EP2984161B1 - Improvements relating to fabric conditioners - Google Patents
Improvements relating to fabric conditioners Download PDFInfo
- Publication number
- EP2984161B1 EP2984161B1 EP14710836.9A EP14710836A EP2984161B1 EP 2984161 B1 EP2984161 B1 EP 2984161B1 EP 14710836 A EP14710836 A EP 14710836A EP 2984161 B1 EP2984161 B1 EP 2984161B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ester
- quaternary ammonium
- electrolyte
- composition
- perfume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000002979 fabric softener Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000002304 perfume Substances 0.000 claims description 44
- 239000003792 electrolyte Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- 150000002148 esters Chemical class 0.000 claims description 33
- -1 chloride Chemical class 0.000 claims description 30
- 239000004744 fabric Substances 0.000 claims description 26
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000002190 fatty acyls Chemical group 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 33
- 239000002518 antifoaming agent Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- 229920001296 polysiloxane Polymers 0.000 description 19
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 18
- 238000007792 addition Methods 0.000 description 17
- 239000012071 phase Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 150000005690 diesters Chemical class 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 8
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000982 direct dye Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000000980 acid dye Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 239000000981 basic dye Substances 0.000 description 6
- 239000002775 capsule Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 6
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 6
- 150000003333 secondary alcohols Chemical class 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000005691 triesters Chemical class 0.000 description 5
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- IYTXKIXETAELAV-UHFFFAOYSA-N Nonan-3-one Chemical compound CCCCCCC(=O)CC IYTXKIXETAELAV-UHFFFAOYSA-N 0.000 description 4
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 4
- ZMQAAUBTXCXRIC-UHFFFAOYSA-N safrole Chemical compound C=CCC1=CC=C2OCOC2=C1 ZMQAAUBTXCXRIC-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NZGWDASTMWDZIW-MRVPVSSYSA-N (+)-pulegone Chemical compound C[C@@H]1CCC(=C(C)C)C(=O)C1 NZGWDASTMWDZIW-MRVPVSSYSA-N 0.000 description 3
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 3
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 3
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 3
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 3
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 3
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 3
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 3
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N O-methyleugenol Chemical compound COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 3
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 150000002194 fatty esters Chemical class 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 3
- NFLGAXVYCFJBMK-UHFFFAOYSA-N isomenthone Natural products CC(C)C1CCC(C)CC1=O NFLGAXVYCFJBMK-UHFFFAOYSA-N 0.000 description 3
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- 239000000155 melt Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
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- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 description 2
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- HVJKZICIMIWFCP-UHFFFAOYSA-N Benzyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OCC1=CC=CC=C1 HVJKZICIMIWFCP-UHFFFAOYSA-N 0.000 description 2
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- 241000640882 Condea Species 0.000 description 2
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- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- BTTMZEBIMDNSPK-UHFFFAOYSA-N icosan-4-ol Chemical compound CCCCCCCCCCCCCCCCC(O)CCC BTTMZEBIMDNSPK-UHFFFAOYSA-N 0.000 description 1
- WLIISNIPNDLIFS-UHFFFAOYSA-N icosan-5-ol Chemical compound CCCCCCCCCCCCCCCC(O)CCCC WLIISNIPNDLIFS-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- XAOGXQMKWQFZEM-UHFFFAOYSA-N isoamyl propanoate Chemical compound CCC(=O)OCCC(C)C XAOGXQMKWQFZEM-UHFFFAOYSA-N 0.000 description 1
- RGFNRWTWDWVHDD-UHFFFAOYSA-N isobutyl butyrate Chemical compound CCCC(=O)OCC(C)C RGFNRWTWDWVHDD-UHFFFAOYSA-N 0.000 description 1
- VDBNYAPERZTOOF-UHFFFAOYSA-N isoquinolin-1(2H)-one Chemical compound C1=CC=C2C(=O)NC=CC2=C1 VDBNYAPERZTOOF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229930007503 menthone Natural products 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 1
- 229940102398 methyl anthranilate Drugs 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 229940116837 methyleugenol Drugs 0.000 description 1
- PRHTXAOWJQTLBO-UHFFFAOYSA-N methyleugenol Natural products COC1=CC=C(C(C)=C)C=C1OC PRHTXAOWJQTLBO-UHFFFAOYSA-N 0.000 description 1
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N n-hexan-3-ol Natural products CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001702 nutmeg Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical class CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- YWXLSHOWXZUMSR-UHFFFAOYSA-N octan-4-one Chemical compound CCCCC(=O)CCC YWXLSHOWXZUMSR-UHFFFAOYSA-N 0.000 description 1
- YSIMAPNUZAVQER-UHFFFAOYSA-N octanenitrile Chemical compound CCCCCCCC#N YSIMAPNUZAVQER-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- UPPSFGGDKACIKP-UHFFFAOYSA-N p-Tolyl isobutyrate Chemical compound CC(C)C(=O)OC1=CC=C(C)C=C1 UPPSFGGDKACIKP-UHFFFAOYSA-N 0.000 description 1
- 229930007459 p-menth-8-en-3-one Natural products 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- QQBPIHBUCMDKFG-UHFFFAOYSA-N phenazopyridine hydrochloride Chemical group Cl.NC1=NC(N)=CC=C1N=NC1=CC=CC=C1 QQBPIHBUCMDKFG-UHFFFAOYSA-N 0.000 description 1
- JDQVBGQWADMTAM-UHFFFAOYSA-N phenethyl isobutyrate Chemical compound CC(C)C(=O)OCCC1=CC=CC=C1 JDQVBGQWADMTAM-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 229950009215 phenylbutanoic acid Drugs 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229940068965 polysorbates Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- NPFVOOAXDOBMCE-UHFFFAOYSA-N trans-3-hexenyl acetate Natural products CCC=CCCOC(C)=O NPFVOOAXDOBMCE-UHFFFAOYSA-N 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- XMLSXPIVAXONDL-UHFFFAOYSA-N trans-jasmone Natural products CCC=CCC1=C(C)CCC1=O XMLSXPIVAXONDL-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- UUJLHYCIMQOUKC-UHFFFAOYSA-N trimethyl-[oxo(trimethylsilylperoxy)silyl]peroxysilane Chemical compound C[Si](C)(C)OO[Si](=O)OO[Si](C)(C)C UUJLHYCIMQOUKC-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000016788 valerian Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- YEIGUXGHHKAURB-UHFFFAOYSA-N viridine Natural products O=C1C2=C3CCC(=O)C3=CC=C2C2(C)C(O)C(OC)C(=O)C3=COC1=C23 YEIGUXGHHKAURB-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/44—Multi-step processes
Definitions
- the present invention concerns a process for the preparation of fabric conditioner compositions having superior viscosity control, comprising a plurality of encapsulated benefit agents and a fabric softening active.
- WO 20111139578 discloses a process for manufacturing a fabric conditioner containing up to 20% diester quat, in which a first measure of a water-soluble salt (CaCl 2 ) is included in an initial dispersion with the quat. Subsequent additions of silicone emulsion and/or encapsulated perfume are disclosed, both of which may contain some salt.
- a water-soluble salt CaCl 2
- JP 2007/237050 discloses a process for making an oil-in-water emulsion containing 10-40% quaternary ammonium salt, which may be ester linked. Some inorganic electrolyte is present in the aqueous phase and the quaternary ammonium salt is present in the oil phase. The water and oil phases are mixed to form an emulsion and then larger amounts of electrolyte ( ⁇ 80% of the total) are added to this emulsified matter. Specific examples of adding more salt before the active leads to an unstable products that thicken unacceptably and separate.
- WO 2004/046290 discloses aqueous ester-linked quat based softeners where calcium chloride is added to the liquid mixture after the active. Examples describe the addition of 0.25% CaCl 2 to stabilise superconcs containing up to 27 wt % active. When all salt is added at the end of the preparation process, the product viscosity drops 24 hours after making.
- WO 2004/027002 discloses ester quat based fabric conditioners in which calcium chloride is post-dosed at the end of the preparation process.
- EP 1264874 discloses the manufacture of fabric softener compositions, comprising mixed actives, for improved softness under certain wash conditions.
- magnesium chloride is mixed into a water phase before the addition of a di-ester softening active.
- EP 1077251 discloses the manufacture of a liquid fabric conditioner composition, comprising 15 wt % of a diester active.
- magnesium chloride is pre-mixed with water prior to adding a cationic/nonionic/anti-foam pre-mix.
- Example 3 discloses the addition of 0.6 wt % of CaCl 2 to the water phase. Unusually high salt levels are employed (0.6 to 1%).
- US 5880086 discloses a concentrated fabric softening composition comprising 20 wt % of TEA ester quat active and magnesium chloride as an optional ingredient.
