wt% NH4 C12.14 alkyl sulfate, 8 wt% NH4 C12.14 alkyl ether sulfate, 3 wt% cocamide MEA, 1.9 wt% of the ULTRAMULSION™ dispersion of Example 3, water, perfume, preservative, color (qs to 100%)
36. 16 wt% NH4 C12.14 alkyl sulfate, 3 wt% cocamide MEA, 2 wt% of the ULTRAMULSION™ dispersion of Example 6, water, perfume, preservative, color (qs to 100%)
37. 8 wt% NH4 C12.14 alkyl sulfate, 8 wt% NH4 C12.14 alkyl ether sulfate, 1.5 wt% cocamide MEA, 1 wt% cetearyl alcohol, 0.75 wt% ethylene glycol distearate, 2 wt% of the ULTRAMULSION™ dispersion of Example 10, water, perfume, preservative, color (qs to 100%)
Examples 38 - 59 are directed to ULTRAMULSION™ based skin care compositions. Like the hair care compositions of die preceding examples, these
examples are formed as follows; the Poloxamer is heated to 70-90°C to melt the solid material. Once melted, die Poloxamer is stirred with an overhead mixing blade. Dimethicone is added and die entire mass is mixed to obtain a uniform dispersion while maintaining the melt temperature. The material is then transferred to the homogenizer (a ROSS Homogenizer, Model M.E. 100LC), and homogenized for 1/2 hour at 5000-10,000 RPM. The material is then cooled by a suitable cooling apparatus. The cooled material is men ready for use. In addition to die ULTRAMULSION™ dispersions of Examples 1-10 above, the following additional examples of such dispersions have been found to be especially useful in skin care composition:
38. 10 wt% Dimethicone (30,000,000 cs) and 90 wt% Poloaxmer-338
39. 10 wt% Dimethicone (50,000,000 cs) and 90 wt% Poloxamer-338
40. 33 wt% Dimethicone (100,000 cs) and 67 wt% Poloxamer-188
41. 10 wt% Dimethicone (2,500,000 cs) and 90 wt% Poloxamer-238 Specific poloxamer/polydimethylsiloxane ULTRAMULSION™ dispersions suitable for use witii various skin care products were prepared as described in Examples 42- 47:
42. 10 wt% dimethicone (2,500,000 cs), 88 wt% Poloxamer-338, 2 wt% salicylic acid 43. 10 wt% dimethicone (4,000,000 cs), 88 wt% Poloxamer-338, 2 wt% salicylic acid
44. 10 wt% dimethicone (30,000,000 cs), 88 wt% Poloxamer-338, 2 wt% salicylic acid
45. 10 wt% dimethicone (50,000,000 cs), 88 wt% Poloxamer-338, 2 wt% salicylic acid
46. 20 wt% dimethicone (2,500,000 cs), 76 wt% Poloxamer-338, 4 wt% octyl dimethyl PABA
47. 20 wt% dimethicone (30,000,000 cs), 76 wt% Poloxamer-338, 4 wt% octyl dimethyl PABA The discontinuous silicone phase of die ULTRAMULSION™ dispersion can also contain a wide range of lipid soluble and/or lipid dispersible skin care ingredients ranging from colorants to essential fragrances such as menthol and camphor to
protectants such as U.V. absorbers, to repellents such as N,N.-diethyl-toluamide (DEET) to moisturizers, such as petrolatum, glycerin, etc; to medicinals such as Vitamin E, aloe, etc., to deodorants/antiperspirants such as triclosan, aluminum zirconium trichlorohydrex gly, etc.; to antimicrobials such as triclosan; to antiseptics such as benzalkonium chloride, etc.; to antihistamines such as diphenylhydramine hydrochloride; to seborrheic dermatitis as psoriasis actives such as coal tar and steroids to analgesics such as benzocaine, lidocaine, etc.
These various ingredients are contained at least to some extent in the silicone phase of the ULTRAMULSION™ dispersion to perform various skin functions as though they are contained in a "reservoir" as they continue to be available at the ULTRAMULSION™ skin care interface, as long as the ULTRAMULSION™ dispersion coating remains substantive to the skin. The sustained moisturizing, protecting, healing, etc. effects on skin obtained witii tiiese improved skin care products are discussed in various examples below. The skin care products containing die ULTRAMULSION™ dispersions of the present invention will contain a variety of essential components ranging from surfactants for cleaning, to various moisturizing substances. These are detailed in various Examples described below.
Water is an essential component of most skin care products of die present invention which contain one or more of the various ULTRAMULSION™ dispersions described above. The water in these products is generally present at a level of from about 20% to about 95%, preferably from between about 60% and about 90%.
