CA2042979C - Fabric treatment composition - Google Patents
Fabric treatment composition Download PDFInfo
- Publication number
- CA2042979C CA2042979C CA002042979A CA2042979A CA2042979C CA 2042979 C CA2042979 C CA 2042979C CA 002042979 A CA002042979 A CA 002042979A CA 2042979 A CA2042979 A CA 2042979A CA 2042979 C CA2042979 C CA 2042979C
- Authority
- CA
- Canada
- Prior art keywords
- absent
- hydrogen
- independently selected
- alkyl
- polymer
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000004744 fabric Substances 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000839 emulsion Substances 0.000 claims abstract description 41
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 35
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 18
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000002304 perfume Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 150000001408 amides Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical group N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Chemical group 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 125000004350 aryl cycloalkyl group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 11
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 claims 6
- 238000010348 incorporation Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- -1 acrylic acid Chemical class 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 244000060011 Cocos nucifera Species 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 239000003760 tallow Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004166 Lanolin Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000004665 cationic fabric softener Substances 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 229940039717 lanolin Drugs 0.000 description 4
- 235000019388 lanolin Nutrition 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 235000019271 petrolatum Nutrition 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229940091181 aconitic acid Drugs 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- PGZPBNJYTNQMAX-UHFFFAOYSA-N dimethylazanium;methyl sulfate Chemical compound C[NH2+]C.COS([O-])(=O)=O PGZPBNJYTNQMAX-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- MMKRHZKQPFCLLS-UHFFFAOYSA-N ethyl myristate Chemical compound CCCCCCCCCCCCCC(=O)OCC MMKRHZKQPFCLLS-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- LUKNLVTZDZMBOU-UHFFFAOYSA-N n-ethoxymethanamine Chemical compound CCONC LUKNLVTZDZMBOU-UHFFFAOYSA-N 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WWQQDCCLJXJJSZ-UHFFFAOYSA-N (2-dodecylphenyl) 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC(=O)C(C)=C WWQQDCCLJXJJSZ-UHFFFAOYSA-N 0.000 description 1
- QFLLGSOYCXRUCR-UHFFFAOYSA-N (2-dodecylphenyl) prop-2-enoate Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC(=O)C=C QFLLGSOYCXRUCR-UHFFFAOYSA-N 0.000 description 1
- XTJDUBPOTVNQPI-UHFFFAOYSA-N (2-nonylphenyl) 2-methylprop-2-enoate Chemical compound CCCCCCCCCC1=CC=CC=C1OC(=O)C(C)=C XTJDUBPOTVNQPI-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- FQKSRGCBHCFRTN-UHFFFAOYSA-N (4-nonylphenyl) prop-2-enoate Chemical compound CCCCCCCCCC1=CC=C(OC(=O)C=C)C=C1 FQKSRGCBHCFRTN-UHFFFAOYSA-N 0.000 description 1
- ORKBYCQJWQBPFG-WOMZHKBXSA-N (8r,9s,10r,13s,14s,17r)-13-ethyl-17-ethynyl-17-hydroxy-1,2,6,7,8,9,10,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-3-one;(8r,9s,13s,14s,17r)-17-ethynyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.O=C1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 ORKBYCQJWQBPFG-WOMZHKBXSA-N 0.000 description 1
- BSSNZUFKXJJCBG-OWOJBTEDSA-N (e)-but-2-enediamide Chemical compound NC(=O)\C=C\C(N)=O BSSNZUFKXJJCBG-OWOJBTEDSA-N 0.000 description 1
- JLJNZJNPAYILPJ-XYJRJTJESA-M 1-[1-[(z)-octadec-9-enyl]-4,5-dihydroimidazol-1-ium-1-yl]tetradecan-1-ol;chloride Chemical compound [Cl-].CCCCCCCC\C=C/CCCCCCCC[N+]1(C(O)CCCCCCCCCCCCC)CCN=C1 JLJNZJNPAYILPJ-XYJRJTJESA-M 0.000 description 1
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical group OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- PABGQABTFFNYFH-UHFFFAOYSA-N 2-methyl-n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C(C)=C PABGQABTFFNYFH-UHFFFAOYSA-N 0.000 description 1
- WCCVMVPVUAVUFI-UHFFFAOYSA-N 2-methylprop-2-enamide;hydrochloride Chemical compound Cl.CC(=C)C(N)=O WCCVMVPVUAVUFI-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical compound C=CN1CCOCC1 CFZDMXAOSDDDRT-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
Landscapes
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Abstract
A fabric treatment composition comprising an aqueous base, one or more, fabric-softening materials and an emulsion component, said composition having a structure of lamellar droplets of the fabric-softening material in combination with an emulsion, said composition also comprising a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side chains.
The deflocculating polymer allows the incorporation of greater amounts of softening materials and/or emulsion components that would otherwise be compatible with the need for a stable, easily dispersible product of acceptable viscosity.
The deflocculating polymer allows the incorporation of greater amounts of softening materials and/or emulsion components that would otherwise be compatible with the need for a stable, easily dispersible product of acceptable viscosity.
Description
20429'9 FABRIC TREATMEZJT COMPOSITIONS
The present invention relates to fabric treatment compositions in aqueous medium and containing a relatively high proportion of fabric conditioner. In particular, the present invention relates to fabric treatment compositions which comprise as conditioners one or more fabric-softening materials and one or more emulsion forming components to result in a structure of a dispersion of an emulsion and a dispersion of lamellar droplets in a continuous aqueous phase.
Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry:
Industrial Applications', J.Wiley & Sons, Letchworth 1980.
Lamellar fabric-softening compositions are for example known from EP 303 473 (Albright and Wilson). This patent application describes fabric-softening compositions comprising an aqueous base, a cationic fabric softener 2~4~9~9 having two long alkyl or alkenyl groups and dissolved electrolyte to form an optically anisotropic spherulitic composition.
The presence of lamellar droplets in a fabric-softening product may be detected my means known to those skilled in the art, for example optical techniques, various rheometrical measurements, X-ray or neutron diffraction, and electron microscopy.
The droplets consist of an onion-like configuration of concentric bi-layers of molecules of fabric-softening material, between which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are nearly or fully close-packed provide a very desirable combination of physical stability and useful flow properties.
It is desirable to add other components to fabric softening compositions in the form of emulsions in the aqueous phase, to provide added benefits such as crease reduction and ease of ironing as well as improving softening. For example hydrocarbons such as mineral oils which give added softening and lubricating effects when applied to textile fibres and fabrics, perfume emulsions and solutions of perfumes in carrier emulsions.
In the past it has been recognised that certain stability problems arise when hydrocarbons are added to a dispersion of fabric softening material. For example in GB 1 601 360 (Procter and Gamble Co/Goffinet) certain textile treatment compositions are disclosed comprising a water insoluble cationic fabric softener, a hydrocarbon and a relatively high proportion of a cationic surfactant which is water soluble. It is believed that such water soluble surfactants are not lamellar phase forming and are present to solubilise the hydrocarbon. Such compositions can still suffer from high viscosity. In EP 13 780 (Procter and Gamble/Verbruggen) low levels of non-cyclic hydrocarbons of fatty acids are suggested as viscosity control aids in compositions comprising up to 20% of certain imidazolinium salts. There is no disclosure of how to incorporate higher levels of the hydrocarbon or fatty acid without encountering viscosity problems.
It is believed that the presence of the lamellar dispersion of fabric softening material can flocculate the emulsion component by a mechanism of depletion. This phenomenon is well known in mixed disperse systems and in systems containing either a structured surfactant phase or a non-adsorbed polymer for example D.Fairhurst, M.Aronson, M.Gun and E.Goddard Colloids Surf. 1983, 7, 153. This depletion flocculation leads to increases in the viscosity of the fabric treatment composition due to reduction of the inter-particle spacings.
There are two main factors determining the viscosity and stability of the fabric softening composition, the combined volume fraction of the dispersed lamellar phase and the emulsion and their state of aggregation.
Generally speaking, the higher the volume fraction of the dispersed lamellar phase (droplets) and emulsion phase (particles), the higher the viscosity which in the limit can result in an unpourable or gelled product. When the volume fraction is around 0.6, or higher, the droplets are just touching (space-filling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas most preferably no more than 0.5Pas at a shear rate of 21s 1). However, flocculation of the particles can also occur. As 2~429~~
The present invention relates to fabric treatment compositions in aqueous medium and containing a relatively high proportion of fabric conditioner. In particular, the present invention relates to fabric treatment compositions which comprise as conditioners one or more fabric-softening materials and one or more emulsion forming components to result in a structure of a dispersion of an emulsion and a dispersion of lamellar droplets in a continuous aqueous phase.
Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry:
Industrial Applications', J.Wiley & Sons, Letchworth 1980.
Lamellar fabric-softening compositions are for example known from EP 303 473 (Albright and Wilson). This patent application describes fabric-softening compositions comprising an aqueous base, a cationic fabric softener 2~4~9~9 having two long alkyl or alkenyl groups and dissolved electrolyte to form an optically anisotropic spherulitic composition.
The presence of lamellar droplets in a fabric-softening product may be detected my means known to those skilled in the art, for example optical techniques, various rheometrical measurements, X-ray or neutron diffraction, and electron microscopy.
The droplets consist of an onion-like configuration of concentric bi-layers of molecules of fabric-softening material, between which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are nearly or fully close-packed provide a very desirable combination of physical stability and useful flow properties.
It is desirable to add other components to fabric softening compositions in the form of emulsions in the aqueous phase, to provide added benefits such as crease reduction and ease of ironing as well as improving softening. For example hydrocarbons such as mineral oils which give added softening and lubricating effects when applied to textile fibres and fabrics, perfume emulsions and solutions of perfumes in carrier emulsions.
In the past it has been recognised that certain stability problems arise when hydrocarbons are added to a dispersion of fabric softening material. For example in GB 1 601 360 (Procter and Gamble Co/Goffinet) certain textile treatment compositions are disclosed comprising a water insoluble cationic fabric softener, a hydrocarbon and a relatively high proportion of a cationic surfactant which is water soluble. It is believed that such water soluble surfactants are not lamellar phase forming and are present to solubilise the hydrocarbon. Such compositions can still suffer from high viscosity. In EP 13 780 (Procter and Gamble/Verbruggen) low levels of non-cyclic hydrocarbons of fatty acids are suggested as viscosity control aids in compositions comprising up to 20% of certain imidazolinium salts. There is no disclosure of how to incorporate higher levels of the hydrocarbon or fatty acid without encountering viscosity problems.
It is believed that the presence of the lamellar dispersion of fabric softening material can flocculate the emulsion component by a mechanism of depletion. This phenomenon is well known in mixed disperse systems and in systems containing either a structured surfactant phase or a non-adsorbed polymer for example D.Fairhurst, M.Aronson, M.Gun and E.Goddard Colloids Surf. 1983, 7, 153. This depletion flocculation leads to increases in the viscosity of the fabric treatment composition due to reduction of the inter-particle spacings.
There are two main factors determining the viscosity and stability of the fabric softening composition, the combined volume fraction of the dispersed lamellar phase and the emulsion and their state of aggregation.
Generally speaking, the higher the volume fraction of the dispersed lamellar phase (droplets) and emulsion phase (particles), the higher the viscosity which in the limit can result in an unpourable or gelled product. When the volume fraction is around 0.6, or higher, the droplets are just touching (space-filling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas most preferably no more than 0.5Pas at a shear rate of 21s 1). However, flocculation of the particles can also occur. As 2~429~~
previously explained, the lamellar dispersion can cause depletion flocculation of the emulsion component.
Flocculation of either the lamellar dispersion or the emulsion can lead to instability because reduction of the inter-particle inter-droplet spacings will make their packing more efficient. Consequently, more lamellar droplets or emulsion will be required for stabilisation which will again lead to a further increase of the viscosity.
The volume fraction of the droplets is increased by increasing the softener concentration, and may be reduced by increasing the electrolyte level. However, the stability of the emulsion component is very sensitive to electrolyte levels. When electrolyte is added to an emulsion it reduces the effects of depletion but the levels required to prevent depletion are sufficient to cause flocculation of the emulsion by an electrostatic mechanism and thus the problem is not solved.
Thus, in practice, there are limits to the amounts of fabric softening material, emulsion component and optionally electrolyte which can be incorporated whilst still having an acceptable product. In principle, higher levels of fabric softening materials are desired for convenience and for reduction of costs, the presence of emulsion components are desired for providing added benefits such as fabric lubrication and perfume delivery and certain levels of electrolyte are desired to give, in certain circumstances, better delivery and anionic carry-over protection.