- the concentrates are prepared by simply mixing or dispersing the individual components in water.
- WO 98/12293 discloses a process for adding a cationic polymer to an ester-based quaternary ammonium fabric conditioner.
- Some electrolyte can be added prior to milling if the composition is too thick to mix, but preferably should be added at the end of the process after addition of the perfume.
- WO 96/21715 discloses preparation of stabilised DEEDMAC- based aqueous fabric conditioners, comprising greater than 1 % total electrolyte.
- the DEEDMAC is added to water, then electrolyte is added to this dispersion to transform it from a viscous paste to a thin liquid.
- WO 96/15212 and WO 94/20597 disclose a process for making fabric conditioner compositions with ester linked quats, in which CaCl 2 is added to the mixture after the diester.
- WO 95/16766 discloses a DEEDMAC based softener in which CaCl 2 is added to an aqueous solution after the active, to allow mixing.
- EP 634475 discloses fabric conditioner compositions where calcium chloride is added to an aqueous dispersion of the ester-linked active.
- JP 2007 237050 discloses a method for manufacturing an oil-in-water-type emulsion where the concentration of a quaternary ammonium salt is 10 to 40 weight percent as a reference of the whole oil-in-water-type emulsion.
- WO 2010/012590 discloses a composition
- a composition comprising: i) encapsulated perfume components, ii) a fabric softening active, which is selected from an ester-linked quaternary ammonium compound and an oily sugar derivative and mixtures thereof; iii) a stabilising active selected from the group consisting of from 0.05 to 0.2 wt percent by the total weight of the composition of water soluble non- ester-linked cationic quaternary ammonium compound (s), from 0.65 to 1.5 wt percent by the total weight of the composition of non-ionic surfactant (s) and mixtures thereof, and iv) from 0.005 to 0.1 wt percent by the total weight of the composition of salt, wherein the encapsulates comprise a capsule wall having surface weak acid groups.
- WO 2011/139578 discloses a process for making a liquid fabric softening composition, comprising the steps of; a) Providing a first composition comprising a fabric softening active, the fabric softening active comprising a multilamellar phase of cationic vesicles; b) Adding to, and mixing with the first composition, a silicone emulsion, and a polyol, to produce a second composition, the second composition comprising from 0.0001 percent to 0.1 percent by weight of the second composition of a water-soluble salt; c) Adding to the second composition, a third composition, the third composition comprising, 20 percent to 50 percent by weight of the third composition of a perfume microcapsule and from 0.01 percent to 2.5 percent by weight of the third composition of a water-soluble salt; d) Mixing the second and third compositions to make a final fabric softening composition.
- Electrolyte is commonly added to quat-based fabric conditioner formulations in order to control viscosity and viscostability.
- electrolyte typically CaCl 2
- the addition of electrolyte (typically CaCl 2 ) after the active has been added to the water is common practice and enables the viscosity to be tailored in terms of desired thickness, depending on the amount of electrolyte added.
- aqueous concentrated fabric conditioning composition which is an aqueous dispersion, comprising
- electrolyte is added before and after addition of ester-linked quaternary ammonium softening active to a water phase.
- a proportion of the electrolyte is added to the water phase before the combination of the softening active with the water phase; and the remaining portion of electrolyte is added after the combination of the softening active with the water phase.
- the amount of electrolyte added before the addition of the fabric softening active is preferably 0.05 to 0.2 wt %, more preferably from 0.9 to 0.15 wt %, by total weight of the composition.
- the water phase may also contain minor and/or optional components, for example, dye, preservatives, polymer, antioxidants and antifoam.
- Encapsulated perfume may be added to the water phase.
- Non-confined perfume oil is preferably added in the conventional way, after the active and water phases have been combined and cooled.
- a preferred process of the invention comprises the steps of:-
- the optional ingredients are added to the heated water before the addition of the ester-linked quaternary ammonium softening active.
- ester-linked quaternary ammonium softening active The ester-linked quaternary ammonium softening active
- the ester-linked quaternary ammonium softening active is present in an amount of from 10 to 30 wt %, preferably from 12 to 25 wt %, most preferably from 14 to 22 wt %, by weight of the total composition.
- the ester-linked quaternary ammonium softening active is a fabric-substantive quaternary ammonium compound which, in pure form as a strong acid salt (e.g. chloride), has a solubility in distilled water at pH 2.5 and 20°C of less than 1g/l, preferably less than 0.1g/l more preferably less than 0.01 g/l or can be a mixture of such compounds.
- a strong acid salt e.g. chloride
- Preferred quaternary ammonium compounds for use in the process of the invention have unsaturated chains, i.e. are the so-called "soft" quats.
- Such compounds are typically derived from fatty acyl or fatty acid feed stock having an Iodine Value of from 20 to 140, preferably from 20 to 60, more preferably from 20 to 50, most preferably from 25 to 45.
- the unsaturated chains come from the unsaturated fatty feed stock.
- the iodine value represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all of the quaternary ammonium materials present.
- the iodine value represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all of the quaternary ammonium materials present.
- Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993 ).
- Particularly preferred materials are water insoluble ester-linked triethanolammonium (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.
- TAA water insoluble ester-linked triethanolammonium
- such TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound.
- the di-ester linked component comprises no more than 70 % by weight of the fabric softening compound, preferably no more than 60 %, e.g. no more than 55 %, or even no more than 45 % of the fabric softening compound and at least 10 % of the monoester linked component.
- a first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I): [(CH 2 ) n (TR)] m -(R 1 ).N + -[(CH 2 ) n (OH)] 3-m X - (I) wherein each R is independently selected from a C 5-35 alkyl or alkenyl group; R 1 represents a C 1-4 alkyl, C 2-4 alkenyl or a C 1-4 hydroxyalkyl group; T is generally O-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO.O (i.e.
- TEA ester quats preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".
- StepantexTM UL85 Ex Stepan, PrapagenTM TQL, ex Clariant, and TetranylTM AHT-1
- Ex Kao both di-[hardened tallow ester] of triethanolammonium methylsulphate
- AT-1 di-[tallow ester] of triethanolammonium methylsulphate
- L5/90 di-[palm ester] of triethanolammonium methylsulphate
- RewoquatTM WE15 a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C 10 -C 20 and C 16 -C 18 unsaturated fatty acids
- soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable.
- a second group of quaternary ammonium compounds suitable for use in the invention is represented by formula (II): (R 1 ) 3 N + -(CH 2 ) n -CH.(CH 2 TR 2 )-TR 2 X - (II) wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; and wherein n, T, and X - are as defined above.
- Preferred materials of this second group include 1,2 bis [tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 and 1,2- bis [oleoyloxy]-3-trimethylammonium propane chloride. Such materials are described in US 4,137,180 (Lever Brothers ). Preferably, these materials also comprise an amount of the corresponding mono-ester.
- a third group of quaternary ammonium compounds suitable for use in the invention is represented by formula (III): (R 1 ) 2 -N + -[(CH 2 ) n -T-R 2 ] 2 X - (III) wherein each R 1 group is independently selected from C 1-4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; and n, T, and X - are as defined above.
- Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride.
- the electrolyte is a salt.
- the salt is preferably a mineral salt.
- any of the alkaline metals or alkaline earth metal salts of the mineral acids can be used as the salt. Based on their availability, solubility and low toxicity, NaCl, CaCl2, MgCl2 and MgSO4 and similar salts of alkaline and alkaline earth metals are preferred, and CaCl2 is especially preferred.
- electrolytes which are suitable for use in the present invention, include water soluble organic salts.
- the electrolyte is present in an amount of from 0.001 to 1% and preferably at from 0.005 to 0.5%, most preferably from 0.1 to 0.3 % by weight of the total composition.
- compositions derived from the process of the present invention comprises one or more perfumes.
- the perfume may be present in encapsulated and non-confined forms.
- the total amount of encapsulated and non-confined perfume present is an amount of from 0.01 to 10 % by weight, more preferably from 0.05 to 5 % by weight, even more preferably from 0.1 to 4.0 %, most preferably from 0.5 to 3.0 % by weight, based on the total weight of the composition.
- the amount of encaps present is preferably from 0.01 to 1.0 %, more preferably from 0.1 to 0.9 and most preferably from 0.3 to 0.8 % by weight of the total composition.
- the encapsulated perfume is preferably in the form of a slurry having a viscosity of from greater than water to 1000 cps at 21 s-1 and 25 °C. Greater than one type of encapsulated perfume may be present.
- the perfume loading of the encaps that is to say the amount of the total encap weight that is perfume, is preferably from 20 to 40 wt %, more preferably from 28 to 32 wt %, by total weight of the encaps.
- the encaps (or "capsules") for use in the process of the present invention comprise a shell.