In addition tiiese skin care products can contain a variety of nonessential optional components suitable for rendering such compositions more cosmetically acceptable. Such conventional optional ingredients are well known to tiiose skilled in die art, e.g., preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidizolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow)- dimethylammonium chloride; thickeners and viscosity modifiers such as dieflianolamide of a long chain fatty acid (e.g., PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF
Wyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and etiryl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc., perfumes; dyes; and, sequestering agents such as disodium etiiylenediamine tetraacetate. Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about 0.5% to about 5.0% by weight of the composition.
The pH of the skin care compositions is not critical and may be in the range of from 2 to about 10. However, as set forth earlier certain zwitterionic/quaternary compositions preferably have pH's of from about 2 to about 4. The skin treatment products of die present invention can be made by mixing the materials together and heating to about 72°C. The mixture is mixed thoroughly for about 10 minutes at the 72°C temperature before being pumped through a heat exchanger to cool it to about 27°C. The skin treatment ULTRAMULSION™ dispersions of the present invention are used in a conventional manner in various cosmetic, OTC Drug and R* drug products for cleaning, moisturizing, coloring, protecting, treating, healing etc. the skin, as shown in the Examples below:
48. Skin Moisturizer: Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSION™ dispersion of Example 2; Phase D - 0.5 wt% triedianolamine; Phase E - preservative and fragrance (qv to 100%)
49. Skin Moisturizer: Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSION™ dispersion of Example 3; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%)
50. Skin Moisturizer: Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSION™ dispersion of Example 5; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%)
51. Skin Moisturizer: Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1
wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSION™ dispersion of Example 8; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%) 52. Skin Moisturizer: Phase A - 2 wt% glyceryl stearate and PEG 100 stearate, 1 wt% stearyl alcohol, 2.5 wt% stearic acid, 4.5 wt% diocetylisostearate; Phase B - 0.3 wt% water and Carbopol 940; Phase C - 3 wt% of the ULTRAMULSION™ dispersion of Example 15; Phase D - 0.5 wt% triethanolamine; Phase E - preservative and fragrance (qv to 100%) 53. Facial Cleanser: 12 wt% disodium cocoamphodiacetate, 10 wt% sodium lauryl sarcosinate, 7 wt% cocoamido beatine, 4 wt% laurylamide DEA, 62.5 wt% water, 0.5 wt% citric acid, 4 wt% of the ULTRAMULSION™ dispersion of Example 6, preservative and fragrance (qv).
54. Facial Cleanser: 12 wt% disodium cocoamphodiacetate, 10 wt% sodium lauryl sarcosinate, 7 wt% cocoamido beatine, 4 wt% laurylamide DEA, 63.5 wt% water, 0.5 wt% citric acid, 3 wt% of the ULTRAMULSION™ dispersion of Example 4, preservative and fragrance (qv).
55. Facial Cleanser: 12 wt% disodium cocoamphodiacetate, 10 wt% sodium lauryl sarcosinate, 7 wt% cocoamido beatine, 4 wt% laurylamide DEA, 63.5 wt% water, 0.5 wt% citric acid, 3 wt% of the ULTRAMULSION™ dispersion of Example 10, preservative and fragrance (qv).
56. Acne Scrub: 73.3 wt% water, 16 wt% sodium C14-C16 olefin sulfonate, 2 wt% cocamide propyl beatine, 4 wt% sodium C12-C15 Pureth sulfonate, 0.1 wt% aloe vera extract, 4 wt% of the ULTRAMULSION™ dispersion of Example 15, 0.6 wt% NaCl, preservative and fragrance (qv).
57. Hand and Face Liquid Detergent: 62.9 wt% water, 25 wt% sodium lauryl sulfate, 6 wt% sodium laureth sulfate, 3 wt% cocoamidopropyl beatine, 2 wt% glyceryl cocoate, 0.5 wt% EDTA, 0.6 wt% NaCl, 3 wt% of the ULTRAMULSION™ dispersion of Example 1, preservative and fragrance (qv).
58. Hand and Face Liquid Detergent: 62.9 wt% water, 25 wt% sodium lauryl sulfate, 6 wt% sodium laureth sulfate, 3 wt% cocoamidopropyl beatine, 2 wt%
glyceryl cocoate, 0.5 wt% EDTA, 0.6 wt% NaCl, 3 wt% of the ULTRAMULSION™ dispersion of Example 4, preservative and fragrance (qv). 59. Hand and Face Liquid Detergent: 62.9 wt% water, 25 wt% sodium lauryl sulfate, 6 wt% sodium laureth sulfate, 3 wt% cocoamidopropyl beatine, 2 wt% glyceryl cocoate, 0.5 wt% EDTA, 0.6 wt% NaCl, 3 wt% of the ULTRAMULSION™ dispersion of Example 17, preservative and fragrance
(qv).
The present invention has been described in detail, including d e preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on is invention and still be within the scope and spirit of this invention as set forth in the following claims.