We have now found that the dependency of stability and/or viscosity upon the volume fraction of softening material and the volume fraction of the emulsion component 2~42~~~
Flocculation of either the lamellar dispersion or the emulsion can lead to instability because reduction of the inter-particle inter-droplet spacings will make their packing more efficient. Consequently, more lamellar droplets or emulsion will be required for stabilisation which will again lead to a further increase of the viscosity.
The volume fraction of the droplets is increased by increasing the softener concentration, and may be reduced by increasing the electrolyte level. However, the stability of the emulsion component is very sensitive to electrolyte levels. When electrolyte is added to an emulsion it reduces the effects of depletion but the levels required to prevent depletion are sufficient to cause flocculation of the emulsion by an electrostatic mechanism and thus the problem is not solved.
Thus, in practice, there are limits to the amounts of fabric softening material, emulsion component and optionally electrolyte which can be incorporated whilst still having an acceptable product. In principle, higher levels of fabric softening materials are desired for convenience and for reduction of costs, the presence of emulsion components are desired for providing added benefits such as fabric lubrication and perfume delivery and certain levels of electrolyte are desired to give, in certain circumstances, better delivery and anionic carry-over protection.
We have now found that the dependency of stability and/or viscosity upon the volume fraction of softening material and the volume fraction of the emulsion component 2~42~~~
can be favourably influenced by incorporating into the compositions a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side chains.
Accordingly, the present invention relates to a fabric treatment composition comprising an aqueous base, one or more fabric-softening materials, and an emulsion component, said composition having a structure of lamellar droplets of the fabric-softening material in combination with an emulsion, said composition also comprising a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side chains.
The deflocculating polymer allows, if desired, the incorporation of greater amounts of softening materials and/or emulsion components than would otherwise be compatible with the need for a stable, easily dispersable product of acceptable viscosity. It also allows (if desired) incorporation of greater amounts of certain other ingredients to which lamellar dispersions and emulsions have been highly stability-sensitive.
The present invention allows formulation of stable, pourable products wherein the volume fraction of the lamellar droplets and the emulsion is 0.5 or higher.
The volume fraction of the lamellar droplet phase and emulsion component may be determined by the following method. The composition is centrifuged, say at 40,000 G
for 12 hours, to separate the composition into a clear (continuous aqueous) layer, a turbid active-rich (lamellar/emulsion) layer and (if solids or liquids are suspended) a third layer. The conductivity of the continuous aqueous phase, the lamellar phase and of the i ~~4~~~~
Accordingly, the present invention relates to a fabric treatment composition comprising an aqueous base, one or more fabric-softening materials, and an emulsion component, said composition having a structure of lamellar droplets of the fabric-softening material in combination with an emulsion, said composition also comprising a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side chains.
The deflocculating polymer allows, if desired, the incorporation of greater amounts of softening materials and/or emulsion components than would otherwise be compatible with the need for a stable, easily dispersable product of acceptable viscosity. It also allows (if desired) incorporation of greater amounts of certain other ingredients to which lamellar dispersions and emulsions have been highly stability-sensitive.
The present invention allows formulation of stable, pourable products wherein the volume fraction of the lamellar droplets and the emulsion is 0.5 or higher.
The volume fraction of the lamellar droplet phase and emulsion component may be determined by the following method. The composition is centrifuged, say at 40,000 G
for 12 hours, to separate the composition into a clear (continuous aqueous) layer, a turbid active-rich (lamellar/emulsion) layer and (if solids or liquids are suspended) a third layer. The conductivity of the continuous aqueous phase, the lamellar phase and of the i ~~4~~~~
total composition before centrifugation are measured.
From these, the volume fraction of the lamellar phase and emulsion component is calculated or estimated, using the Bruggeman equation, as disclosed in American Physics, 24, 636 (1935). The volume fraction of the emulsion component can be calculated if desired, provided the density is known and the volume fraction of the lamellar phase calculated.
Preferably, the viscosity of the aqueous continuous phase is less than 25mPas, most preferably less than lSmPas, especially less than lOmPas, these viscosities being measured using a capillary viscometer, for example an Ostwald viscometer.
In practical terms, i.e. as determining product properties, the term 'deflocculating' in respect of the polymer means that the equivalent composition, minus the polymer, has a significantly higher viscosity and/or becomes unstable. It is not intended to embrace the use of polymers which would increase the viscosity but not enhance the stability of the composition. It is also not intended to embrace polymers which would lower the viscosity simply by a dilution effect, i.e. only by adding to the volume of the continuous phase. Although within the ambit of the present invention, relatively high levels of the deflocculating polymers can be used in those systems where a viscosity reduction is brought about;
typically levels as low as from about 0.01 by weight to about 5.0~ by weight can be capable of reducing the viscosity at 21 s 1 by up to 2 orders of magnitude.
Especially preferred embodiments of the present invention exhibit less phase separation on storage and n 1 f 2~429~"~
From these, the volume fraction of the lamellar phase and emulsion component is calculated or estimated, using the Bruggeman equation, as disclosed in American Physics, 24, 636 (1935). The volume fraction of the emulsion component can be calculated if desired, provided the density is known and the volume fraction of the lamellar phase calculated.
Preferably, the viscosity of the aqueous continuous phase is less than 25mPas, most preferably less than lSmPas, especially less than lOmPas, these viscosities being measured using a capillary viscometer, for example an Ostwald viscometer.
In practical terms, i.e. as determining product properties, the term 'deflocculating' in respect of the polymer means that the equivalent composition, minus the polymer, has a significantly higher viscosity and/or becomes unstable. It is not intended to embrace the use of polymers which would increase the viscosity but not enhance the stability of the composition. It is also not intended to embrace polymers which would lower the viscosity simply by a dilution effect, i.e. only by adding to the volume of the continuous phase. Although within the ambit of the present invention, relatively high levels of the deflocculating polymers can be used in those systems where a viscosity reduction is brought about;
typically levels as low as from about 0.01 by weight to about 5.0~ by weight can be capable of reducing the viscosity at 21 s 1 by up to 2 orders of magnitude.
Especially preferred embodiments of the present invention exhibit less phase separation on storage and n 1 f 2~429~"~
have a lower viscosity than an equivalent composition without any of the deflocculating polymer.
In the context of the present invention, stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 2~ by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
In the case of the compositions where the combined lamellar/emulsion phase volume fraction is 0.5 or greater, it is not always easy to apply this definition. In the case of the present invention, such systems may be stable or unstable, according to whether or not the droplets or particles are flocculated. For those that are unstable, i.e. flocculated, the degree of phase separation may be relatively small, e.g. as for the unstable non-flocculated systems with the lower volume fraction. However, in this case the phase separation will often not manifest itself by the appearance of a distinct layer of continuous phase but will appear distributed as 'cracks' throughout the product. The onset of these cracks appearing and the volume of the material they contain are almost impossible to measure to a very high degree of accuracy. However, those skilled in the art will be able to ascertain instability because the presence of a distributed separate phase greater than 2~ by volume of the total composition will readily be visually identifiable by such persons.
Thus, in formal terms, the above-mentioned definition of 'stable' is also applicable in these situations, but disregarding the requirement for the phase separation to appear as separate layers.
In the context of the present invention, stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 2~ by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
In the case of the compositions where the combined lamellar/emulsion phase volume fraction is 0.5 or greater, it is not always easy to apply this definition. In the case of the present invention, such systems may be stable or unstable, according to whether or not the droplets or particles are flocculated. For those that are unstable, i.e. flocculated, the degree of phase separation may be relatively small, e.g. as for the unstable non-flocculated systems with the lower volume fraction. However, in this case the phase separation will often not manifest itself by the appearance of a distinct layer of continuous phase but will appear distributed as 'cracks' throughout the product. The onset of these cracks appearing and the volume of the material they contain are almost impossible to measure to a very high degree of accuracy. However, those skilled in the art will be able to ascertain instability because the presence of a distributed separate phase greater than 2~ by volume of the total composition will readily be visually identifiable by such persons.
Thus, in formal terms, the above-mentioned definition of 'stable' is also applicable in these situations, but disregarding the requirement for the phase separation to appear as separate layers.
Especially preferred embodiments of the present invention yield less than 0.1% by volume visible phase separation after storage at 25°C for 21 days from the time of preparation.
However, it is usually possible to obtain a figure which, whilst approximate, is still sufficient to indicate the effect of the deflocculating polymer in the compositions according to the present invention. Where this difficulty arises in the compositions exemplified hereinbelow, it is indicated accordingly.
The compositions according to the invention may contain only one, or a mixture of deflocculating polymer types. The term 'polymer types' is used because, in practice, nearly all polymer samples will have a spectrum of structures and molecular weights and often impurities.
Thus, any structure of deflocculation polymers described in this specification refers to polymers which are believed to be effective for deflocculation purposes as defined hereabove. In practice these effective polymers may constitute only part of the polymer sample, provided that the amount of deflocculation polymer in total is sufficient to effect the desired deflocculation effects.
Furthermore, any structure described herein for an individual polymer type, refers to the structure of the predominating deflocculating polymer species and the molecular weight specified is the weight average molecular weight of the deflocculation polymers.
Suitable deflocculating polymer types for use in compositions of the invention are for instance described in Canadian Patent No. 1,336,385 and in PCT publications WO 91/06622 and WO 91 /06623.
However, it is usually possible to obtain a figure which, whilst approximate, is still sufficient to indicate the effect of the deflocculating polymer in the compositions according to the present invention. Where this difficulty arises in the compositions exemplified hereinbelow, it is indicated accordingly.
The compositions according to the invention may contain only one, or a mixture of deflocculating polymer types. The term 'polymer types' is used because, in practice, nearly all polymer samples will have a spectrum of structures and molecular weights and often impurities.
Thus, any structure of deflocculation polymers described in this specification refers to polymers which are believed to be effective for deflocculation purposes as defined hereabove. In practice these effective polymers may constitute only part of the polymer sample, provided that the amount of deflocculation polymer in total is sufficient to effect the desired deflocculation effects.
Furthermore, any structure described herein for an individual polymer type, refers to the structure of the predominating deflocculating polymer species and the molecular weight specified is the weight average molecular weight of the deflocculation polymers.
Suitable deflocculating polymer types for use in compositions of the invention are for instance described in Canadian Patent No. 1,336,385 and in PCT publications WO 91/06622 and WO 91 /06623.
A preferred class of polymers are biodegradeable polymers having a hydrophilic backbone and at least one hydrophobic side chain. The basic structure of polymers having a hydrophilic backbone and one or more hydrophobic side chains is described in Canadian Patent No. 1,336,385.
The hydrophilic backbone of the polymer generally is a linear, branched or cross-linked molecular composition containing one or more types of relatively hydrophilic monomer units, possibly in combination with minor amounts of relatively hydrophobic units. The only limitations to the structure of the hydrophilic backbone are that the polymer must be suitable for incorporation in an active-structured aqueous liquid softener composition and the hydrophilic backbone is relatively soluble in water in that the solubility in water of 20°C at a pH of 7.0 is preferably more than 1 g/1, more preferably more than g/1, most preferably more than 10 g/1.
Preferably the hydrophilic backbone is predominantly linear in that the main chain of the backbone constitutes at least 50% by weight, preferably more than 75%, most preferably more than 90% by weight of the backbone.
The hydrophilic backbone is constituted by monomer units, which can be selected from a variety of units available for the preparation of polymers. The polymers can be linked by any possible chemical link, although the following types of linkages are preferred:
O Q
-O-, -C-O, -C-C-, -C-, -C-N-, -N-~U4~J'~9 Water-soluble monomers suitably employed to form the hydrophilic backbone are for example those which are sufficiently water-soluble to form at least a one weight percent solution when dissolved in water and readily undergo polymerisation to form polymers which are water-soluble at ambient temperature and at a pH of 3.0 to 12.5, preferably more than 1 gram per litre, more preferably more than 5 grams per litre, most preferably more than 10 grams per litre. Exemplary water-soluble monomers include ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaramide and their N-substituted derivatives such as 2-acrylamido-2-methylpropane sulphonic acid, N-(dimethylaminomethyl) acrylamide as well as N-(trimethylammoniummethyl) acrylamide chloride and N-(trimethylammoniumpropyl) methacrylamide chloride; ethylenically unsaturated carboxylic acids or dicarboxylic acids such as acrylic acid, malefic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citroconic acid; and other ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride; sulphoalkyl esters of unsaturated carboxylic acids such as 2 sulphoethyl methacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl methacrylate, dimethyl aminoethyl (meth)acrylate, diethyl aminoethyl (meth)acrylate, dimethyl aminomethyl (meth)acrylate, diethyl aminomethyl (meth)acrylate), and their quaternary ammonium salts;
vinyl or allyl amines such as vinyl pyridine and vinyl morpholine or allylamine; dially amines and diallyl ammonium compounds such as diallyl methyl ammonium chloride; vinyl heterocyclic amides such as vinyl pyrrolidone; vinyl aryl sulphonates such as vinylbenzyl sulphonate; vinyl alcohol obtained by the hydrolysis of vinyl acetate; acrolein; allyl alcohol; vinyl acetic acid;
:. ~ 20429'~~
The hydrophilic backbone of the polymer generally is a linear, branched or cross-linked molecular composition containing one or more types of relatively hydrophilic monomer units, possibly in combination with minor amounts of relatively hydrophobic units. The only limitations to the structure of the hydrophilic backbone are that the polymer must be suitable for incorporation in an active-structured aqueous liquid softener composition and the hydrophilic backbone is relatively soluble in water in that the solubility in water of 20°C at a pH of 7.0 is preferably more than 1 g/1, more preferably more than g/1, most preferably more than 10 g/1.