- the shell is preferably comprised of materials including aminoplasts, proteins, polyurethanes, polysaccharides, gums, celluloses, and any other encapsulating material which may be used effectively in the present invention, such as polymethylmethacrylate.
- Preferred encapsulating polymers include those formed from melamine formaldehyde or urea formaldehyde condensates, as well as similar types of aminoplasts.
- Most preferably the shell comprises melamine formaldehyde.
- microcapsules made via the simple or complex coacervation of gelatin are also preferred for use with the coating.
- Microcapsules having shell walls comprised of polyurethane, polyamide, polyolefin, polysaccaharide, protein, silicone, lipid, modified cellulose, gums, polyacrylate, polystyrene, and polyesters or combinations of these materials are also possible.
- a representative process used for aminoplast encapsulation is disclosed in 3516941USA U.S. Patent No. 3,516,941 though it is recognized that many variations with regard to materials and process steps are possible.
- a representative process used for gelatin encapsulation is disclosed in 2800457USA U.S. Patent No, 2,800,457 though it is recognized that many variations with regard to materials and process steps are possible. Both of these processes are discussed in the context of fragrance encapsulation for use in consumer products in 4145184USA U.S. Patent Nos. 4,145,184 and 5112688USA 5,112,688 respectively.
- Encapsulation can provide pore vacancies or interstitial openings depending on the encapsulation techniques employed.
- Fragrance capsules known in the art and suitable for use in the present invention comprise a wall or shell comprising a three-dimensional cross-linked network of an aminoplast resin, more specifically a substituted or un-substituted acrylic acid polymer or co-polymer cross-linked with a urea-formaidehyde pre-condensate or a melamine-formaldehyde pre-condensate.
- Microcapsule formation using mechanisms similar to the foregoing mechanism, using (i) melamine-formaldehyde or urea-formaldehyde pre-condensates and (ii) polymers containing substituted vinyl monomeric units having proton-donating functional group moieties (e.g. sulfonic acid groups or carboxylic acid anhydride groups) bonded thereto is disclosed in 44068162USBU.S.
- Patent 4,406,816 (2-acrylamido-2-methyl-propane sulfonic acid groups), 2062570GBAUK published Patent Application GB 2,062,570 A (styrene sulfonic acid groups) and 2006709GBAUK published Patent Application GB 2,006,709 A (carboxylic acid anhydride groups).
- Particle size and average diameter of the capsules can vary from about 10 nanometers to about 1000 microns, preferably from about 50 nanometers to about 100 microns, more preferably from about 2 to about 40 microns, even more preferably from about 3 to 30 microns. A particularly preferred range is from about 5 to 10 microns, for example 6 to 7 microns.
- the capsule distribution can be narrow, broad or multimodal. Multimodal distributions may be composed of different types of capsule chemistries.
- Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press ; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostr and; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ).
- perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
- Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
- perfume components which have a low Clog P (i.e. those which will be partitioned into water), preferably with a Clog P of less than 3.0.
- These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials: Allyl Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisole, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Iso Valerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor Gum, Laevo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formate, Cis-Jasmone, cis-3-Hexenyl Acetate, Cuminic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benz
- Suitable non-encapsulated perfume ingredients include those hydrophobic perfume components with a ClogP above 3.
- ClogP means the logarithm to base 10 of the octanol/water partition coefficient (P).
- the octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the hydrophobicity of a material--the higher the ClogP value, the more hydrophobic the material.
- ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563 .
- Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1-Ethyl-4-nitrobenzene, Heptyl formate, 4-l
- perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
- Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition.
- Preferred co-softeners include fatty esters, and fatty N-oxides.
- Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
- compositions of the present invention will preferably comprise a fatty complexing agent.
- suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.
- the fatty complexing material improves the viscosity profile of the composition by complexing with mono-ester component of the fabric conditioner material thereby providing a composition which has relatively higher levels of di-ester and tri-ester linked components.
- the di-ester and tri-ester linked components are more stable and do not affect initial viscosity as detrimentally as the mono-ester component.
- compositions comprising quaternary ammonium materials based on TEA may destabilise the composition through depletion flocculation.
- depletion flocculation is significantly reduced.
- the fatty complexing agent at the increased levels as required by the present invention, "neutralises” the mono-ester linked component of the quaternary ammonium material. This in situ di-ester generation from mono-ester and fatty alcohol also improves the softening of the composition.
- Preferred fatty acids include hardened tallow fatty acid (available under the trade name PristereneTM, ex Uniqema).
- Preferred fatty alcohols include hardened tallow alcohol (available under the trade names StenolTM and HydrenolTM, ex Cognis and LaurexTM CS, ex Albright and Wilson).
- the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%.
- the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1:5, more preferably 4:1 to 1:4, most preferably 3:1 to 1:3, e.g. 2:1 to 1:2.
- An antifoam may be present in an amount of from 0.025 to 0.45 wt %, preferably 0.03 to 0.4 wt %, most preferably from 0.05 to 0.35 wt %, for example 0.07 to 0.4 wt %, by weight of the total composition and based on 100 % antifoam activity.
- antifoams A wide variety of materials may be used as antifoams, and antifoams are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979 ).
- Suitable antifoams include, for example, silicone antifoam compounds, alcohol antifoam compounds, for example 2-alkyl alcanol antifoam compounds, fatty acids, paraffin antifoam compounds, and mixtures thereof.
- antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
- Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Many such silicone antifoam compounds also contain a silica component.
- silicone antifoam compounds also contain a silica component.
- silica component The term "silicone” as used herein, and in genera!
- siloxane oils such as polydimethyl-siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
- Silica particles are often hydrophobed, e.g. as Trimethylsiloxysilicate. Silicone antifoam agents are well known in the art and are, for example, disclosed in U. S.
- Patent 4, 265, 779 issued May 5, 25 1981 to Gandolfo et al and European Patent Application No. 89307851. 9, published February 7, 1990, by Starch, M. S.
- Other silicone antifoams are disclosed in U. S. Patent 3, 455, 839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2, 124, 526 . Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U. S. Patent 3, 933, 672, 35 Bartolotta et al , and in U. S. Patent 4, 652, 392, Baginski et al, issued March 24, 1987 . Examples of suitable silicone antifoam compounds are the combinations of polyorganosiloxane with silica particles commercially available from Dow Corning, Wacker Chemie and Momentive.
- Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2, 954, 347 .
- the monocarboxylic fatty acids, and salts thereof, for use as antifoam agents typically have hydrocarbyl chains of about 10 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms like the tallow amphopolycarboxyglycinate commercially available under the trade name TAPAC.
- Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
- Suitable antifoam compounds include, for example, high molecular weight hydrocarbons such as paraffin, light petroleum odourless hydrocarbons, fatty esters (e. g. fatty acid triglycerides, glyceryl derivatives, polysorbates), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e. g.
- N-alkylated amino triazines such as tri- to hexa- 10 alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters, and nonionic polyhydroxyl derivatives.
- the hydrocarbons such as paraffin and 15 haloparaffin, can be utilized in liquid form.
- the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. Hydrocarbon suds suppressers are described, for example, in U. S. Patent 4, 265, 779 .
- the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
- the term "paraffin", as used in this suds suppresser discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
- Copolymers of ethylene oxide and propylene oxide particularly the mixed ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from about 10 to about 16 carbon atoms, a degree of ethoxylation of from about 3 to about 30 and a degree of propoxylation of from about 1 to about 10, are also suitable antifoam compounds for use herein.
- antifoams useful herein comprise the secondary alcohols (e.g. , 2-alkyl alkanols as described in DE 40 21 265 ) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US 4,798,679 , US 4,075,118 and EP 150,872 .
- the secondary alcohols include the C6-C16 alkyl alcohols having a CI-C16 chain like the 2-Hexyldecanol commercially available under the trade name ISOFOL16, 2-Octyidodecanol commercially available under the tradename ISOFOL20, and 2-butyl octanol, which is available under the trademark ISOFOL 12 from Condea.
- a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
- Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
- Mixed antifoams typically comprise mixtures of alcohol to silicone at a weight ratio of about 1:5 to about 5:1.
- antifoam agents are Silicone SRE grades and Silicone SE 47M, SE39, SE2, SE9 and SE10 available from Wacker Chemie; BF20+, DB310, DC1410, DC1430, 22210, HV495 and Q2-1607 ex Dow Corning; FD20P and BC2600 supplied by Basildon; and SAG 730 ex Momentive.
- antifoams are selected from dimethicone, poloxamer, polypropyleneglycol, tallow derivatives, and mixtures thereof.
- Preferred among the antifoams described above are the silicone antifoams, in particular the combinations of polyorganosiloxane with silica particles.