Claims
1. An aqueous hair and skin ULTRAMULSION™ based product, selected from the group consisting of hair care products and skin care products; said product containing an aqueous-free ULTRAMULSION™ dispersion of a silicone in a surfactant wherein: a. the silicone is insoluble in said surfactant, has a viscosity up to about 50 million cs, and a mean particle size up to about 10 microns. b. the surfactant to silicone ratio in the ULTRAMULSION™ dispersion is from between about 400:1 and about 1:1; and the surfactant has an orienting effect on the silicone, c. the ULTRAMULSION™ dispersion forms stable dispersions in said non-ingestible product, and d. said non-ingestible product exhibits enhanced performance characteristics.
2. A non-ingestible product according to claim 1 , wherein said
ULTRAMULSION™ dispersions comprises a nonionic poloxamer surfactant and polydimethylsiloxane wherein: a. said polydimethylsiloxane has the chemical composition (CH3)3SiO[SiO(CH3)2]nSi(CH3)3, wherein n is a whole number; b. said surfactant has the chemical composition
CH3
I OH-(CH2CH2))x - (CH2CHO)y - (CH2CH2O)x. - H
wherein x, y, and x' are whole numbers; c. the viscosity of the polydimethylsiloxane ranges from between about 2.5 million and about 50 million cs; d. the particle size of most of the polydimethylsiloxane in the ULTRAMULSION™ dispersion is from between about 0.1 and about 10 microns; e. substantially all of said polydimethylsiloxane particles in the ULTRAMULSION™ dispersions are from between about 1 and about 10 microns; f. the nonionic surfactant is a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight from between about 1,100 and about 150,000; g. die ratio of surfactant to polydimethylsiloxane is from between about
400:1 and about 1:2; and h. the ULTRAMULSION™ dispersion dispersed in water based hair care products is stable.
3. A stable aqueous based hair care product containing an aqueous free ULTRAMULSION™ dispersion comprised of a nonionic poloxamer surfactant and a polydimethylsiloxane insoluble in said surfactant wherein: a. said polydimethylsiloxane has the chemical composition (CH3)3SiO[SiO(CH3)2]nSi(CH3)3, wherein n is a whole number; b. said surfactant has the chemical composition
CH3
I OH-(CH2CH2))x - (CH2CHO)y - (CH2CH2O)x, - H
wherein x, y, and x' are whole numbers; c. the viscosity of the polydimethylsiloxane ranges from between about 2.5 million and about 50 million cs; d. die particle size of the polydimethylsiloxane in the ULTRAMULSION™ dispersion is from between about 0.1 and about 10 microns; e. substantially all of said polydimethylsiloxane particles in the ULTRAMULSION™ dispersions are from between about 1 and about 10 microns; f. the nonionic surfactant is a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight from between about 1,100 and about 150,000; g. the ratio of surfactant to polydimethylsiloxane is from between about 400:1 and about 1:2; and h. the ULTRAMULSION™ dispersion dispersed in water is stable.
4. A hair care product according to claim 3, wherein the ratio of said surfactant to said silicone is 9:1 and 90% of the silicone particles are from between about 1 and 3 microns.
5. A hair care product according to claim 3, wherein the ratio of said surfactant to said silicone is 2:1 and 100% of the silicone dispersion is less than 10 microns.
6. A hair care product according to claim 3, wherein the ratio of said surfactant to said silicone is 1 : 1 and the silicone particles in said ULTRAMULSION™ dispersion are less than 10 microns.
7. A stable skin care product wherein said product contains an aqueous- free ULTRAMULSION™ dispersion of a silicone in a surfactant wherein: a. the silicone is insoluble in said surfactant, has a viscosity up to about 50 million cs, and a particle size from between about 0.1 and about 10 microns; b. the surfactant to silicone ratio in the ULTRAMULSION™ dispersion is from between about 400:1 and about 1:1; and die surfactant has an orienting effect on the silicone, c. the ULTRAMULSION™ dispersion forms stable dispersions in aqueous containing skin care products, and d. said skin care product exhibits enhanced substantivity to skin while the dispersed silicone phase of said ULTRAMULSION™ dispersion functions as a reservoir for various lipid soluble and lipid dispersible skin treatment ingredients.
8. A skin care product according to claim 7, wherein said ULTRAMULSION™ dispersion comprises a surfactant and polydimethylsiloxane wherein: a. said polydimethylsiloxane has the chemical composition (CH3)3SiO[SiO(CH3)2]nSi(CH3)3, wherein n is a whole number; b. said polydimethylsiloxane contains a lipid soluble active ingredient; c. the viscosity of the polydimethylsiloxane ranges from between about 2.5 million and about 4 million cs; d. the particle size of most of the polydimethylsiloxane in the ULTRAMULSION™ dispersion is from between about 0.5 and about 10 microns; e. from between about 80% and 95% of said polydimethylsiloxane particles in the ULTRAMULSION™ dispersions are from between about 1 and about 10 microns; f. the ratio of surfactant to polydimethylsiloxane is from between about 400:1 and about 1:2; and g. die ULTRAMULSION™ dispersion dispersed in water based skin care products is stable.