Preferably the hydrophilic backbone is predominantly linear in that the main chain of the backbone constitutes at least 50% by weight, preferably more than 75%, most preferably more than 90% by weight of the backbone.
The hydrophilic backbone is constituted by monomer units, which can be selected from a variety of units available for the preparation of polymers. The polymers can be linked by any possible chemical link, although the following types of linkages are preferred:
O Q
-O-, -C-O, -C-C-, -C-, -C-N-, -N-~U4~J'~9 Water-soluble monomers suitably employed to form the hydrophilic backbone are for example those which are sufficiently water-soluble to form at least a one weight percent solution when dissolved in water and readily undergo polymerisation to form polymers which are water-soluble at ambient temperature and at a pH of 3.0 to 12.5, preferably more than 1 gram per litre, more preferably more than 5 grams per litre, most preferably more than 10 grams per litre. Exemplary water-soluble monomers include ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaramide and their N-substituted derivatives such as 2-acrylamido-2-methylpropane sulphonic acid, N-(dimethylaminomethyl) acrylamide as well as N-(trimethylammoniummethyl) acrylamide chloride and N-(trimethylammoniumpropyl) methacrylamide chloride; ethylenically unsaturated carboxylic acids or dicarboxylic acids such as acrylic acid, malefic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citroconic acid; and other ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride; sulphoalkyl esters of unsaturated carboxylic acids such as 2 sulphoethyl methacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl methacrylate, dimethyl aminoethyl (meth)acrylate, diethyl aminoethyl (meth)acrylate, dimethyl aminomethyl (meth)acrylate, diethyl aminomethyl (meth)acrylate), and their quaternary ammonium salts;
vinyl or allyl amines such as vinyl pyridine and vinyl morpholine or allylamine; dially amines and diallyl ammonium compounds such as diallyl methyl ammonium chloride; vinyl heterocyclic amides such as vinyl pyrrolidone; vinyl aryl sulphonates such as vinylbenzyl sulphonate; vinyl alcohol obtained by the hydrolysis of vinyl acetate; acrolein; allyl alcohol; vinyl acetic acid;
:. ~ 20429'~~
sodium vinyl sulphonate; sodium ally sulphonate, as well as the salts of the foregoing monomers. These monomers may be used singly or as mixtures thereof.
Optionally, the hydrophilic backbone may contain small amounts of relatively hydrophobic units, e.g. those derived from polymers having a solubility of less than 1 g/1 in water, provided that the overall solubility of the hydrophilic polymer backbone still satisfies the solubility requirements as specified here above. Examples ( of relatively water-insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide, polyhydroxypropyl acrylate.
Suitable hydrophobic monomers for forming the side chains generally include those which are (1) water-insoluble, i.e. less than 0.2 weight part of the hydrophobic monomer will dissolve in 100 weight parts water and (2) ethylenically unsaturated compounds having hydrophobic moieties. The hydrophobic moieties (when isolated from their polymerisable linkage) are relatively water-insoluble, preferably less than 1 g/1, more preferably less than 0.5 g/1, most preferably less than 0.1 g/1 at ambient temperature and a pH of 3.0 to 12.5.
The hydrophobic moieties preferably have at least 3 carbon atoms and are most preferably pendant organic groups having hydrophobicities comparable to one of the following:~aliphatic hydrogen groups having at least three carbons such as C3 to C50 alkyls and cycloalkyls;
polynuclear aromatic hydrocarbon groups such as napthyls;
alkylaryls wherein the alkyl groups has one or more carbons; haloalkyls of 3 or more carbons, preferably perfluoroalkyls; polyalkyleneoxy groups wherein alkylene 2p429~~
Optionally, the hydrophilic backbone may contain small amounts of relatively hydrophobic units, e.g. those derived from polymers having a solubility of less than 1 g/1 in water, provided that the overall solubility of the hydrophilic polymer backbone still satisfies the solubility requirements as specified here above. Examples ( of relatively water-insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide, polyhydroxypropyl acrylate.
Suitable hydrophobic monomers for forming the side chains generally include those which are (1) water-insoluble, i.e. less than 0.2 weight part of the hydrophobic monomer will dissolve in 100 weight parts water and (2) ethylenically unsaturated compounds having hydrophobic moieties. The hydrophobic moieties (when isolated from their polymerisable linkage) are relatively water-insoluble, preferably less than 1 g/1, more preferably less than 0.5 g/1, most preferably less than 0.1 g/1 at ambient temperature and a pH of 3.0 to 12.5.
The hydrophobic moieties preferably have at least 3 carbon atoms and are most preferably pendant organic groups having hydrophobicities comparable to one of the following:~aliphatic hydrogen groups having at least three carbons such as C3 to C50 alkyls and cycloalkyls;
polynuclear aromatic hydrocarbon groups such as napthyls;
alkylaryls wherein the alkyl groups has one or more carbons; haloalkyls of 3 or more carbons, preferably perfluoroalkyls; polyalkyleneoxy groups wherein alkylene 2p429~~
is propylene or high alkylene and there is at least one alkyleneoxy unit per hydrophobic moiety; and siloxane moieties. Exemplaryhydrophobic monomers include butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and the corresponding methacrylates, the higher alkyl esters of alpha, beta-ethylenically unsaturated carboxylic acids such as dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl, methacrylate, tetradeculacrylate, octadecyl acrylate, octadecyl methacrylate, octyl half ester of malefic anhydride, doictyl diethyl maleate, and other alkyl esters and half esters derived from the reactions of alkanols having from 3 to 50 carbon atoms with ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, malefic anhydride, fumaric acid, itaconic acid and aconitic acid; alkylaryl esters of ethylenically unsaturated carboxylic acid such as nonyl- -phenyl acrylate, nonyl- -phenyl methacrylate, dodecyl- -phenyl acrylate and dodecyl- -phenyl methacrylate; N-alkyl, ethylenically unsaturated amides such as N-octadecyl acrylamide; N-octadecyl methacrylamide, N,N-dioctyl acrylamide and similar derivatives thereof, -olefins such as octene-1, decene-1, dodecene-1 and hexadecene-1; vinyl alkylates wherein alkyl has at least 4 carbon atoms such as vinyl laurate and vinyl stearate; vinyl alkyl ethers such as dodecyl vinyl ether and hexadecyl vinyl ether; N-vinyl amides such as N-vinyl lauramide and N-vinyl stearamide; and alkylstyrenes such as t-butyl styrene. The hydrophobic monomer may be used singly or mixtures thereof may be employed. The ratio of hydrophilic to hydrophobic monomers may vary from about 500:1 to 5:1. The weight average molecular weights (Mw.) of the resultant polymers vary from 500 to 500,000 or above when measured by gel permeation chromatography using a polyacrylate standard, or by specific viscosity (SV) measurements using a polyacrylate standard.
v 2~4297~
v 2~4297~
Products of the invention preferably comprise polymers of the general formula:
1 ~ 2 ~ 15 I1 i2 x y R
R
~4 R n (z) ~ J z wherein z is 1; (x+y):z is from 4:1 to 1,000:1; preferably from 6:1 to 250:1 in which the monomer units may be in random order; y being from 0 up to a maximum equal to the value of x; and n is at least 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide or propylene oxide groups, or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a 01_24 alkyl or C2_24 alkenyl group, with the provisos that:
20429°~~
1 ~ 2 ~ 15 I1 i2 x y R
R
~4 R n (z) ~ J z wherein z is 1; (x+y):z is from 4:1 to 1,000:1; preferably from 6:1 to 250:1 in which the monomer units may be in random order; y being from 0 up to a maximum equal to the value of x; and n is at least 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide or propylene oxide groups, or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a 01_24 alkyl or C2_24 alkenyl group, with the provisos that:
20429°~~
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H40)tH wherein t is from 1-50, and wherein the monomer units may be in random order.
Each B1 is independently selected from -CH20H, -OH or -H.
Another class of polymers in accordance with the present invention comprises those of formula II:
I10 9 ~ r v q P
(II) n wherein:
Q2 is a molecular entity of formula IIa:
~, 20429'9 1 2 ~ 3 15 I1 C02A x C02A C02A ~ R R
'2 R
R
R
z (IIa) ' wherein z and R1 6 are as defined for formula (I);
Al 4 are as defined for formula (I);
Q1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q1 in any direction, in any order, therewith possibly resulting in a branched polymer.
Preferably Q1 is trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol;
n and z are as defined above; v is 1; and (x + y + p + q + r):z is from 5:1 to 500:1; in which the monomer units may be in random order; and preferably either p and q are zero, or r is zero;
R7 and R8 represent -CH3 or -H;
R9 and R10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups, or ~~429'~9 (C2H40)tH, wherein t is from 1-50, and wherein the monomer units may be in random order. Preferably they are selected from -S03Na, -CO-O-C2H4, -OS03Na, -CO-NH-C(CH3)2-CH2-S03Na, -CO-NH2, -O-CO-CH3, -OH. In any particular sample of polymer material in which polymers of formulae I and II are in the form of a salt, usually some polymers will be full salts (A1-Ay4 all other than hydrogen), some will be full acids (A1-A4 all hydrogen) and some will be part-salts (one or more A1-A4 hydrogen and one or more other than hydrogen).
The salts of the polymers of formulae I and II may be formed with any organic or inorganic cation defined for A1-A4 and which is capable of forming a water-soluble salt with a low molecular weight carboxylic acid. Preferred are the alkali metal salts, especially of sodium or potassium.
Another class of polymers in accordance with the present invention comprises those of formula III:
20429'~~
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H40)tH wherein t is from 1-50, and wherein the monomer units may be in random order.
Each B1 is independently selected from -CH20H, -OH or -H.
Another class of polymers in accordance with the present invention comprises those of formula II:
I10 9 ~ r v q P
(II) n wherein:
Q2 is a molecular entity of formula IIa:
~, 20429'9 1 2 ~ 3 15 I1 C02A x C02A C02A ~ R R
'2 R
R
R
z (IIa) ' wherein z and R1 6 are as defined for formula (I);
Al 4 are as defined for formula (I);
Q1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q1 in any direction, in any order, therewith possibly resulting in a branched polymer.
Preferably Q1 is trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol;
n and z are as defined above; v is 1; and (x + y + p + q + r):z is from 5:1 to 500:1; in which the monomer units may be in random order; and preferably either p and q are zero, or r is zero;
R7 and R8 represent -CH3 or -H;
R9 and R10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups, or ~~429'~9 (C2H40)tH, wherein t is from 1-50, and wherein the monomer units may be in random order. Preferably they are selected from -S03Na, -CO-O-C2H4, -OS03Na, -CO-NH-C(CH3)2-CH2-S03Na, -CO-NH2, -O-CO-CH3, -OH. In any particular sample of polymer material in which polymers of formulae I and II are in the form of a salt, usually some polymers will be full salts (A1-Ay4 all other than hydrogen), some will be full acids (A1-A4 all hydrogen) and some will be part-salts (one or more A1-A4 hydrogen and one or more other than hydrogen).
The salts of the polymers of formulae I and II may be formed with any organic or inorganic cation defined for A1-A4 and which is capable of forming a water-soluble salt with a low molecular weight carboxylic acid. Preferred are the alkali metal salts, especially of sodium or potassium.