- a non-ionic ethoxylated surfactant may be present in order to improve the appearance of the rinse liquor. It prevents the formation of scum which could potentially lead to deposition of scummy deposits on the laundered fabric. In particular it disperses the reaction product of the anionic surfactant from the wash and monoquat compound preventing flocculation and formation of scum resulting in a translucent dispersion.
- Suitable non-ionic surfactants are alkoxylated materials, particularly addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
- Preferred materials are of the general formula: R-Y-(CH 2 CH 2 O) z H
- R is a hydrophobic moiety, typically being an alkyl or alkenyl group, said group being linear or branched, primary or secondary, and preferably having from 8 to 25, more preferably 10 to 20, and most preferably 10 to 18 carbon atoms; R may also be an aromatic group, such as a phenolic group, substituted by an alkyl or alkenyl group as described above; Y is a linking group, typically being O, CO.O, or CO.N(R 1 ), where R 1 is H or a C 1-4 alkyl group; and z represents the average number of ethoxylate (EO) units present, said number being 20 or more, preferably at least 25, more preferably at least 30.
- EO ethoxylate
- non-ionic surfactants include the ethoxylates of mixed natural or synthetic alcohols in the "coco” or "tallow” chain length.
- Preferred materials are condensation products of coconut fatty alcohol with 20-50 moles of ethylene oxide and condensation products of tallow fatty alcohol with 20-50 moles of ethylene oxide.
- ethoxylates of secondary alcohols such as 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol may also be used.
- Exemplary ethoxylated secondary alcohols have formulae C 12 -EO(20); C 14 -EO(20); C 14 -EO(25); and C 16 -EO(30).
- Suitable commercially available non-ionic surfactants include Lutensol AT25, Lutensol AT50 and Unitol CE 200F.
- compositions may comprise other optional nonionic surfactants, especially where the level of quaternary ammonium compound is above about 8 % by weight of the total composition. Typically these can be included for the purpose of stabilising the compositions.
- Suitable surfactants may conform to the general formula given above, where R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 8 to about 25, preferably 10 to 20, e.g. 14 to 18 carbon atoms.
- Y is the same as described above and Z is at least about 8, preferably at least about 10 or 11.
- the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 20, e.g. 12 to 16, and even more preferably from 15 to 20.
- GenapolTM C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonoionic surfactant.
- a particular surfactant may be useful in the present compositions alone or in combination with other surfactants.
- the preferred amounts of non-ionic surfactant indicated below refer to the total amount of such materials that are present in the composition.
- the non-ionic surfactant is generally from 0.05 to 10%, usually 0.1 to 5%, and often 3 to 4% by weight, based on the total weight of the composition.
- Optional shading dyes can be used. Preferred dyes are violet or blue. Suitable and preferred classes of dyes are discussed below. Moreover the unsaturated quaternary ammonium compounds are subject to some degree of UV light and/or transition metal ion catalysed radical auto-oxidation, with an attendant risk of yellowing of fabric. The presence of a shading dye also reduces the risk of yellowing from this source.
- the level of shading dye present in the compositions of the present invention depend, therefore, on the type of shading dye.
- Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt %, more preferably 0.0001 to 0.01 wt %, most preferably 0.0005 to 0.005 wt % by weight of the total composition.
- Direct dyes are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
- the dye are bis -azo or tris- azo dyes are used.
- the direct dye is a direct violet of the following structures: or wherein:
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
- Bis-azo copper containing dyes such as direct violet 66 may be used.
- the benzidene based dyes are less preferred.
- the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
- the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612 .
- Cotton substantive acid dyes give benefits to cotton containing garments.
- Preferred dyes and mixes of dyes are blue or violet.
- Preferred acid dyes are:
- Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
- non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
- the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
- the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
- Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
- Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
- Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
- Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue 96.
- Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
- Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
- compositions of the invention may contain one or more other ingredients.
- ingredients include photobleaches, fluorescent agents, dyes, preservatives (e.g. bactericides), pH buffering agents, preferably inorganic or organic based such as hydrochloric acid, lactic acid and sodium lactate, etc, perfume carriers, hydrotropes, antiredeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
- cationic polymeric deposition aids include cationic guar polymers such as JaguarTM (ex Rhone Poulenc), cationic cellulose derivatives such as CelquatsTM (ex National Starch), FlocaidTM (ex National Starch), cationic potato starch such as SoftGelTM (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids).
- Short chain alcohols may also be included, for example primary alcohols, such as ethanol, propanol, and butanol, and secondary alcohols such as isopropanol.
- the short chain alcohol may be added with the ester linked quaternary ammonium softening active during the preparation of the composition.
- compositions of the invention are liquids.
- the compositions are aqueous dispersions.
- the composition may be a concentrate to be diluted, rehydrated and/or dissolved in a solvent, including water, before use.
- the composition may also be a ready-to-use (in-use) composition.
- the composition is provided as a ready to use liquid comprising an aqueous phase.
- the composition being a fabric softener or fabric conditioner composition, is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use.
- the compositions may also be used in a domestic hand-washing laundry operation.
- Example 1 Preparation of compositions 1, 2 and 3 in accordance with the invention, and comparative examples A and B
- compositions 1 and 2 The following process was used to make compositions 1 and 2:-
- Comparative examples A and B were made as above, but all the electrolyte was added at step 4, and none at step 1.
- Compositions of the fabric conditioners 1-3, A and B are shown in Table 1 below.
- Table 1 Composition of Compositions 1-3 and Comparative Examples A and B Ingredient Amount (wt %) 1 A 2 3 B TEAQ 1 20 20 20 20 20 20 20 Antifoam 2 0.02 0.02 0.02 0.02 0.02 0.02 Hydrochloric acid 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Perfume A1 1.15 1.15 - - - Encapsulated Perfume A2 1.0 1.0 - - - Perfume B1 - - 1.0 1.0 1.0 Encapsulated Perfume B2 - - 0.7 0.7 CaCl 2 before active 0.105 0 0.1 0.11 0 CaCl 2 after active 0.105 0.22 0.1 0.09 0.12 water & minors 3 balance balance balance balance balance balance balance 1 Softening active - Palm
- Example 2 Viscosity behaviour of Compositions 1-3. A and B initially and after storage for 1 day, 2 days. 7 days at ambient temperature, and 10 weeks at 40 °C
- Viscosities of compositions 1-3, A and B were measured using an air bearing viscometer with "cup and bob” geometry; the viscosity being continuously measured under shear at 106s -1 , at 25°C.
- Table 2 Viscosities of Compositions 1-3, A and B initially and after storage for 1 day, 2 days, 7 days at ambient temperature and 10 weeks at 40 °C Composition Viscosity (mPas) Initial 1 day 2 day 7 day 10 weeks @ 40°C A 42 32 24 16 23 1 50 46 36 32 49 B 76 43 - 35 48 2 39 30 - 25 50 3 38 33 - 30 52
- compositions in accordance with the invention have a much more stable viscosity than the comparative examples, which experience a dramatic drop in viscosity after preparation.
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Description
- The present invention concerns a process for the preparation of fabric conditioner compositions having superior viscosity control, comprising a plurality of encapsulated benefit agents and a fabric softening active.
-
WO 20111139578 -
JP 2007/237050 -
WO 2004/046290 (Colgate) discloses aqueous ester-linked quat based softeners where calcium chloride is added to the liquid mixture after the active. Examples describe the addition of 0.25% CaCl2 to stabilise superconcs containing up to 27 wt % active. When all salt is added at the end of the preparation process, the product viscosity drops 24 hours after making. -
WO 2004/027002 (Unilever) discloses ester quat based fabric conditioners in which calcium chloride is post-dosed at the end of the preparation process. -
EP 1264874 (Kao) discloses the manufacture of fabric softener compositions, comprising mixed actives, for improved softness under certain wash conditions. In the examples, magnesium chloride is mixed into a water phase before the addition of a di-ester softening active. -
EP 1077251 (Givaudan) discloses the manufacture of a liquid fabric conditioner composition, comprising 15 wt % of a diester active. In the examples, magnesium chloride is pre-mixed with water prior to adding a cationic/nonionic/anti-foam pre-mix. Example 3 discloses the addition of 0.6 wt % of CaCl2 to the water phase. Unusually high salt levels are employed (0.6 to 1%). -
US 5880086 (Clariant) discloses a concentrated fabric softening composition comprising 20 wt % of TEA ester quat active and magnesium chloride as an optional ingredient. The concentrates are prepared by simply mixing or dispersing the individual components in water. -
WO 98/12293 WO 98/03619 WO 97/34975 WO 97/34972 -
WO 96/21715 -
WO 96/15212 WO 94/20597 -
WO 95/16766 - (P&G, 15/09/1994) discloses a process for making a liquid ester-based fabric conditioner in which CaCl2 is added at three different stages in the process, namely about half to two-thirds of the way through the addition of the quat premix into the water, at the end of the addition of the quat and after the addition of perfume.