9. A stable aqueous based skin care product containing a dispersed therein an ULTRAMULSION™ dispersion comprising a surfactant and a polydimediylsiloxane insoluble in said surfactant wherein: a. said polydimethylsiloxane has the chemical composition (CH3)3SiO[SiO(CH3)2]nSi(CH3)3) wherein n is a whole number; b. said polydimethylsiloxane contains a lipid soluble active ingredient selected from the group consisting of cosmetic, OTC Drug and R drug active ingredients; c. die viscosity of the polydimethylsiloxane ranges from between about 2.5 million and about 50 million cs; d. the particle size of most of the polydimethylsiloxane in the ULTRAMULSION™ dispersion is from between about 0.1 and about 10 microns; e. from between about 80% and 95% of said polydimethylsiloxane particles in the ULTRAMULSION™ dispersions are from between about 1 and about 10 microns; f. the ratio of surfactant to polydimethylsiloxane is from between about 400:1 and about 1:2; and g. the ULTRAMULSION™ dispersion dispersed in water is stable.
10. A skin care product according to claim 9, wherein the ratio of said surfactant to said silicone is 9:1 and 90% of die silicone particles are from between about 1 and 3 microns.
11. A skin care product according to claim 9, wherein the ratio of said surfactant to said silicone is 2:1 and 100% of the silicone dispersion is less than 10 microns.
12. A skin care product according to claim 9, wherein the ratio of said surfactant to said silicone is 1:1 and the silicone particles in said ULTRAMULSION™ dispersion are less than 10 microns.
13. An aqueous based moisturizing lotion containing an ULTRAMULSION™ dispersion comprising a nonionic poloxamer surfactant and polydimethylsiloxane insoluble in said surfactant wherein: a. said polydimethylsiloxane has the chemical composition (CH3)3SiO[SiO(CH3)2]nSi(CH3)3, wherein n is a whole number; b. the viscosity of the polydimethylsiloxane ranges from between about 2.5 million and about 4 million cs; c. the particle size of most of the polydimethylsiloxane in the ULTRAMULSION™ dispersion is from between about 0.5 and about 10 microns; d. from between about 80% and 95% of said polydimethylsiloxane particles in the ULTRAMULSION™ dispersions are from between about 1 and about 10 microns; e. the ratio of surfactant to polydimethylsiloxane is from between about 400:1 and about 1:2; and f. the ULTRAMULSION™ dispersion dispersed in water based lotion/moisturizer is stable.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU62605/96A AU6260596A (en) | 1995-06-05 | 1996-06-04 | Hair and skin ultramulsion based products |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/462,613 | 1995-06-05 | ||
US08/462,613 US5733536A (en) | 1995-06-05 | 1995-06-05 | Ultramulsion based hair care compositions |
US08/462,600 US5730967A (en) | 1995-06-05 | 1995-06-05 | Ultramulsion based skin care compositions |
US08/462,600 | 1995-06-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996039114A1 true WO1996039114A1 (en) | 1996-12-12 |
Family
ID=27040390
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/009459 WO1996039114A1 (en) | 1995-06-05 | 1996-06-04 | Hair and skin ultramulsion based products |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU6260596A (en) |
WO (1) | WO1996039114A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999032084A1 (en) * | 1997-12-22 | 1999-07-01 | Edko Trading And Representation Company Limited | Compositions for the treatment of skin and anorectal conditions |
CN108366935A (en) * | 2015-11-09 | 2018-08-03 | 梅里亚股份有限公司 | Pet Care Cleaning Compositions |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5538667A (en) * | 1993-10-28 | 1996-07-23 | Whitehill Oral Technologies, Inc. | Ultramulsions |
-
1996
- 1996-06-04 WO PCT/US1996/009459 patent/WO1996039114A1/en active Application Filing
- 1996-06-04 AU AU62605/96A patent/AU6260596A/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5538667A (en) * | 1993-10-28 | 1996-07-23 | Whitehill Oral Technologies, Inc. | Ultramulsions |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999032084A1 (en) * | 1997-12-22 | 1999-07-01 | Edko Trading And Representation Company Limited | Compositions for the treatment of skin and anorectal conditions |
GB2349819A (en) * | 1997-12-22 | 2000-11-15 | Edko Trading Representation | Compositions for the treatment of skin and anorectal conditions |
CN108366935A (en) * | 2015-11-09 | 2018-08-03 | 梅里亚股份有限公司 | Pet Care Cleaning Compositions |
Also Published As
Publication number | Publication date |
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AU6260596A (en) | 1996-12-24 |
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