Another class of polymers in accordance with the present invention comprises those of formula III:
20429'~~
H ' Q ~ CH2 C CH2 C Q H
I II
~a d (CH2)w ~ (CH2)w 11 It 11 R N --R N
11 ~ 1 b c n (III) wherein Q3 is derived from a monomeric unit IIIa comprising:
11*
N+ B2 11*
~11 R
(IIIa) Q4 is derived from the molecular entity IIIb:
2~D42~'~9 ..H- C Q CH2 C CH2 C
.5 f '2 R (CH2)w ~ (CH2)w ~+
R3 R12 - - R1 ~ N
i~
14 12 3 12 ~ 1 R R B ~ R R
a g h (IIIb) and Q5 is derived from a monomeric unit IIIc:
N+ B4 'll R
(IIIc) R1-R6 are defined as in formula I;
' ' (a + b + c): Q4 is from 5:1 to 500:1, in which the monomer units may be in random order, a, b, c, d, e, f, g, h may be an integer or zero, n is at least 1;
B1, B2, B3, B4 are organic or inorganic anions;
w is zero to 4;
R11 is independently selected from hydrogen or C1-C4 alkyl; and R12 is independently selected from C5 to C24 alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl.
The anions represented by B1, B2, B3, B4 are exemplified by the halide ions, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, sulphide, cyanate, acetate and the other common inorganic and organic ions. Preferred anions are chloride and methosulphate.
Another class of polymers in accordance with the present invention comprise those of formula IV
2~14297~
I II
~a d (CH2)w ~ (CH2)w 11 It 11 R N --R N
11 ~ 1 b c n (III) wherein Q3 is derived from a monomeric unit IIIa comprising:
11*
N+ B2 11*
~11 R
(IIIa) Q4 is derived from the molecular entity IIIb:
2~D42~'~9 ..H- C Q CH2 C CH2 C
.5 f '2 R (CH2)w ~ (CH2)w ~+
R3 R12 - - R1 ~ N
i~
14 12 3 12 ~ 1 R R B ~ R R
a g h (IIIb) and Q5 is derived from a monomeric unit IIIc:
N+ B4 'll R
(IIIc) R1-R6 are defined as in formula I;
' ' (a + b + c): Q4 is from 5:1 to 500:1, in which the monomer units may be in random order, a, b, c, d, e, f, g, h may be an integer or zero, n is at least 1;
B1, B2, B3, B4 are organic or inorganic anions;
w is zero to 4;
R11 is independently selected from hydrogen or C1-C4 alkyl; and R12 is independently selected from C5 to C24 alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl.
The anions represented by B1, B2, B3, B4 are exemplified by the halide ions, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, sulphide, cyanate, acetate and the other common inorganic and organic ions. Preferred anions are chloride and methosulphate.
Another class of polymers in accordance with the present invention comprise those of formula IV
2~14297~
H CH2 C CH c H
j R R
R R
R
IV
where R1-R6 are defined as in formula I, z is 1 and j:z is from 5:1 to 500:1, in which the monomer units may be in random order, and n is at least 1;
R13 represents -CH2-, -C2H4-, -C3H6- or is absent.
R14 represents from 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide groups, or is absent.
R15 represents -OH or hydrogen.
Other preferred polymers are hydrophobically modified polysaccharides. Possible sugar units for use in those polymers include glucosides and fructosides for example maltoses, fructoses, lactoses, glucoses and galactoses.
Also mixtures of sugar groups may be used. The sugar groups may be connected to each other via any suitable linkage, although 1-4 linkages and/or 1-6 linkages are 2~429'~~
j R R
R R
R
IV
where R1-R6 are defined as in formula I, z is 1 and j:z is from 5:1 to 500:1, in which the monomer units may be in random order, and n is at least 1;
R13 represents -CH2-, -C2H4-, -C3H6- or is absent.
R14 represents from 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide groups, or is absent.
R15 represents -OH or hydrogen.
Other preferred polymers are hydrophobically modified polysaccharides. Possible sugar units for use in those polymers include glucosides and fructosides for example maltoses, fructoses, lactoses, glucoses and galactoses.
Also mixtures of sugar groups may be used. The sugar groups may be connected to each other via any suitable linkage, although 1-4 linkages and/or 1-6 linkages are 2~429'~~
preferred. The polysaccharides are preferably predominantly linear, but also branched polymers may be used. An example of a preferred polysaccharide has the following formula:
H O
7' CH ----CH CH O
R CH CH CH O
~7 17 ~ 7' R R v CH CH R
7~
R CH CH
7' ~y I
R i ~w Wherein:
Each R7 is R7 or -R1-R2-R3-R4;
R7 is independently selected from -OH, -NH-CO-CH3, -S03A1, -OS03A1, -NHS03A1, -COOA1; R7 is preferably -OH
n is the total number of -R1-R2-R3-R4 groups per molecule;
n is at least 1;
~p429'~9 m is the total number of R7 and R7 groups that are not _R1-R2-R3-R4 i the ratio m:n is from 12:1 to 3,000:1, preferably from 18:1 to 750:1; wherein the monomer units may be in random order. v and w are determined by the molecular weight of the polymer.
It is believed that on the basis of this formula, the skilled person will be able to derive similar formulas for other polysaccharide polymers for use in compositions of the invention.
R1 is as defined above for formula I, or can be -NHCO;
-OCH2CONH; or -O-CH2-CO-O-;
R2 4 are as defined for formula I;
A1 is as defined for formula I.
Other preferred polymers are of the formula:
2fl4~9'~9 s s CH
~ y ~ ~
I 8 i 9 1 5 I
R i; ~ R R1 R
~
I
OH ~ OS ~ R2 I
~
f x y i t (,VI z ) n Wherein:
z z and is n from are 4:1 as defined for formula I;
(x+y):
to preferably 1,000:1, preferably from 6:1 to 250:1;
y being value from of zero x;
up to a maximum equal to the wherein rder.
the monomer units may be in random o are as defined for formula I;
R$
and represent or are absent;
S OOA1, is selected fro -CO(CH2i2CO0A1, -CO( H) C
i i -COCH2C(OH) (CODA
)CH
COOA
, -COCH
COOA
, 2 CH(CH
2 )COOA1 -CO(CH(OH))2COOA1, -COCH2CH(OH)COOA1, -COCH
and -COCH2C(=CH2)COOA1;
is as defined for formula I;
Other preferred polymers as of the formula:
20429'9 D A B -~-- D
i I
VII ~ ~n Wherein:
D is -H or -OH; n is at least 1;
(Q1 (Q2 ~
A is O----CH-----CH or O CH H
1 ~ 1 ~ 2 CODA COOA COOA CO
OR
Wherein:
Each A2 is A1 or R10~
Q1:Q2 is from 4:1 to 1,000:1, preferably from 6:1 to 250:1;
R10 represents a C5-24 alk(en)yl group;
B is ---~O CO-~tll-~CO
R11 represents -CH2-, -C2H4-, C3H6-, or an aryl link said aryl link optionally being substituted with one or more -COOA1 groups, or a benzophenone link;
A1 is as defined in formula I.
For the polymers of formula I, II and IV and their salts, it is preferred to have a weigth average molecular weight in the region of from 500 to 500,000, preferably from 1000 to 200,000 more preferably from 1500 to 50,000, even more preferably from 3,000 to 6,000 when measured by GPC using polyacrylate standards. For the purposes of this definition, the molecular weights of the standards are measured by the absolute intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.
It is difficult to determine accurately the molecular weight distribution of polymers of Formula III, because of ( the highly cationic nature of these polymers and subsequently adsorption on the GPC columns. Instead, a measure of molecular weight can be made by measuring a standard viscosity (S.V.), determined at 15.0% solids, 23°C in a 1.0 molar sodium chloride solution using a Brookfield Synchro-lectric(R) viscometer, Model LVT with an LCP adaptor, at a speed of 60 RPM. It is preferred to have a polymer with an S.V. from 1 to 100 mPas, more preferably from 2-50 mPas, most preferably 3-25 mPas.
Polymers according to formulas V-VII preferably have a molecular weight of 500-250,000, more preferably from 2,000 to 50,000, even more preferably from 3,000 to 6,000.
Generally, the deflocculating polymer will be used at from 0.01% to 5.0% by weight in the composition, preferably from 0.02 to 2.0%, most preferably from 0.03 to 1%.
Compositions of the present invention preferably comprise from 1 to 80%, by weight of fabric-softening materials, more preferably from 2 to 70o by weight, most preferably from 5 to 50°s by weight of the composition.
The fabric softening materials may be selected from cationic, nonionic, amphoteric or anionic fabric softening material.
Suitable amphoteric fabric-conditioning materials for use in a composition according to the invention are fabric-substantive amphoteric materials forming a particulate dispersion at a concentration of less than 1 g/1 at at least one temperture between 0 and 100°C, preferably at least one temperature between 10 and 90°C, more preferably between 20 and 80°C. For the purpose of this invention a fabric-substantive amphoteric material is preferably an amphoteric or zwitterionic tertiary or quaternary ammonium compound having either one single long hydrocarbyl side chain or two long hydrocarbyl chains.
From these compounds the use of amphoteric or zwitterionic ammonium compounds having two long hydrocarbyl chains is particularly preferred for many reasons including costs, ease of processing and better stability and performance.
Suitable amphoteric materials are for example disclosed in EP 236 213.
In this specification the expression hydrocarbyl chain refers to linear or branched alkyl or alkenyl chains optionally substituted or interrupted by functional groups such as -OH, -O-, -CONH-, -COO-, etc.
Preferably the amphoteric fabric-substantive materials are water insoluble and have a solubility in water at pH 2.5 at 20°C of less than 10 g/1. The HLB of the amphoteric fabric-substantive material is preferably less than 10Ø
H O
7' CH ----CH CH O
R CH CH CH O
~7 17 ~ 7' R R v CH CH R
7~
R CH CH
7' ~y I
R i ~w Wherein:
Each R7 is R7 or -R1-R2-R3-R4;
R7 is independently selected from -OH, -NH-CO-CH3, -S03A1, -OS03A1, -NHS03A1, -COOA1; R7 is preferably -OH
n is the total number of -R1-R2-R3-R4 groups per molecule;
n is at least 1;
~p429'~9 m is the total number of R7 and R7 groups that are not _R1-R2-R3-R4 i the ratio m:n is from 12:1 to 3,000:1, preferably from 18:1 to 750:1; wherein the monomer units may be in random order. v and w are determined by the molecular weight of the polymer.
It is believed that on the basis of this formula, the skilled person will be able to derive similar formulas for other polysaccharide polymers for use in compositions of the invention.
R1 is as defined above for formula I, or can be -NHCO;
-OCH2CONH; or -O-CH2-CO-O-;
R2 4 are as defined for formula I;
A1 is as defined for formula I.
Other preferred polymers are of the formula:
2fl4~9'~9 s s CH
~ y ~ ~
I 8 i 9 1 5 I
R i; ~ R R1 R
~
I
OH ~ OS ~ R2 I
~
f x y i t (,VI z ) n Wherein:
z z and is n from are 4:1 as defined for formula I;
(x+y):
to preferably 1,000:1, preferably from 6:1 to 250:1;
y being value from of zero x;
up to a maximum equal to the wherein rder.
the monomer units may be in random o are as defined for formula I;
R$
and represent or are absent;
S OOA1, is selected fro -CO(CH2i2CO0A1, -CO( H) C
i i -COCH2C(OH) (CODA
)CH
COOA
, -COCH
COOA
, 2 CH(CH
2 )COOA1 -CO(CH(OH))2COOA1, -COCH2CH(OH)COOA1, -COCH
and -COCH2C(=CH2)COOA1;
is as defined for formula I;
Other preferred polymers as of the formula:
20429'9 D A B -~-- D
i I
VII ~ ~n Wherein:
D is -H or -OH; n is at least 1;
(Q1 (Q2 ~
A is O----CH-----CH or O CH H
1 ~ 1 ~ 2 CODA COOA COOA CO
OR
Wherein:
Each A2 is A1 or R10~
Q1:Q2 is from 4:1 to 1,000:1, preferably from 6:1 to 250:1;
R10 represents a C5-24 alk(en)yl group;
B is ---~O CO-~tll-~CO
R11 represents -CH2-, -C2H4-, C3H6-, or an aryl link said aryl link optionally being substituted with one or more -COOA1 groups, or a benzophenone link;
A1 is as defined in formula I.
For the polymers of formula I, II and IV and their salts, it is preferred to have a weigth average molecular weight in the region of from 500 to 500,000, preferably from 1000 to 200,000 more preferably from 1500 to 50,000, even more preferably from 3,000 to 6,000 when measured by GPC using polyacrylate standards. For the purposes of this definition, the molecular weights of the standards are measured by the absolute intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.
It is difficult to determine accurately the molecular weight distribution of polymers of Formula III, because of ( the highly cationic nature of these polymers and subsequently adsorption on the GPC columns. Instead, a measure of molecular weight can be made by measuring a standard viscosity (S.V.), determined at 15.0% solids, 23°C in a 1.0 molar sodium chloride solution using a Brookfield Synchro-lectric(R) viscometer, Model LVT with an LCP adaptor, at a speed of 60 RPM. It is preferred to have a polymer with an S.V. from 1 to 100 mPas, more preferably from 2-50 mPas, most preferably 3-25 mPas.