-
EP 634475 -
JP 2007 237050 -
WO 2010/012590 (Unilever PLC) discloses a composition comprising: i) encapsulated perfume components, ii) a fabric softening active, which is selected from an ester-linked quaternary ammonium compound and an oily sugar derivative and mixtures thereof; iii) a stabilising active selected from the group consisting of from 0.05 to 0.2 wt percent by the total weight of the composition of water soluble non- ester-linked cationic quaternary ammonium compound (s), from 0.65 to 1.5 wt percent by the total weight of the composition of non-ionic surfactant (s) and mixtures thereof, and iv) from 0.005 to 0.1 wt percent by the total weight of the composition of salt, wherein the encapsulates comprise a capsule wall having surface weak acid groups. -
WO 2011/139578 (Procter & Gamble) discloses a process for making a liquid fabric softening composition, comprising the steps of; a) Providing a first composition comprising a fabric softening active, the fabric softening active comprising a multilamellar phase of cationic vesicles; b) Adding to, and mixing with the first composition, a silicone emulsion, and a polyol, to produce a second composition, the second composition comprising from 0.0001 percent to 0.1 percent by weight of the second composition of a water-soluble salt; c) Adding to the second composition, a third composition, the third composition comprising, 20 percent to 50 percent by weight of the third composition of a perfume microcapsule and from 0.01 percent to 2.5 percent by weight of the third composition of a water-soluble salt; d) Mixing the second and third compositions to make a final fabric softening composition. - Electrolyte is commonly added to quat-based fabric conditioner formulations in order to control viscosity and viscostability. The addition of electrolyte (typically CaCl2) after the active has been added to the water is common practice and enables the viscosity to be tailored in terms of desired thickness, depending on the amount of electrolyte added.
- However, we have found that a problem persists in that the viscosity of the fabric conditioner continues to drop for around 1 week after the manufacturing process has finished. This is particularly problematic as, by the time the product reaches the consumer, it has become thin and less appealing.
- This is seen, for example, in
WO 2004/046290 (Colgate ); the examples disclose the use of 0.25% CaCl2 to stabilise fabric conditioners comprising up to 27% active. The viscosity is seen to drop rapidly from the initial measurement immediately following preparation, and continues to drop until it equilibrates at a lower level. - One approach to solving this problem is to produce the composition with less electrolyte, such that it is above the target viscosity for the consumer, with the expectation that viscosity will drop to a desirable level by the time it reaches the consumer. This, however, introduces the risk that if for some reason the viscosity does not drop, then an unacceptably thick product will be received by consumers. It is also more difficult to control the viscosity fall exactly into spec.
- There remains a need for ways of improving viscostability and viscosity control of such fabric conditioner compositions, which enables delivery of reliable and predictable product quality to consumers
- We have surprisingly found that the incorporation of electrolyte into the product using a specific process route, whereby the electrolyte is partially added to the water phase before and after the addition of the ester-linked quaternary ammonium fabric softening active, is critical to achieving improved viscostability of the end product. The result is that the viscosity drop after the process is either completely eliminated or at least substantially reduced to within the specification range. This new process still delivers good long term stability.
- In a first aspect of the invention there is provided a process for preparing an aqueous concentrated fabric conditioning composition, which is an aqueous dispersion, comprising
- a) from 10 to 30 wt % of an ester-linked quaternary ammonium fabric softening active,
- b) water;
- c) perfume present in encapsulated and non-confined forms, the total amount of encapsulated and non-confined perfume present being an amount of from 0.01 to 10 % by weight; and
- d) from 0.001 to 1 % electrolyte;
- i) adding from 55 to 75 wt % of electrolyte by total weight of electrolyte to the water before the addition of the ester-linked quaternary ammonium fabric softening active to the water, and
- ii) adding a proportion of the electrolyte after the addition of the ester-linked quaternary ammonium fabric softening active.
- In the process of the invention, electrolyte is added before and after addition of ester-linked quaternary ammonium softening active to a water phase.
- A proportion of the electrolyte is added to the water phase before the combination of the softening active with the water phase; and the remaining portion of electrolyte is added after the combination of the softening active with the water phase.
- 55 to 75 wt %, of electrolyte, by total weight of electrolyte, is added before the addition of the fabric softening active to the water.
- The amount of electrolyte added before the addition of the fabric softening active is preferably 0.05 to 0.2 wt %, more preferably from 0.9 to 0.15 wt %, by total weight of the composition.
- The water phase may also contain minor and/or optional components, for example, dye, preservatives, polymer, antioxidants and antifoam. Encapsulated perfume may be added to the water phase. Non-confined perfume oil is preferably added in the conventional way, after the active and water phases have been combined and cooled.
- A preferred process of the invention comprises the steps of:-
- 1) mix a portion of the electrolyte (along with optional ingredients, for example, polymer, minors and perfume encaps) with heated water to form a water phase;
- 2) melt the ester-linked quaternary ammonium softening active [and optional non-ionic surfactant] to form a melt;
- 3) combine the water phase and the melt with agitation to form an aqueous dispersion;
- 4) add a further portion of electrolyte;
- 5) allow the resulting mixture to cool; and
- 6) add optional non-confined perfume oil and optional antifoam to the cooled mixture.
- Preferably, the optional ingredients (polymer, dye, preservatives, antioxidants, perfume encaps, etc) are added to the heated water before the addition of the ester-linked quaternary ammonium softening active.
- The ester-linked quaternary ammonium softening active is present in an amount of from 10 to 30 wt %, preferably from 12 to 25 wt %, most preferably from 14 to 22 wt %, by weight of the total composition.
- The ester-linked quaternary ammonium softening active is a fabric-substantive quaternary ammonium compound which, in pure form as a strong acid salt (e.g. chloride), has a solubility in distilled water at pH 2.5 and 20°C of less than 1g/l, preferably less than 0.1g/l more preferably less than 0.01 g/l or can be a mixture of such compounds.
- Preferred quaternary ammonium compounds for use in the process of the invention have unsaturated chains, i.e. are the so-called "soft" quats. Such compounds are typically derived from fatty acyl or fatty acid feed stock having an Iodine Value of from 20 to 140, preferably from 20 to 60, more preferably from 20 to 50, most preferably from 25 to 45. The unsaturated chains come from the unsaturated fatty feed stock.
- If there is a mixture of quaternary ammonium materials present in the composition, the iodine value, referred to above, represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all of the quaternary ammonium materials present. Likewise, if there is any saturated quaternary ammonium quaternary ammonium materials present in the composition, the iodine value, referred to above, represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all of the quaternary ammonium materials present.
- Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in
EP 593,542 (Unilever, 1993 - Particularly preferred materials are water insoluble ester-linked triethanolammonium (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.
- Typically, such TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound. Typically the di-ester linked component comprises no more than 70 % by weight of the fabric softening compound, preferably no more than 60 %, e.g. no more than 55 %, or even no more than 45 % of the fabric softening compound and at least 10 % of the monoester linked component.
- A first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I):
[(CH2)n(TR)]m-(R1).N+-[(CH2)n(OH)]3-mX- (I)
wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R1 represents a C1-4 alkyl, C2-4 alkenyl or a C1-4 hydroxyalkyl group; T is generally O-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO.O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate. Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the present invention. - Most preferably, n = 2 and T = O-CO, to form a triethanolamine quaternary ammonium compound.
- Especially preferred agents are preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".
- Commercial examples include Stepantex™ UL85, ex Stepan, Prapagen™ TQL, ex Clariant, and Tetranyl™ AHT-1, ex Kao, (both di-[hardened tallow ester] of triethanolammonium methylsulphate), AT-1 (di-[tallow ester] of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and Rewoquat™ WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated fatty acids), ex Degussa.
- Also, soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable.
- A second group of quaternary ammonium compounds suitable for use in the invention is represented by formula (II):
(R1)3N+-(CH2)n-CH.(CH2TR2)-TR2X- (II)
wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and wherein n, T, and X- are as defined above. - Preferred materials of this second group include 1,2 bis[tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 and 1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride. Such materials are described in
US 4,137,180 (Lever Brothers ). Preferably, these materials also comprise an amount of the corresponding mono-ester. - A third group of quaternary ammonium compounds suitable for use in the invention is represented by formula (III):
(R1)2-N+-[(CH2)n-T-R2]2X- (III)
wherein each R1 group is independently selected from C1-4 alkyl, or C2-4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and n, T, and X- are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride. - The electrolyte is a salt.
- The salt is preferably a mineral salt. Generally, any of the alkaline metals or alkaline earth metal salts of the mineral acids can be used as the salt. Based on their availability, solubility and low toxicity, NaCl, CaCl2, MgCl2 and MgSO4 and similar salts of alkaline and alkaline earth metals are preferred, and CaCl2 is especially preferred.
- Other, less preferred electrolytes, which are suitable for use in the present invention, include water soluble organic salts.
- The electrolyte is present in an amount of from 0.001 to 1% and preferably at from 0.005 to 0.5%, most preferably from 0.1 to 0.3 % by weight of the total composition.
- The compositions derived from the process of the present invention comprises one or more perfumes. The perfume may be present in encapsulated and non-confined forms. The total amount of encapsulated and non-confined perfume present is an amount of from 0.01 to 10 % by weight, more preferably from 0.05 to 5 % by weight, even more preferably from 0.1 to 4.0 %, most preferably from 0.5 to 3.0 % by weight, based on the total weight of the composition. The amount of encaps present is preferably from 0.01 to 1.0 %, more preferably from 0.1 to 0.9 and most preferably from 0.3 to 0.8 % by weight of the total composition.
- Where present, the encapsulated perfume is preferably in the form of a slurry having a viscosity of from greater than water to 1000 cps at 21 s-1 and 25 °C. Greater than one type of encapsulated perfume may be present.
- The perfume loading of the encaps, that is to say the amount of the total encap weight that is perfume, is preferably from 20 to 40 wt %, more preferably from 28 to 32 wt %, by total weight of the encaps.
- The encaps (or "capsules") for use in the process of the present invention comprise a shell. The shell is preferably comprised of materials including aminoplasts, proteins, polyurethanes, polysaccharides, gums, celluloses, and any other encapsulating material which may be used effectively in the present invention, such as polymethylmethacrylate. Preferred encapsulating polymers include those formed from melamine formaldehyde or urea formaldehyde condensates, as well as similar types of aminoplasts. Most preferably the shell comprises melamine formaldehyde.
- Additionally, microcapsules made via the simple or complex coacervation of gelatin are also preferred for use with the coating. Microcapsules having shell walls comprised of polyurethane, polyamide, polyolefin, polysaccaharide, protein, silicone, lipid, modified cellulose, gums, polyacrylate, polystyrene, and polyesters or combinations of these materials are also possible.
- A representative process used for aminoplast encapsulation is disclosed in 3516941USA
U.S. Patent No. 3,516,941 though it is recognized that many variations with regard to materials and process steps are possible. A representative process used for gelatin encapsulation is disclosed in 2800457USAU.S. Patent No, 2,800,457 though it is recognized that many variations with regard to materials and process steps are possible. Both of these processes are discussed in the context of fragrance encapsulation for use in consumer products in 4145184USAU.S. Patent Nos. 4,145,184 and 5112688USA5,112,688 respectively. - Encapsulation can provide pore vacancies or interstitial openings depending on the encapsulation techniques employed.
- Fragrance capsules known in the art and suitable for use in the present invention comprise a wall or shell comprising a three-dimensional cross-linked network of an aminoplast resin, more specifically a substituted or un-substituted acrylic acid polymer or co-polymer cross-linked with a urea-formaidehyde pre-condensate or a melamine-formaldehyde pre-condensate.
- Microcapsule formation using mechanisms similar to the foregoing mechanism, using (i) melamine-formaldehyde or urea-formaldehyde pre-condensates and (ii) polymers containing substituted vinyl monomeric units having proton-donating functional group moieties (e.g. sulfonic acid groups or carboxylic acid anhydride groups) bonded thereto is disclosed in 44068162USBU.S. Patent
4,406,816 (2-acrylamido-2-methyl-propane sulfonic acid groups), 2062570GBAUK published Patent ApplicationGB 2,062,570 A GB 2,006,709 A - Particle size and average diameter of the capsules can vary from about 10 nanometers to about 1000 microns, preferably from about 50 nanometers to about 100 microns, more preferably from about 2 to about 40 microns, even more preferably from about 3 to 30 microns. A particularly preferred range is from about 5 to 10 microns, for example 6 to 7 microns. The capsule distribution can be narrow, broad or multimodal. Multimodal distributions may be composed of different types of capsule chemistries.
- Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products, i.e., of imparting an odour and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.
- By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
- Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
- It is advantageous to encapsulate perfume components which have a low Clog P (i.e. those which will be partitioned into water), preferably with a Clog P of less than 3.0. These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials:
Allyl Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisole, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Iso Valerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor Gum, Laevo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formate, Cis-Jasmone, cis-3-Hexenyl Acetate, Cuminic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Aceto Acetate, Ethyl Amyl Ketone, Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (tricyclo Decenyl Acetate), Frutene (tricyclco Decenyl Propionate), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydratropic Alcohol, Hydroxycitronellal, Indone, Isoamyl Alcohol, Iso Menthone, Isopulegyl Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Formate, Menthone, Menthyl Acetphenone, Methyl Amyl Ketone, Methyl Anthranilate, Methyl Benzoate, Methyl Benyl Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptine Carbonate, Methyl Heptyl Ketone, Methyl Hexyl Ketone, Methyl Phenyl Carbinyl Acetate, Methyl Salicylate, Methyl-N-Methyl Anthranilate, Nerol, Octalactone, Octyl Alcohol, p-Cresol, p-Cresol Methyl Ether, p-Methoxy Acetophenone, p-Methyl Acetophenone, Phenoxy Ethanol, Phenyl Acetaldehyde, Phenyl Ethyl Acetate, Phenyl Ethyl Alcohol, Phenyl Ethyl Dimethyl Carbinol, Prenyl Acetate, Propyl Bornate, Pulegone, Rose Oxide, Safrole, 4-Terpinenol, Alpha-Terpinenol, and /or Viridine. - Suitable non-encapsulated perfume ingredients include those hydrophobic perfume components with a ClogP above 3. As used herein, the term "ClogP" means the logarithm to base 10 of the octanol/water partition coefficient (P). The octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the hydrophobicity of a material--the higher the ClogP value, the more hydrophobic the material. ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in
U.S. Pat. No. 5,578,563 . - Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1-Ethyl-4-nitrobenzene, Heptyl formate, 4-lsopropylphenol, 2-Isopropylphenol, 3-IsopropyIphenol, Allyl disulfide, 4-Methyl-1-phenyl-2-pentanone, 2-Propylfuran, Allyl caproate, Styrene, Isoeugenyl methyl ether, Indonaphthene, Diethyl suberate, L-Menthone, Menthone racemic, p-Cresyl isobutyrate, Butyl butyrate, Ethyl hexanoate, Propyl valerate, n-Pentyl propanoate, Hexyl acetate, Methyl heptanoate, trans-3,3,5-Trimethylcyclohexanol, 3,3,5-Trimethylcyclohexanol, Ethyl p-anisate, 2-Ethyl-1-hexanol, Benzyl isobutyrate, 2,5-Dimethylthiophene, Isobutyl 2-butenoate, Caprylnitrile, gamma-Nonalactone, Nerol, trans-Geraniol, 1-Vinylheptanol, Eucalyptol, 4-Terpinenol, Dihydrocarveol, Ethyl 2-methoxybenzoate, Ethyl cyclohexanecarboxylate, 2-Ethylhexanal, Ethyl amyl carbinol, 2-Octanol, 2-Octanol, Ethyl methylphenylglycidate, Diisobutyl ketone, Coumarone, Propyl isovalerate, Isobutyl butanoate, Isopentyl propanoate, 2-Ethylbutyl acetate, 6-Methyl-tetrahydroquinoline, Eugenyl methyl ether, Ethyl dihydrocinnamate, 3,5-Dimethoxytoluene, Toluene, Ethyl benzoate, n-Butyrophenone, alpha-Terpineol, Methyl 2-methylbenzoate, Methyl 4-methylbenzoate, Methyl 3, methylbenzoate, sec.Butyl n-butyrate, 1,4-Cineole, Fenchyl alcohol, Pinanol, cis-2-Pinanol, 2,4, Dimethylacetophenone, Isoeugenol, Safrole, Methyl 2-octynoate, o-Methylanisole, p-Cresyl methyl ether, Ethyl anthranilate, Linalool, Phenyl butyrate, Ethylene glycol dibutyrate, Diethyl phthalate, Phenyl mercaptan, Cumic alcohol, m-Toluquinoline, 6-Methylquinoline, Lepidine, 2-Ethylbenzaldehyde, 4-Ethylbenzaldehyde, o-Ethylphenol, p-Ethylphenol, m-Ethylphenol, (+)-Pulegone, 2,4-Dimethylbenzaldehyde, Isoxylaldehyde, Ethyl sorbate, Benzyl propionate, 1,3-Dimethylbutyl acetate, Isobutyl isobutanoate, 2,6-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 3,5-Xylenol, Methyl cinnamate, Hexyl methyl ether, Benzyl ethyl ether, Methyl salicylate, Butyl propyl ketone, Ethyl amyl ketone, Hexyl methyl ketone, 2,3-Xylenol, 3,4, Xylenol, Cyclopentadenanolide and Phenyl ethyl 2 phenylacetate 2.