Polymers according to formulas V-VII preferably have a molecular weight of 500-250,000, more preferably from 2,000 to 50,000, even more preferably from 3,000 to 6,000.
Generally, the deflocculating polymer will be used at from 0.01% to 5.0% by weight in the composition, preferably from 0.02 to 2.0%, most preferably from 0.03 to 1%.
Compositions of the present invention preferably comprise from 1 to 80%, by weight of fabric-softening materials, more preferably from 2 to 70o by weight, most preferably from 5 to 50°s by weight of the composition.
The fabric softening materials may be selected from cationic, nonionic, amphoteric or anionic fabric softening material.
Suitable amphoteric fabric-conditioning materials for use in a composition according to the invention are fabric-substantive amphoteric materials forming a particulate dispersion at a concentration of less than 1 g/1 at at least one temperture between 0 and 100°C, preferably at least one temperature between 10 and 90°C, more preferably between 20 and 80°C. For the purpose of this invention a fabric-substantive amphoteric material is preferably an amphoteric or zwitterionic tertiary or quaternary ammonium compound having either one single long hydrocarbyl side chain or two long hydrocarbyl chains.
From these compounds the use of amphoteric or zwitterionic ammonium compounds having two long hydrocarbyl chains is particularly preferred for many reasons including costs, ease of processing and better stability and performance.
Suitable amphoteric materials are for example disclosed in EP 236 213.
In this specification the expression hydrocarbyl chain refers to linear or branched alkyl or alkenyl chains optionally substituted or interrupted by functional groups such as -OH, -O-, -CONH-, -COO-, etc.
Preferably the amphoteric fabric-substantive materials are water insoluble and have a solubility in water at pH 2.5 at 20°C of less than 10 g/1. The HLB of the amphoteric fabric-substantive material is preferably less than 10Ø
Suitable cationic fabric-softener materials for use in a composition according to the present invention are cationic materials which are water-insoluble in that the material has a solubility in water at pH 2.5 and 20°C of less than 10 g/1. Highly preferred materials are cationic quaternary ammonium salts having two C12-C24 hydrocarbyl chains.
Well-known species of substantially water-insoluble quaternary ammonium compounds have the formula:
Rl ~ R3 +
N X
wherein R1 and R2 represent hydrocarbyl groups from about 12 to about 24 carbon atoms; R3 and R4 represent hydrocarbyl groups containing from 1 to about 4 carbon atoms; and X is an anion, preferably selected from halide, methosulphate and ethyl sulphate radicals.
Representative examples of these quaternary softeners include ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulphate; dihexadecyl diethyl ammonium chloride; di(coconut) dimethyl ammonium chloride.
Ditallow dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, di(coconut) dimethyl ammonium chloride and di(coconut) dimethyl ammonium methosulphate are preferred.
Well-known species of substantially water-insoluble quaternary ammonium compounds have the formula:
Rl ~ R3 +
N X
wherein R1 and R2 represent hydrocarbyl groups from about 12 to about 24 carbon atoms; R3 and R4 represent hydrocarbyl groups containing from 1 to about 4 carbon atoms; and X is an anion, preferably selected from halide, methosulphate and ethyl sulphate radicals.
Representative examples of these quaternary softeners include ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulphate; dihexadecyl diethyl ammonium chloride; di(coconut) dimethyl ammonium chloride.
Ditallow dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, di(coconut) dimethyl ammonium chloride and di(coconut) dimethyl ammonium methosulphate are preferred.
Suitable materials also include dialkyl ethoxyl methyl ammonium methosulphate based on soft fatty acid, dialkyl ethoxyl methyl ammonium methosulphate based on hard fatty acid, and a material in which R3 and R4 represent methyl, R1 is C13-15' R2 is CH2CH20COR, where R
is stearyl, and X is methosulphate. Ditallow dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, di(coconut alkyl) dimethyl ammonium chloride and di(coconut alkyl) dimethyl ammonium methosulfate are preferred.
Other preferred cationic compounds include those materials as disclosed in EP 239 910 (P&G), Other preferred materials are the materials of formula O
N+
O CH3S04_ R5 being tallow, which is available from Stepan under the trademark stepantex vRH 90, and ~~,N
20429'~~
is stearyl, and X is methosulphate. Ditallow dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, di(coconut alkyl) dimethyl ammonium chloride and di(coconut alkyl) dimethyl ammonium methosulfate are preferred.
Other preferred cationic compounds include those materials as disclosed in EP 239 910 (P&G), Other preferred materials are the materials of formula O
N+
O CH3S04_ R5 being tallow, which is available from Stepan under the trademark stepantex vRH 90, and ~~,N
20429'~~
R6COOCH2~
CH-CH2N+R8R9R10X_ where R8, R9 and R10 are each alkyl or hydroxyalkyl groups containing from 1 to 4 carbon atoms, or a benzyl group.
R6 and R7 are each an alkyl or alkenyl chain containing from 11 to 23 carbon atoms, and X is a water-soluble anion. These materials and their method of preparation are described in US 4 137 180 (LEVER BROTHERS).
Another class of preferred water-insoluble cationic materials are the hydrocarbylimidazolinium salts believed to have the formula:
N +N . C2H4 N - C --~tli A-wherein R13 is a hydrocarbyl group containing from 1 to 4, preferably 1 or 2 carbon atoms, R11 is a hydrocarbyl group containing from 8 to 25 carbon atoms, R14 is an hydrocarbyl group containing from 8 to 25 carbon atoms and R12 is hydrogen or an hydrocarbyl containing from 1 to 4 carbon atoms and A is an anion, preferably a halide, methosulphate or ethosulphate.
CH-CH2N+R8R9R10X_ where R8, R9 and R10 are each alkyl or hydroxyalkyl groups containing from 1 to 4 carbon atoms, or a benzyl group.
R6 and R7 are each an alkyl or alkenyl chain containing from 11 to 23 carbon atoms, and X is a water-soluble anion. These materials and their method of preparation are described in US 4 137 180 (LEVER BROTHERS).
Another class of preferred water-insoluble cationic materials are the hydrocarbylimidazolinium salts believed to have the formula:
N +N . C2H4 N - C --~tli A-wherein R13 is a hydrocarbyl group containing from 1 to 4, preferably 1 or 2 carbon atoms, R11 is a hydrocarbyl group containing from 8 to 25 carbon atoms, R14 is an hydrocarbyl group containing from 8 to 25 carbon atoms and R12 is hydrogen or an hydrocarbyl containing from 1 to 4 carbon atoms and A is an anion, preferably a halide, methosulphate or ethosulphate.
Preferred imidazolinium salts include 1-methyl-1-(tallowylamido-) ethyl -2-tallowyl- 4,5-dihydro imidazolinium methosulphate and 1-methyl-1-(palmitoylamido) ethyl -2-octadecyl-4,5- dihydro-imidazolinium chloride. Other useful imidazolinium materials are 2-heptadecul-1-methyl-1- (2-stearylamido)-ethyl-imidazolinium chloride and 2-lauryl-1-hydroxyethyl -1-oleyl-imidazolinium chloride. Also suitable herein are the imidazolinium fabric-softening components of US patent No. 4 127 489.
Representative commercially available materials of the above classes are the quaternary ammonium compounds *Arquad 2HT (Ex Ax2o) *Noramium M2SH (ex cECA) ; Aliquat-2HT
(Trade Mark of General Mills Inc), Stepantex Q185 (ex Stepan); Stepantex VP85 (ex Stepan); Stepantex VRH90 (ex Stepan); *Synprolam FS (ex ICI) and the imidazolinium compounds Varisoft 475 (Trade Mark of Sherex Company, Columbus Ohio) and Rewoquat W7500 (Trade Mark of REWO).
The compositions according to the invention may also - contain, possibly in addition to the above mentioned softening agents, one or more amine softening materials.
The term "amine" as used herein can refer to (i) amines of formula:
R16 N ~ (I) wherein R15, R16 and R17 are defined as below;
*denotes trade mark (ii) amines of formula:
Ri8 R2 R19 N ( CH2 ) n N 1 (II) _.
wherein R18, Ri9, R20 and R21, m and d are defined as below.
(iii) imidazolines of formula:
O
N N C2H4 N-C-Ril wherein R11, R12 and R14 are defined as above.
(iv) condensation products formed from the reaction of fatty acids with a polyamine selected from the group consisting of hydroxy alkylalkylenediamines and dialkylenetriamines and mixtures thereof. Suitable materials are disclosed in European Patent Application 199 382 (Procter and Gamble).
When the amine is of the formula I above, R15 is a C6 to C24, hydrocarbyl group, R16 is a C1 to C24 hydrocarbyl group and R17 is a C1 to C1~ hydrocarbyl group. Suitable amines include those materials from which the quaternary ammonium compounds disclosed above are derived, in which R15 is R1, R16 is R2 and R17 is R3. Preferably, the amine is such that both R15 and R16 are C6-C20 alkyl with C16-Ci$ being most preferred and with R17 as C1-3 alkyl, or R15 is an alkyl or alkenyl group with at least 22 carbon atoms and R16 and R12 are C1-3 alkyl. Preferably these amines are protonated with hydrochloric acid, orthophosphoric acid (OPA), C1-5 carboxylic acids or any other similar acids, for use in the fabric-conditioning compositions of the invention.
When the amine is of formula II above, Ri$ is a C6 to C24 hydrocarbyl group, R19 is an alkoxylated group of formula -(CH2CH20)yH, where y is within the range from 0 to 6, R20 is an alkoxylated group of formula -(CH2CH20)ZH
where z is within the range from 0 to 6 and m is an integer within the range from 0 to 6, and is preferably 3.
When m is 0, it is preferred that Ri8 is a Cl6 to C22 alkyl and that the sum total of z and y is within the range from 1 to 6, more preferably 1 to 3. When m is 1, it is preferred that R1$ is a C16 to C22 alkyl and that the sum total of x and y and z is within the range from 3 to 10.
Representative commercially available materials of this class include *Ethomeen (ex Armour) and *Ethoduomeen (ex Armour).
Preferably the amines of type (ii) or (iii) are also protonated for use in the fabric-conditioning compositions of the invention.
When the amine is of type (iv) given above, a particularly preferred material is:
* denotes trade mark ~s~;r.
Representative commercially available materials of the above classes are the quaternary ammonium compounds *Arquad 2HT (Ex Ax2o) *Noramium M2SH (ex cECA) ; Aliquat-2HT
(Trade Mark of General Mills Inc), Stepantex Q185 (ex Stepan); Stepantex VP85 (ex Stepan); Stepantex VRH90 (ex Stepan); *Synprolam FS (ex ICI) and the imidazolinium compounds Varisoft 475 (Trade Mark of Sherex Company, Columbus Ohio) and Rewoquat W7500 (Trade Mark of REWO).
The compositions according to the invention may also - contain, possibly in addition to the above mentioned softening agents, one or more amine softening materials.
The term "amine" as used herein can refer to (i) amines of formula:
R16 N ~ (I) wherein R15, R16 and R17 are defined as below;
*denotes trade mark (ii) amines of formula:
Ri8 R2 R19 N ( CH2 ) n N 1 (II) _.
wherein R18, Ri9, R20 and R21, m and d are defined as below.
(iii) imidazolines of formula:
O
N N C2H4 N-C-Ril wherein R11, R12 and R14 are defined as above.
(iv) condensation products formed from the reaction of fatty acids with a polyamine selected from the group consisting of hydroxy alkylalkylenediamines and dialkylenetriamines and mixtures thereof. Suitable materials are disclosed in European Patent Application 199 382 (Procter and Gamble).
When the amine is of the formula I above, R15 is a C6 to C24, hydrocarbyl group, R16 is a C1 to C24 hydrocarbyl group and R17 is a C1 to C1~ hydrocarbyl group. Suitable amines include those materials from which the quaternary ammonium compounds disclosed above are derived, in which R15 is R1, R16 is R2 and R17 is R3. Preferably, the amine is such that both R15 and R16 are C6-C20 alkyl with C16-Ci$ being most preferred and with R17 as C1-3 alkyl, or R15 is an alkyl or alkenyl group with at least 22 carbon atoms and R16 and R12 are C1-3 alkyl. Preferably these amines are protonated with hydrochloric acid, orthophosphoric acid (OPA), C1-5 carboxylic acids or any other similar acids, for use in the fabric-conditioning compositions of the invention.
When the amine is of formula II above, Ri$ is a C6 to C24 hydrocarbyl group, R19 is an alkoxylated group of formula -(CH2CH20)yH, where y is within the range from 0 to 6, R20 is an alkoxylated group of formula -(CH2CH20)ZH
where z is within the range from 0 to 6 and m is an integer within the range from 0 to 6, and is preferably 3.
When m is 0, it is preferred that Ri8 is a Cl6 to C22 alkyl and that the sum total of z and y is within the range from 1 to 6, more preferably 1 to 3. When m is 1, it is preferred that R1$ is a C16 to C22 alkyl and that the sum total of x and y and z is within the range from 3 to 10.
Representative commercially available materials of this class include *Ethomeen (ex Armour) and *Ethoduomeen (ex Armour).
Preferably the amines of type (ii) or (iii) are also protonated for use in the fabric-conditioning compositions of the invention.
When the amine is of type (iv) given above, a particularly preferred material is:
* denotes trade mark ~s~;r.
N~R23 N
O O
R24 C__R24 where R22 and R23 are divalent alkenyl chains having from 1 to 3 carbon atoms, and R24 is an acyclic aliphatic hydrocarbon chain having from 15 to 21 carbon atoms. A
commercially available material of this class is~Ceranine HC39 (ex Sandoz).
The compositions also contain an emulsion component such as hydrocarbons, perfumes, natural fats and oils, fatty acids and/or esters thereof, fatty alcohols and silicones.
Highly preferred hydrocarbons are paraffins and olefines but alkynes and halogenated paraffins such as myristyl chloride are not excluded. Materials known generally as paraffin oil, soft paraffin wax, petroleum and petroleum jelly are especially suitable. Examples of specific materials are tetradecane, hexadecane, octadecane and octodecene.
Preferred perfumes are *Portia 40 ex IFF Ltd, *LFU 384 ex Quest and *Coccoon SN3000 ex Givaudan.
Examples of natural oils are coconut, corn, olive and sunflower as well as naturally occuring waxy solids such as lanolin. Examples of animal fats are butter, tallow and sardine.
* denotes trade mark Preferred fatty acids and esters are lauric, myristic, palmitic and stearic acids, methyl laurate, ethyl myristate, ethyl stearate, methyl palmitate and ethylene glycol monostearate. Examples of fatty alcohols include decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol and lauryl and palmityl alcohols. Examples of estols include isopropylmyristate.
Examples of silicones and aminosilicones suitable for use in the invention are disclosed in DE 2 631 419 (Procter and Gamble/Dumbrell) and those supplied commercially as *Vp 1487E ex Wacker and the *Magnasoft range ex Union Carbide.
We have found that deposition of the emulsion component is improved when the particles are positively charged. When a cationic fabric softener is used it is convenient to make the fabric treatment composition in a one-stage process where the fabric softener acts as emulsifier. When this is not possible it may be necessary to make the emulsion separately in which case a separate emulsifier may be required. Suitable emulsifiers are single or di-alkyl ammonium salts, the esters of sorbitan, glycerol or polyethylene glycol and ethoxylated alcohols.
The levels of emulsion component in the composition is typically from 1 to 80%, by weight preferably from 2 to 70% and most preferably from 5 to 50%. The compositions according to the invention may optionally contain electrolyte. The level of dissolved electrolyte is typically from 0% to 0.2%, preferably 0.05 to 0.2%.
Compositions according to the present invention preferably have a pH of less than 6.0, more preferred less than 5.0, especially from 1.5 to 4.5, most preferred from 2.0 to 4Ø
* denotes trade mark ~~4~~79 The compositions can also contain one or more optional ingredients selected from non-aqueous solvents such as C1-C4 alkanols and polyhydric alcohols, pH-buffering agents such as weak acids, e.g. phosphoric, benzoic or citric acids, re-wetting agents, viscosity modifiers, aluminium chlorohydrate, antigelling agents, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, anti-shrinking agents, antioxidants, anti-corrosion agnets, preservatives such as Bronopol (Trade Mark), a commercially available form of 2-bromo-2-nitropropane-1,3-diol, to preserve the fabric treatment composition, dyes, bleaches and bleach precursors, drape-imparting agents, antistatic agents and ironing aids.
These optional ingredients, if added, are each present at levels up to 5~ by weight of the composition.
The invention will be further illustrated by means of the following examples.
Examples In Examples I-II the following polymers were used.
Each polymer was obtained from National Starch as an aqueous solution of from 30-60~ by weight solids level.
All percentages for the polymer refer to 100 active polymers.
Basic Structures of Polymers: General Formula II
wherein R8 = H, r = O, v = 1 wherein Q2; x = y = O, R1 = COO, R3 absent, R5 = H, R6 = CH3.
Polymer R10 q R7 R9 p R4 SV(cps) Ref 435/173 COOC2H40H 25 - - O C12H25 3~5 435/174 COOC2H40H 25 - - O C12H25 4~3 Basic Structure of Polymers~ General Formula III
wherein b = c = O, R4 - -C12H25' R6 - CH3, d = 1. In IIIa, R11 - 11, R11* = CH , B2 = C1. In IIIb, a = 1, f = g = h = i = O, R1 - COO, R3 is absent, R5 - H, B3 - C1.
Polymer a d R4 R6 SV(cps) Ref 433/20 10 1 C18H37 CH3 5.5 442/25 10 1 C12H25 CH3 4.6 442/44 10 1 C12H25 CH3 6.3 Example 1 Fabric softening compositions were made by adding the deflocculating polymer under sturring, to a preheated (70°C) mixture of the emulsion component and fabric softening material in aqueous dispersion. The fabric softening material was Arquad 2HT (a dimethyl ditallow ammonium chloride) ex Atlas. The emulsion component was a combination of *Sirius M85 a mineral oil, ex Dalton & Co., *Silkolene 910 ex Dalton & Co., a petroleum jelly and optionally lanolin.
The following compositions were obtained:
* denotes trade mark v 20429'9 Component A B C D E F
by weight Arquad 2HT 4.25 4.25 4.25 4.25 9 9 Sirius M85 10.70 10.70 10.70 10.70 24 24 Silkolene 910 5.30 5.30 5.30 5.30 12 12 Lanolin 2.0 2.0 3.0 3.0 - -Polymer 433/20- 0.13 - 0.09 - 0.1 Water - - - - balance - - - - - - - - -- - - -In all compositions B, D and F a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer. In compositions E and F a reduction in viscosity from 0.7 Pas to 0.3 Pas was measured at a shear rate of 21s 1.
Example II
Fabric softening compositions were made according to the method of Example I. The fabric softening material was either Arquad 2HT as used in Example I or Arquad 2T ex Atlas. In Arquad 2T the tallow is not hardened.
2fl429'~9 Component A B C D
by weight Arquad 2HT 7 7 - -Arquad 2T - - 7 7 Sirius M85 18.7 18.7 18.7 18.7 Silkolene 910 9.3 9.3 9.3 9.3 Polymer 435/174 - 0.27 - 0.3 Water - - - - - balance - - - - - - --Viscosity mPas 2952 338 729 182 110s 1 21s 1 14721 709 3458 404 Example III
Fabric softening compositions were made according to the method of Example 1 excepting that the electrolyte (when present) was added along with the polymer.
Component A B C D E
Arquad 2HT 7 7 7 7 7 Sirius M85 18.7 18.7 18.7 18.7 18.7 Silkolene 910 9.3 9.3 9.3 9.3 9.3 Polymer 435/173 0.3 0.3 0.3 0.3 0.3 NaCl - 0.05 0.1 0.15 0.2 Water - - - - - - - balance - - - - - - -- -Viscosity mPas 110s 1 210 65 125 160 295 21s 1 658 473 431 616 879 From comparison with Example IIA it can be seen that a reduction in viscosity from 14.7 Pas o 0.6 occurs t Pas ~0429'~9 on addition of the deflocculating polymer. The addition of electrolyte (Example IIIB) then reduces this viscosity further. Continued addition of electrolyte however leads eventually to a viscosity increase.
Example IV
A typical formulation for use as a rinse conditioner comprises:
by weight Arquad 2HT 7 Sirius M85 18.7 Silkolene 910 9.3 Lanolin 0.5 Polymer 442/25 0.04 Water to balance This composition has a viscosity at 21s 1 of 0.44 Pas.
O O
R24 C__R24 where R22 and R23 are divalent alkenyl chains having from 1 to 3 carbon atoms, and R24 is an acyclic aliphatic hydrocarbon chain having from 15 to 21 carbon atoms. A
commercially available material of this class is~Ceranine HC39 (ex Sandoz).
The compositions also contain an emulsion component such as hydrocarbons, perfumes, natural fats and oils, fatty acids and/or esters thereof, fatty alcohols and silicones.
Highly preferred hydrocarbons are paraffins and olefines but alkynes and halogenated paraffins such as myristyl chloride are not excluded. Materials known generally as paraffin oil, soft paraffin wax, petroleum and petroleum jelly are especially suitable. Examples of specific materials are tetradecane, hexadecane, octadecane and octodecene.
Preferred perfumes are *Portia 40 ex IFF Ltd, *LFU 384 ex Quest and *Coccoon SN3000 ex Givaudan.
Examples of natural oils are coconut, corn, olive and sunflower as well as naturally occuring waxy solids such as lanolin. Examples of animal fats are butter, tallow and sardine.
* denotes trade mark Preferred fatty acids and esters are lauric, myristic, palmitic and stearic acids, methyl laurate, ethyl myristate, ethyl stearate, methyl palmitate and ethylene glycol monostearate. Examples of fatty alcohols include decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol and lauryl and palmityl alcohols. Examples of estols include isopropylmyristate.
Examples of silicones and aminosilicones suitable for use in the invention are disclosed in DE 2 631 419 (Procter and Gamble/Dumbrell) and those supplied commercially as *Vp 1487E ex Wacker and the *Magnasoft range ex Union Carbide.
We have found that deposition of the emulsion component is improved when the particles are positively charged. When a cationic fabric softener is used it is convenient to make the fabric treatment composition in a one-stage process where the fabric softener acts as emulsifier. When this is not possible it may be necessary to make the emulsion separately in which case a separate emulsifier may be required. Suitable emulsifiers are single or di-alkyl ammonium salts, the esters of sorbitan, glycerol or polyethylene glycol and ethoxylated alcohols.
The levels of emulsion component in the composition is typically from 1 to 80%, by weight preferably from 2 to 70% and most preferably from 5 to 50%. The compositions according to the invention may optionally contain electrolyte. The level of dissolved electrolyte is typically from 0% to 0.2%, preferably 0.05 to 0.2%.
Compositions according to the present invention preferably have a pH of less than 6.0, more preferred less than 5.0, especially from 1.5 to 4.5, most preferred from 2.0 to 4Ø
* denotes trade mark ~~4~~79 The compositions can also contain one or more optional ingredients selected from non-aqueous solvents such as C1-C4 alkanols and polyhydric alcohols, pH-buffering agents such as weak acids, e.g. phosphoric, benzoic or citric acids, re-wetting agents, viscosity modifiers, aluminium chlorohydrate, antigelling agents, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, anti-shrinking agents, antioxidants, anti-corrosion agnets, preservatives such as Bronopol (Trade Mark), a commercially available form of 2-bromo-2-nitropropane-1,3-diol, to preserve the fabric treatment composition, dyes, bleaches and bleach precursors, drape-imparting agents, antistatic agents and ironing aids.
These optional ingredients, if added, are each present at levels up to 5~ by weight of the composition.
The invention will be further illustrated by means of the following examples.
Examples In Examples I-II the following polymers were used.
Each polymer was obtained from National Starch as an aqueous solution of from 30-60~ by weight solids level.
All percentages for the polymer refer to 100 active polymers.
Basic Structures of Polymers: General Formula II
wherein R8 = H, r = O, v = 1 wherein Q2; x = y = O, R1 = COO, R3 absent, R5 = H, R6 = CH3.
Polymer R10 q R7 R9 p R4 SV(cps) Ref 435/173 COOC2H40H 25 - - O C12H25 3~5 435/174 COOC2H40H 25 - - O C12H25 4~3 Basic Structure of Polymers~ General Formula III
wherein b = c = O, R4 - -C12H25' R6 - CH3, d = 1. In IIIa, R11 - 11, R11* = CH , B2 = C1. In IIIb, a = 1, f = g = h = i = O, R1 - COO, R3 is absent, R5 - H, B3 - C1.