- It is commonplace for a plurality of perfume components to be present in a formulation.
- Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
- Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed
WO 01/46361 - The compositions of the present invention will preferably comprise a fatty complexing agent. Especially suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.
- Without being bound by theory it is believed that the fatty complexing material improves the viscosity profile of the composition by complexing with mono-ester component of the fabric conditioner material thereby providing a composition which has relatively higher levels of di-ester and tri-ester linked components. The di-ester and tri-ester linked components are more stable and do not affect initial viscosity as detrimentally as the mono-ester component.
- It is also believed that the higher levels of mono-ester linked component present in compositions comprising quaternary ammonium materials based on TEA may destabilise the composition through depletion flocculation. By using the fatty complexing material to complex with the mono-ester linked component, depletion flocculation is significantly reduced.
- In other words, the fatty complexing agent at the increased levels, as required by the present invention, "neutralises" the mono-ester linked component of the quaternary ammonium material. This in situ di-ester generation from mono-ester and fatty alcohol also improves the softening of the composition.
- Preferred fatty acids include hardened tallow fatty acid (available under the trade name Pristerene™, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the trade names Stenol™ and Hydrenol™, ex Cognis and Laurex™ CS, ex Albright and Wilson).
- The fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%. The weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1:5, more preferably 4:1 to 1:4, most preferably 3:1 to 1:3, e.g. 2:1 to 1:2.
- An antifoam may be present in an amount of from 0.025 to 0.45 wt %, preferably 0.03 to 0.4 wt %, most preferably from 0.05 to 0.35 wt %, for example 0.07 to 0.4 wt %, by weight of the total composition and based on 100 % antifoam activity.
- A wide variety of materials may be used as antifoams, and antifoams are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
- Suitable antifoams include, for example, silicone antifoam compounds, alcohol antifoam compounds, for example 2-alkyl alcanol antifoam compounds, fatty acids, paraffin antifoam compounds, and mixtures thereof. By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
- Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Many such silicone antifoam compounds also contain a silica component. The term "silicone" as used herein, and in genera! throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types like the polyorganosiloxane oils, such as polydimethyl-siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silica particles are often hydrophobed, e.g. as Trimethylsiloxysilicate. Silicone antifoam agents are well known in the art and are, for example, disclosed in
U. S. Patent 4, 265, 779 , issued May 5, 25 1981 to Gandolfo et al and European Patent Application No.89307851. 9, published February 7, 1990, by Starch, M. S. U. S. Patent 3, 455, 839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent ApplicationDOS 2, 124, 526 U. S. Patent 3, 933, 672, 35 Bartolotta et al , and inU. S. Patent 4, 652, 392, Baginski et al, issued March 24, 1987 . Examples of suitable silicone antifoam compounds are the combinations of polyorganosiloxane with silica particles commercially available from Dow Corning, Wacker Chemie and Momentive. - Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in
US Patent 2, 954, 347 . The monocarboxylic fatty acids, and salts thereof, for use as antifoam agents typically have hydrocarbyl chains of about 10 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms like the tallow amphopolycarboxyglycinate commercially available under the trade name TAPAC. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. - Other suitable antifoam compounds include, for example, high molecular weight hydrocarbons such as paraffin, light petroleum odourless hydrocarbons, fatty esters (e. g. fatty acid triglycerides, glyceryl derivatives, polysorbates), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e. g. stearone) N-alkylated amino triazines such as tri- to hexa- 10 alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters, and nonionic polyhydroxyl derivatives. The hydrocarbons, such as paraffin and 15 haloparaffin, can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. Hydrocarbon suds suppressers are described, for example, in
U. S. Patent 4, 265, 779 . The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in this suds suppresser discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Copolymers of ethylene oxide and propylene oxide, particularly the mixed ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from about 10 to about 16 carbon atoms, a degree of ethoxylation of from about 3 to about 30 and a degree of propoxylation of from about 1 to about 10, are also suitable antifoam compounds for use herein. - Other antifoams useful herein comprise the secondary alcohols (e.g. , 2-alkyl alkanols as described in
DE 40 21 265 ) and mixtures of such alcohols with silicone oils, such as the silicones disclosed inUS 4,798,679 ,US 4,075,118 andEP 150,872 - Further preferred antifoam agents are Silicone SRE grades and Silicone SE 47M, SE39, SE2, SE9 and SE10 available from Wacker Chemie; BF20+, DB310, DC1410, DC1430, 22210, HV495 and Q2-1607 ex Dow Corning; FD20P and BC2600 supplied by Basildon; and SAG 730 ex Momentive.
- Other suitable antifoams, described in the literature such as in Hand Book of Food Additives, ISBN 0-566-07592-X, p. 804, are selected from dimethicone, poloxamer, polypropyleneglycol, tallow derivatives, and mixtures thereof. Preferred among the antifoams described above are the silicone antifoams, in particular the combinations of polyorganosiloxane with silica particles.
- A non-ionic ethoxylated surfactant may be present in order to improve the appearance of the rinse liquor. It prevents the formation of scum which could potentially lead to deposition of scummy deposits on the laundered fabric. In particular it disperses the reaction product of the anionic surfactant from the wash and monoquat compound preventing flocculation and formation of scum resulting in a translucent dispersion.
- Suitable non-ionic surfactants are alkoxylated materials, particularly addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
- Preferred materials are of the general formula:
R-Y-(CH2CH2O)zH
- Where R is a hydrophobic moiety, typically being an alkyl or alkenyl group, said group being linear or branched, primary or secondary, and preferably having from 8 to 25, more preferably 10 to 20, and most preferably 10 to 18 carbon atoms; R may also be an aromatic group, such as a phenolic group, substituted by an alkyl or alkenyl group as described above; Y is a linking group, typically being O, CO.O, or CO.N(R1), where R1 is H or a C1-4 alkyl group; and z represents the average number of ethoxylate (EO) units present, said number being 20 or more, preferably at least 25, more preferably at least 30.
- Examples of suitable non-ionic surfactants include the ethoxylates of mixed natural or synthetic alcohols in the "coco" or "tallow" chain length. Preferred materials are condensation products of coconut fatty alcohol with 20-50 moles of ethylene oxide and condensation products of tallow fatty alcohol with 20-50 moles of ethylene oxide.
- The ethoxylates of secondary alcohols such as 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol may also be used. Exemplary ethoxylated secondary alcohols have formulae C12-EO(20); C14-EO(20); C14-EO(25); and C16-EO(30). Suitable commercially available non-ionic surfactants include Lutensol AT25, Lutensol AT50 and Unitol CE 200F.
- The compositions may comprise other optional nonionic surfactants, especially where the level of quaternary ammonium compound is above about 8 % by weight of the total composition. Typically these can be included for the purpose of stabilising the compositions.
- Suitable surfactants may conform to the general formula given above, where R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 8 to about 25, preferably 10 to 20, e.g. 14 to 18 carbon atoms.
- Y is the same as described above and Z is at least about 8, preferably at least about 10 or 11.
- Preferably the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 20, e.g. 12 to 16, and even more preferably from 15 to 20. Genapol™ C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonoionic surfactant.
- A particular surfactant may be useful in the present compositions alone or in combination with other surfactants. The preferred amounts of non-ionic surfactant indicated below refer to the total amount of such materials that are present in the composition.
- The non-ionic surfactant is generally from 0.05 to 10%, usually 0.1 to 5%, and often 3 to 4% by weight, based on the total weight of the composition.
- Optional shading dyes can be used. Preferred dyes are violet or blue. Suitable and preferred classes of dyes are discussed below. Moreover the unsaturated quaternary ammonium compounds are subject to some degree of UV light and/or transition metal ion catalysed radical auto-oxidation, with an attendant risk of yellowing of fabric. The presence of a shading dye also reduces the risk of yellowing from this source.
- Different shading dyes give different levels of colouring. The level of shading dye present in the compositions of the present invention depend, therefore, on the type of shading dye. Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt %, more preferably 0.0001 to 0.01 wt %, most preferably 0.0005 to 0.005 wt % by weight of the total composition.
- Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
- Preferably the dye are bis-azo or tris-azo dyes are used.