Polymer a d R4 R6 SV(cps) Ref 433/20 10 1 C18H37 CH3 5.5 442/25 10 1 C12H25 CH3 4.6 442/44 10 1 C12H25 CH3 6.3 Example 1 Fabric softening compositions were made by adding the deflocculating polymer under sturring, to a preheated (70°C) mixture of the emulsion component and fabric softening material in aqueous dispersion. The fabric softening material was Arquad 2HT (a dimethyl ditallow ammonium chloride) ex Atlas. The emulsion component was a combination of *Sirius M85 a mineral oil, ex Dalton & Co., *Silkolene 910 ex Dalton & Co., a petroleum jelly and optionally lanolin.
The following compositions were obtained:
* denotes trade mark v 20429'9 Component A B C D E F
by weight Arquad 2HT 4.25 4.25 4.25 4.25 9 9 Sirius M85 10.70 10.70 10.70 10.70 24 24 Silkolene 910 5.30 5.30 5.30 5.30 12 12 Lanolin 2.0 2.0 3.0 3.0 - -Polymer 433/20- 0.13 - 0.09 - 0.1 Water - - - - balance - - - - - - - - -- - - -In all compositions B, D and F a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer. In compositions E and F a reduction in viscosity from 0.7 Pas to 0.3 Pas was measured at a shear rate of 21s 1.
Example II
Fabric softening compositions were made according to the method of Example I. The fabric softening material was either Arquad 2HT as used in Example I or Arquad 2T ex Atlas. In Arquad 2T the tallow is not hardened.
2fl429'~9 Component A B C D
by weight Arquad 2HT 7 7 - -Arquad 2T - - 7 7 Sirius M85 18.7 18.7 18.7 18.7 Silkolene 910 9.3 9.3 9.3 9.3 Polymer 435/174 - 0.27 - 0.3 Water - - - - - balance - - - - - - --Viscosity mPas 2952 338 729 182 110s 1 21s 1 14721 709 3458 404 Example III
Fabric softening compositions were made according to the method of Example 1 excepting that the electrolyte (when present) was added along with the polymer.
Component A B C D E
Arquad 2HT 7 7 7 7 7 Sirius M85 18.7 18.7 18.7 18.7 18.7 Silkolene 910 9.3 9.3 9.3 9.3 9.3 Polymer 435/173 0.3 0.3 0.3 0.3 0.3 NaCl - 0.05 0.1 0.15 0.2 Water - - - - - - - balance - - - - - - -- -Viscosity mPas 110s 1 210 65 125 160 295 21s 1 658 473 431 616 879 From comparison with Example IIA it can be seen that a reduction in viscosity from 14.7 Pas o 0.6 occurs t Pas ~0429'~9 on addition of the deflocculating polymer. The addition of electrolyte (Example IIIB) then reduces this viscosity further. Continued addition of electrolyte however leads eventually to a viscosity increase.
Example IV
A typical formulation for use as a rinse conditioner comprises:
by weight Arquad 2HT 7 Sirius M85 18.7 Silkolene 910 9.3 Lanolin 0.5 Polymer 442/25 0.04 Water to balance This composition has a viscosity at 21s 1 of 0.44 Pas.
Example V
Fabric softening compositions were made according to the method of Example I. The fabric softening material was Rewoquat W75 (a 1-methyl-1 (tallowylamido-) ethyl-2-tallowyl-4,5-dihydroimidazolinium methosulphate).
Component Composition A B C D E F
Rewoquat W75 16 16 16 16 16 16 Sirius M85 1 2 2 1 2 2 CaCl2 0.01 0.01 0.01 0.01 0.01 0.01 Polymer 442/44 - - - - 0.43 -Polymer 442/60 - - 0.36 0.5 - -Polymer 448/20 - - - - - 0.4 Water -----------balance-----------Viscositv mPas 21s 1 86 756 79 40 122 253 110s 1 45 122 43 26 49 121 In compositions C, D, E and F a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer. For example composition A compared to composition D or composition B
compared to compositions C, E or F.
20429'9 Example VI
Fabric softening compositions were made according to the method of Example I.
Component Compositions A B C D
Rewoquat W75 16 16 16 16 Sirius M85 3 3 3 3 CaCl2 0.01 0.01 0.01 0.01 Polymer 442/44 - 0.36 - -Polymer 442/60 - - 0.47 -Polymer 448/20 - - - 0.40 Water -------balance-------Viscositv mPas 21s 1 907 160 80 289 110s 1 282 60 37 125 In compositions B, C and D a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer (A).
2~4297g Example VII
Fabric softening compositions were made according to the method of Example I.
Component Composition A B C
Rewoquat W75 16 16 16 Steric Acid 2 2 2 CaCl2 0.025 0.025 0.025 Polymer 442/44 - 0.39 -Polymer 442/60 - - 0.36 Water ------balance------Viscosity mPas 21s 1 12$3 325 215 110s 1 475 129 101 In compositions B and C a significant reduction in viscosity was observed when compared to that of the corresponding compositions without polymer (A).
~Q,~29? 9 Example VIII
Fabric softening compositions were made according to the method of Example I.
Component Composition A B _C D
Rewoquat W75 15 15 15 15 Octadecane 12 12 12 12 Polymer 442/44 - p,g9 - -Polymer 442/60 - - 0.36 -Polymer 448/20 - - - 0.40 Water ------balance-------Viscositv mPas 21s 1 5853 1760 1614 1891 110s 1 1016 453 482 496 In compositions B, C and D a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer (A).
Fabric softening compositions were made according to the method of Example I. The fabric softening material was Rewoquat W75 (a 1-methyl-1 (tallowylamido-) ethyl-2-tallowyl-4,5-dihydroimidazolinium methosulphate).
Component Composition A B C D E F
Rewoquat W75 16 16 16 16 16 16 Sirius M85 1 2 2 1 2 2 CaCl2 0.01 0.01 0.01 0.01 0.01 0.01 Polymer 442/44 - - - - 0.43 -Polymer 442/60 - - 0.36 0.5 - -Polymer 448/20 - - - - - 0.4 Water -----------balance-----------Viscositv mPas 21s 1 86 756 79 40 122 253 110s 1 45 122 43 26 49 121 In compositions C, D, E and F a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer. For example composition A compared to composition D or composition B
compared to compositions C, E or F.
20429'9 Example VI
Fabric softening compositions were made according to the method of Example I.
Component Compositions A B C D
Rewoquat W75 16 16 16 16 Sirius M85 3 3 3 3 CaCl2 0.01 0.01 0.01 0.01 Polymer 442/44 - 0.36 - -Polymer 442/60 - - 0.47 -Polymer 448/20 - - - 0.40 Water -------balance-------Viscositv mPas 21s 1 907 160 80 289 110s 1 282 60 37 125 In compositions B, C and D a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer (A).
2~4297g Example VII
Fabric softening compositions were made according to the method of Example I.
Component Composition A B C
Rewoquat W75 16 16 16 Steric Acid 2 2 2 CaCl2 0.025 0.025 0.025 Polymer 442/44 - 0.39 -Polymer 442/60 - - 0.36 Water ------balance------Viscosity mPas 21s 1 12$3 325 215 110s 1 475 129 101 In compositions B and C a significant reduction in viscosity was observed when compared to that of the corresponding compositions without polymer (A).
~Q,~29? 9 Example VIII
Fabric softening compositions were made according to the method of Example I.
Component Composition A B _C D
Rewoquat W75 15 15 15 15 Octadecane 12 12 12 12 Polymer 442/44 - p,g9 - -Polymer 442/60 - - 0.36 -Polymer 448/20 - - - 0.40 Water ------balance-------Viscositv mPas 21s 1 5853 1760 1614 1891 110s 1 1016 453 482 496 In compositions B, C and D a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer (A).
Claims (13)
1. A fabric treatment composition comprising an aqueous base, one or more, fabric-softening materials and an emulsion component wherein the emulsion component comprises from 2 to 70% of the composition, said composition having a structure of lamellar droplets of the fabric-softening material in combination with an emulsion, said composition also comprising a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side chains and having an average molecular weight of 500 to 500,000 when measured by gel permeation chromatography using a polyacrylate standard, or by specific viscosity (SV) measurements using a polyacrylate standard.
2. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of the general formula (I) wherein z is 1; (x+y):z is from 4:1 to 1,000:1;
in which the monomer units may be in random order; y being from 0 up to a maximum equal to the value of x; and n is at least 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups, or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order; and each B1 is independently selected from -CH2OH, -OH or -H.
in which the monomer units may be in random order; y being from 0 up to a maximum equal to the value of x; and n is at least 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups, or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order; and each B1 is independently selected from -CH2OH, -OH or -H.
3. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of the general formula (II):
wherein:
Q2 is a molecular entity of formula IIa:
wherein z is 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups, or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl;
A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order~
Q1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q1 in any direction, in any order, therewith possibly resulting in a branched polymer;
n is at least 1 and z is defined above; v is 1; and (x + y +p + q + r):z is from 5:1 to 500:1; in which the monomer units may be in random order; and either p and q may be zero, or r is zero;
R7 and R8 represent -CH3 or -H;
R9 and R10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups, or (C2H4O)t H, wherein t is from 1-50, and wherein the monomer units may be in random order.
wherein:
Q2 is a molecular entity of formula IIa:
wherein z is 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups, or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl;
A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order~
Q1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q1 in any direction, in any order, therewith possibly resulting in a branched polymer;
n is at least 1 and z is defined above; v is 1; and (x + y +p + q + r):z is from 5:1 to 500:1; in which the monomer units may be in random order; and either p and q may be zero, or r is zero;
R7 and R8 represent -CH3 or -H;
R9 and R10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups, or (C2H4O)t H, wherein t is from 1-50, and wherein the monomer units may be in random order.
4. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of the general formula (III):
wherein Q3 is derived from a monomeric unit IIIa comprising:
Q4 is derived from the molecular entity IIIb:
and Q5 is derived from a monomeric unit IIIc:
wherein;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl;
(a + b + c): Q4 is from 5:1 to 500:1, in which the monomer units may be in random order, a, b, c, d, e, f, g, h may be an integer or zero, n is at least 1;
B1, B2, B3, B4 are organic or inorganic anions;
w is zero to 4;
R11 is independently selected from hydrogen or C1-C4 alkyl; and R12 is independently selected from C5 to C24 alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl.
wherein Q3 is derived from a monomeric unit IIIa comprising:
Q4 is derived from the molecular entity IIIb:
and Q5 is derived from a monomeric unit IIIc:
wherein;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl;
(a + b + c): Q4 is from 5:1 to 500:1, in which the monomer units may be in random order, a, b, c, d, e, f, g, h may be an integer or zero, n is at least 1;
B1, B2, B3, B4 are organic or inorganic anions;
w is zero to 4;
R11 is independently selected from hydrogen or C1-C4 alkyl; and R12 is independently selected from C5 to C24 alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl.
5. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of the general formula (IV):
wherein z is 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and z is 1 and j:z is from 5:1 to 500:1, in which the monomer units may be in random order, and n is at least 1;
R13 represents -CH2-, -C2H4-, -C3H6- or is absent.
R14 represents from 1 to 50 independently selected alkyleneoxy groups, or is absent.
R15 represents -OH or hydrogen.
wherein z is 1;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and z is 1 and j:z is from 5:1 to 500:1, in which the monomer units may be in random order, and n is at least 1;
R13 represents -CH2-, -C2H4-, -C3H6- or is absent.
R14 represents from 1 to 50 independently selected alkyleneoxy groups, or is absent.
R15 represents -OH or hydrogen.
6. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of the general formula (V):
Wherein:
Each R7' is R7 or -R1-R2-R3-R4;
R7 is independently selected from -OH, -NH-CO-CH~, -SO3A1, -OSO3A1, -NHSO3A1, -COOA1;
n is the total number of -R1-R2-R3-R4 groups per molecule;
n is at least 1;
m is the total number of R7 and R7' groups that are not -R1-R2-R3-R4;
the ratio m:n is from 12:1 to 3,000:1; wherein the monomer units may be in random order. v and w are determined by the molecular weight of the polymer;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent; or can be -NHCO; -OCH2CONH; or -O-CH2-CO-O-;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
A1 is independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order.
Wherein:
Each R7' is R7 or -R1-R2-R3-R4;
R7 is independently selected from -OH, -NH-CO-CH~, -SO3A1, -OSO3A1, -NHSO3A1, -COOA1;
n is the total number of -R1-R2-R3-R4 groups per molecule;
n is at least 1;
m is the total number of R7 and R7' groups that are not -R1-R2-R3-R4;
the ratio m:n is from 12:1 to 3,000:1; wherein the monomer units may be in random order. v and w are determined by the molecular weight of the polymer;
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent; or can be -NHCO; -OCH2CONH; or -O-CH2-CO-O-;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
A1 is independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order.
7. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of general formula (VI):
wherein z is 1; (x+y); z is from 4:1 to 1,000:1, wherein the monomer units may be in random order;
and n is at least 1.
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and R8 and R9 represent -CH2- or are absent;
S is selected from -CO(CH2)2COOA1, -CO(CH)2COOA1, -COCH2C(OH) (COOA1)CH2COOA1, -COCH2COOA1, -CO(CH(OH))2COOA1, -COCH2CH(OH)COOA1, -COCH2CH(CH3)COOA1 and -COCH2C(=CH2)COOA1;
A1 is independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order.
wherein z is 1; (x+y); z is from 4:1 to 1,000:1, wherein the monomer units may be in random order;
and n is at least 1.
R1 represents -CO-O, -O-, -O-CO-, -CH2-, -CO-NH- OR
is absent;
R2 represents from 1 to 50 independently selected alkyleneoxy groups or is absent, provided that when R3 is absent and R4 represents hydrogen, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that:
a) when R2 is absent, R4 is not hydrogen and when R3 is also absent then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;
R6 represents hydrogen or C1-4 alkyl; and R8 and R9 represent -CH2- or are absent;
S is selected from -CO(CH2)2COOA1, -CO(CH)2COOA1, -COCH2C(OH) (COOA1)CH2COOA1, -COCH2COOA1, -CO(CH(OH))2COOA1, -COCH2CH(OH)COOA1, -COCH2CH(CH3)COOA1 and -COCH2C(=CH2)COOA1;
A1 is independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order.
8. A fabric treatment composition as claimed in claim 1 wherein the deflocculating polymer is of general formula (VII);
Wherein:
D is -H or -OH; n is at least 1;
A is Wherein:
Each A2 is A1 or R10;
Q1:Q2 is from 4:1 to 1,000:1;
R10 represents a C5-24 alk(en)yl group;
B is ~O~CO~R11~CO~
R11 represents -CH2-, -C2H4-, C3H6-, or an aryl link said aryl link optionally being substituted with one or more -COOA1 groups, or a benzophenone link;
wherein:
A1 is independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order.
Wherein:
D is -H or -OH; n is at least 1;
A is Wherein:
Each A2 is A1 or R10;
Q1:Q2 is from 4:1 to 1,000:1;
R10 represents a C5-24 alk(en)yl group;
B is ~O~CO~R11~CO~
R11 represents -CH2-, -C2H4-, C3H6-, or an aryl link said aryl link optionally being substituted with one or more -COOA1 groups, or a benzophenone link;
wherein:
A1 is independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4, or (C2H4O)t H wherein t is from 1-50, and wherein the monomer units may be in random order.
9. A fabric treatment composition according to any of the preceding claims wherein the composition comprises from 0.01 to 5% by weight of deflocculating polymer.
10. A fabric treatment composition according to any of the preceding claims wherein the softener material comprises a cationic fabric softening material.
11. A fabric treatment composition according to any of the preceding claims wherein the emulsion component comprises hydrocarbons.
12. A fabric treatment composition according to any of the preceding claims wherein the emulsion component comprises a perfume.
13. A fabric treatment composition according to any of the preceding claims having a pH of less than 6Ø
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB909011785A GB9011785D0 (en) | 1990-05-25 | 1990-05-25 | Fabric treatment compositions |
GB9011785.4 | 1990-05-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2042979A1 CA2042979A1 (en) | 1991-11-26 |
CA2042979C true CA2042979C (en) | 2000-10-31 |
Family
ID=10676592
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002042979A Expired - Lifetime CA2042979C (en) | 1990-05-25 | 1991-05-21 | Fabric treatment composition |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0458599B2 (en) |
JP (1) | JP2818632B2 (en) |
KR (1) | KR940010047B1 (en) |
AU (1) | AU636753B2 (en) |
BR (1) | BR9102126A (en) |
CA (1) | CA2042979C (en) |
DE (1) | DE69124420T3 (en) |
ES (1) | ES2097793T5 (en) |
GB (1) | GB9011785D0 (en) |
MY (1) | MY107162A (en) |
ZA (1) | ZA913958B (en) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL9201939A (en) * | 1992-11-05 | 1994-06-01 | Avebe Coop Verkoop Prod | Liquid fabric softener compositions. |
SK53294A3 (en) | 1993-05-07 | 1995-04-12 | Albright & Wilson | Concentrated aqueous mixture containing surface active matter and its use |
WO1995027035A1 (en) † | 1994-03-31 | 1995-10-12 | Unilever Plc | Detergent compositions |
US6008184A (en) * | 1994-09-30 | 1999-12-28 | The Procter & Gamble Company | Block copolymers for improved viscosity stability in concentrated fabric softeners |
DE69431841D1 (en) * | 1994-09-30 | 2003-01-16 | Procter & Gamble | Block copolymers for improved viscosity stability in concentrated fabric softeners |
EP0802967B2 (en) * | 1995-01-12 | 2003-05-21 | The Procter & Gamble Company | Stabilized liquid fabric softener compositions |
IL116638A0 (en) * | 1995-01-12 | 1996-05-14 | Procter & Gamble | Method and compositions for laundering fabrics |
FR2732031B1 (en) * | 1995-03-23 | 1997-04-30 | Coatex Sa | USE OF AMPHOTERIC AGENTS AS MODIFIERS OF LAMELLAR PHASES OF LIQUID OR PASTY DETERGENT OR COSMETIC COMPOSITIONS |
GB9515805D0 (en) * | 1995-08-02 | 1995-10-04 | Jeyes Group Plc | Compositions |
FR2752584A1 (en) * | 1996-08-26 | 1998-02-27 | Coatex Sa | AGENT COMPATIBLE WITH SURFACTANTS USED IN DETERGENCE OR COSMETICS |
GB9711849D0 (en) * | 1997-06-06 | 1997-08-06 | Unilever Plc | Polymeric materials |
US6503977B1 (en) * | 1999-03-25 | 2003-01-07 | Kimberly-Clark Worldwide, Inc. | Substrate coatings, methods for treating substrates for ink jet printing, and articles produced therefrom |
US6838498B1 (en) | 1999-11-04 | 2005-01-04 | Kimberly-Clark Worldwide, Inc. | Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention |
KR100805584B1 (en) | 2000-01-19 | 2008-02-20 | 킴벌리-클라크 월드와이드, 인크. | Water-soluble ink water-soluble coating for inkjet printing materials and coating method using the same |
US6936648B2 (en) | 2000-10-30 | 2005-08-30 | Kimberly-Clark Worldwide, Inc | Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention, method for treating said substrates, and articles produced therefrom |
EP1468068B1 (en) * | 2002-01-25 | 2007-05-16 | Henkel Kommanditgesellschaft auf Aktien | Conditioning agent for protecting textiles |
JP4813200B2 (en) * | 2005-02-24 | 2011-11-09 | 花王株式会社 | Textile treatment composition |
GB0524659D0 (en) | 2005-12-02 | 2006-01-11 | Unilever Plc | Improvements relating to fabric treatment compositions |
WO2008040785A1 (en) | 2006-10-06 | 2008-04-10 | Dow Corning Corporation | Process for preparing fabric softener compositions |
GB0623005D0 (en) * | 2006-11-17 | 2006-12-27 | Unilever Plc | Fabric treatment method and composition |
US8426351B2 (en) | 2006-12-12 | 2013-04-23 | Kao Corporation | Liquid softener composition or transparent or semitransparent liquid softener composition |
GB0800756D0 (en) | 2008-01-17 | 2008-02-27 | Unilever Plc | Improvements relating tofabric conditioning compositions |
CN102947434A (en) | 2010-05-25 | 2013-02-27 | 荷兰联合利华有限公司 | Improvements relating to fabric conditioning compositions |
WO2018059892A1 (en) | 2016-09-29 | 2018-04-05 | Unilever Plc | Laundry composition |
WO2018060056A1 (en) | 2016-09-29 | 2018-04-05 | Unilever Plc | Laundry composition |
FR3091878B1 (en) | 2019-01-22 | 2023-06-16 | Calyxia | CLEANING PRODUCT COMPOSITIONS WITH ENHANCED OLFACTIVE PROPERTIES |
FR3091877B1 (en) | 2019-01-22 | 2023-06-16 | Calyxia | DETERGENCE COMPOSITIONS WITH ENHANCED OLFACTIVE PROPERTIES |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1439244A (en) * | 1972-09-29 | 1976-06-16 | Procter & Gamble | Liquid crystalline compositions |
GB1604030A (en) * | 1977-11-21 | 1981-12-02 | Procter & Gamble Ltd | Textile conditioning compositions |
DE3066798D1 (en) * | 1979-04-21 | 1984-04-12 | Procter & Gamble | Fabric softening composition |
EP0043622B1 (en) * | 1980-01-07 | 1984-11-21 | THE PROCTER & GAMBLE COMPANY | Fabric softening composition |
PH18436A (en) * | 1980-11-07 | 1985-07-08 | Unilever Nv | A fabric softening composition and a process for preparing it |
US4464273A (en) * | 1982-02-10 | 1984-08-07 | Lever Brothers Company | Fabric softening composition |
DE3220012A1 (en) † | 1982-05-27 | 1983-12-01 | Akzo Gmbh, 5600 Wuppertal | POLYAETHER DERIVATIVES AND THE USE THEREOF AS DISPERGATORS IN MEANS FOR SOFT RINSING OF TEXTILES BASED ON QUATERNAUS AMMONIUM SALTS |
US4767625A (en) * | 1985-09-02 | 1988-08-30 | Kao Corporation | Lamella type single phase liquid crystal composition and oil-base cosmetic compositions using the same |
GB8618428D0 (en) * | 1986-07-29 | 1986-09-03 | Unilever Plc | Conditioning fabrics |
JPS63291999A (en) * | 1987-05-25 | 1988-11-29 | Lion Corp | Softener composition |
JPS6426788A (en) * | 1987-07-17 | 1989-01-30 | Kao Corp | Concentration type softening finish agent for clothing |
US4885102A (en) * | 1987-07-17 | 1989-12-05 | Kao Corporation | Cloth-softening liquid composition containing quaternary ammonium compound and a polyether derivative or cationic surfactant polymer |
JPH01250473A (en) * | 1988-03-31 | 1989-10-05 | Lion Corp | Liquid softening agent composition |
IT1217842B (en) * | 1988-06-17 | 1990-03-30 | Enichem Sintesi | PROCEDURE FOR THE PREPARATION OF ORGANIC GLASSES |
GB8919669D0 (en) * | 1989-08-31 | 1989-10-11 | Unilever Plc | Fabric-softening compositions |
GB8927361D0 (en) * | 1989-12-04 | 1990-01-31 | Unilever Plc | Liquid detergents |
-
1990
- 1990-05-25 GB GB909011785A patent/GB9011785D0/en active Pending
-
1991
- 1991-05-21 CA CA002042979A patent/CA2042979C/en not_active Expired - Lifetime
- 1991-05-21 DE DE69124420T patent/DE69124420T3/en not_active Expired - Lifetime
- 1991-05-21 ES ES91304603T patent/ES2097793T5/en not_active Expired - Lifetime
- 1991-05-21 EP EP91304603A patent/EP0458599B2/en not_active Expired - Lifetime
- 1991-05-22 AU AU77258/91A patent/AU636753B2/en not_active Expired
- 1991-05-23 MY MYPI91000875A patent/MY107162A/en unknown
- 1991-05-24 ZA ZA913958A patent/ZA913958B/en unknown
- 1991-05-24 JP JP3149738A patent/JP2818632B2/en not_active Expired - Fee Related
- 1991-05-24 BR BR919102126A patent/BR9102126A/en not_active IP Right Cessation
- 1991-05-25 KR KR1019910008534A patent/KR940010047B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0458599B2 (en) | 2000-11-29 |
ES2097793T5 (en) | 2001-02-16 |
GB9011785D0 (en) | 1990-07-18 |
EP0458599A3 (en) | 1992-07-08 |
JPH04228680A (en) | 1992-08-18 |
DE69124420T3 (en) | 2001-02-22 |
DE69124420D1 (en) | 1997-03-13 |
MY107162A (en) | 1995-09-30 |
EP0458599B1 (en) | 1997-01-29 |
CA2042979A1 (en) | 1991-11-26 |
EP0458599A2 (en) | 1991-11-27 |
BR9102126A (en) | 1991-12-24 |
KR910020262A (en) | 1991-12-19 |
KR940010047B1 (en) | 1994-10-21 |
JP2818632B2 (en) | 1998-10-30 |
AU636753B2 (en) | 1993-05-06 |
AU7725891A (en) | 1991-11-28 |
DE69124420T2 (en) | 1997-05-15 |
ZA913958B (en) | 1993-01-27 |
ES2097793T3 (en) | 1997-04-16 |
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