-
- ring D and E may be independently naphthyl or phenyl as shown;
- R1 is selected from: hydrogen and C1-C4-alkyl, preferably hydrogen;
- R2 is selected from: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
- R3 and R4 are independently selected from: hydrogen and C1-C4-alkyl, preferably hydrogen or methyl;
- X and Y are independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99. Bis-azo copper containing dyes such as direct violet 66 may be used.
- The benzidene based dyes are less preferred.
- Preferably the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
- In another embodiment the direct dye may be covalently linked to the photo-bleach, for example as described in
WO2006/024612 . - Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:
- (i) azine dyes, wherein the dye is of the following core structure:
- wherein Ra, Rb, Rc and Rd are selected from: H, a branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl;
- the dye is substituted with at least one SO3 - or -COO- group;
- the B ring does not carry a negatively charged group or salt thereof;
- and the A ring may further substituted to form a naphthyl;
- the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.
- Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
- Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
- Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
- The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- Preferably the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
- Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
- Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue 96.
- Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
- Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in
WO2006/055787 . They are not preferred. - Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
- The compositions of the invention may contain one or more other ingredients. Such ingredients include photobleaches, fluorescent agents, dyes, preservatives (e.g. bactericides), pH buffering agents, preferably inorganic or organic based such as hydrochloric acid, lactic acid and sodium lactate, etc, perfume carriers, hydrotropes, antiredeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
- It is believed that those polymers which deposit on cloth as a part of their activity may assist in the deposition of perfume components present. These include cationic polymeric deposition aids. Suitable cationic polymeric deposition aids include cationic guar polymers such as Jaguar™ (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats™ (ex National Starch), Flocaid™ (ex National Starch), cationic potato starch such as SoftGel™ (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids).
- Short chain alcohols may also be included, for example primary alcohols, such as ethanol, propanol, and butanol, and secondary alcohols such as isopropanol. The short chain alcohol may be added with the ester linked quaternary ammonium softening active during the preparation of the composition.
- The compositions of the invention are liquids. The compositions are aqueous dispersions. The composition may be a concentrate to be diluted, rehydrated and/or dissolved in a solvent, including water, before use. The composition may also be a ready-to-use (in-use) composition. Preferably the composition is provided as a ready to use liquid comprising an aqueous phase.
- The composition, being a fabric softener or fabric conditioner composition, is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use. The compositions may also be used in a domestic hand-washing laundry operation.
- Embodiments of the invention are now illustrated with reference to the following nonlimiting examples. Unless stated otherwise, all proportions are given in weight percent by weight of the total composition.
- The following process was used to make compositions 1 and 2:-
- 1) A portion of the electrolyte, along with encapsulated perfume oil, and minor ingredients, was added to heated water to form a water phase.
- 2) The ester-linked quaternary ammonium softening active was melted to form a melt.
- 3) The water phase and melt were then mixed together with stirring.
- 4) The remaining electrolyte was then added to the resultant mixture of step 3.
- 5) The resulting mixture was allowed to cool.
- 6) The non-confined perfume oil and antifoam were then added to the cooled mixture.
- Comparative examples A and B were made as above, but all the electrolyte was added at step 4, and none at step 1.
Compositions of the fabric conditioners 1-3, A and B are shown in Table 1 below.Table 1: Composition of Compositions 1-3 and Comparative Examples A and B Ingredient Amount (wt %) 1 A 2 3 B TEAQ1 20 20 20 20 20 Antifoam2 0.02 0.02 0.02 0.02 0.02 Hydrochloric acid 0.03 0.03 0.03 0.03 0.03 Perfume A1 1.15 1.15 - - - Encapsulated Perfume A2 1.0 1.0 - - - Perfume B1 - - 1.0 1.0 1.0 Encapsulated Perfume B2 - - 0.7 0.7 0.7 CaCl2 before active 0.105 0 0.1 0.11 0 CaCl2 after active 0.105 0.22 0.1 0.09 0.12 water & minors3 balance balance balance balance balance 1Softening active - Palm based soft TEA Quat; ex Stepan
2Comprising silicone; Ex Basildon
3Preservative, sequestrant - Viscosities of compositions 1-3, A and B were measured using an air bearing viscometer with "cup and bob" geometry; the viscosity being continuously measured under shear at 106s-1, at 25°C.
- The results of these assessments are given in Table 2 below:-
Table 2: Viscosities of Compositions 1-3, A and B initially and after storage for 1 day, 2 days, 7 days at ambient temperature and 10 weeks at 40 °C Composition Viscosity (mPas) Initial 1 day 2 day 7 day 10 weeks @ 40°C A 42 32 24 16 23 1 50 46 36 32 49 B 76 43 - 35 48 2 39 30 - 25 50 3 38 33 - 30 52 - It will be seen that the compositions in accordance with the invention have a much more stable viscosity than the comparative examples, which experience a dramatic drop in viscosity after preparation.
Claims (4)
- A process for preparing an aqueous concentrated fabric conditioner composition, which is an aqueous dispersion, comprisinga) from 10 to 30 wt % of an ester-linked quaternary ammonium fabric softening active,b) water;c) perfume present in encapsulated and non-confined forms, the total amount of encapsulated and non-confined perfume present being an amount of from 0.01 to 10 % by weight; andd) from 0.001 to 1% electrolyte;wherein the process comprises the steps ofi) adding from 55 to 75 wt % of electrolyte, by total weight of electrolyte to the water before the addition of the ester-linked quaternary ammonium fabric softening active to the water, andii) adding a proportion of the electrolyte after the addition of the ester-linked quaternary ammonium fabric softening active.wherein the electrolyte is a salt and wherein the ester-linked quaternary ammonium softening active is a fabric-substantive quaternary ammonium compound which, in pure form as a strong acid salt e.g. chloride, has a solubility in distilled water at pH 2.5 and 20°C of less than 1g/l,
- A process as claimed in claim 1, wherein the amount of electrolyte added before the addition of the fabric softening active is 0.05 to 0.2 wt %, by total weight of the composition.
- A process as claimed in any preceding claim, wherein the ester-linked quaternary ammonium fabric softening active is derived from fatty acyl or fatty acid feed stock having an Iodine Value of from 20 to 60.
- A process as claimed in any preceding claim, wherein greater than one type of encapsulated perfume is present.
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EP14710836.9A EP2984161B1 (en) | 2013-04-12 | 2014-03-11 | Improvements relating to fabric conditioners |
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EP13163558 | 2013-04-12 | ||
EP14710836.9A EP2984161B1 (en) | 2013-04-12 | 2014-03-11 | Improvements relating to fabric conditioners |
PCT/EP2014/054660 WO2014166686A1 (en) | 2013-04-12 | 2014-03-11 | Improvements relating to fabric conditioners |
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EP (1) | EP2984161B1 (en) |
CN (1) | CN105102603B (en) |
BR (1) | BR112015024410B1 (en) |
TR (1) | TR201900141T4 (en) |
WO (1) | WO2014166686A1 (en) |
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EP4067465A1 (en) * | 2021-03-29 | 2022-10-05 | Unilever IP Holdings B.V. | Fabric conditioner composition |
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EP3262150A1 (en) * | 2015-02-27 | 2018-01-03 | Rhodia Operations | Composition comprising a quaternary ammonium compound, a cationic polysaccharide and a nonionic polymer |
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JP2007237050A (en) * | 2006-03-07 | 2007-09-20 | Lion Corp | Method for manufacturing oil-in-water-type emulsion containing high-concentration quaternary ammonium salt |
BRPI0916561B1 (en) * | 2008-07-29 | 2018-11-06 | Unilever Nv | liquid softener composition and method of stabilizing a composition |
EP2385099A1 (en) * | 2010-05-06 | 2011-11-09 | The Procter & Gamble Company | Process of making liquid fabric softening compositions |
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2014
- 2014-03-11 BR BR112015024410-6A patent/BR112015024410B1/en not_active IP Right Cessation
- 2014-03-11 WO PCT/EP2014/054660 patent/WO2014166686A1/en active Application Filing
- 2014-03-11 EP EP14710836.9A patent/EP2984161B1/en active Active
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EP4067465A1 (en) * | 2021-03-29 | 2022-10-05 | Unilever IP Holdings B.V. | Fabric conditioner composition |
WO2022207230A1 (en) * | 2021-03-29 | 2022-10-06 | Unilever Ip Holdings B.V. | Fabric conditioner composition |
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EP2984161A1 (en) | 2016-02-17 |
BR112015024410A8 (en) | 2019-12-10 |
BR112015024410A2 (en) | 2017-07-18 |
TR201900141T4 (en) | 2019-01-21 |
WO2014166686A1 (en) | 2014-10-16 |
BR112015024410B1 (en) | 2021-08-03 |
CN105102603A (en) | 2015-11-25 |
CN105102603B (en) | 2018-08-07 |
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