CA2277484A1 - Detergent compositions and copolymers for inhibiting dye transfer - Google Patents
Detergent compositions and copolymers for inhibiting dye transfer Download PDFInfo
- Publication number
- CA2277484A1 CA2277484A1 CA002277484A CA2277484A CA2277484A1 CA 2277484 A1 CA2277484 A1 CA 2277484A1 CA 002277484 A CA002277484 A CA 002277484A CA 2277484 A CA2277484 A CA 2277484A CA 2277484 A1 CA2277484 A1 CA 2277484A1
- Authority
- CA
- Canada
- Prior art keywords
- vinyl
- polymer
- acid
- monomers
- detergent composition
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 229920001577 copolymer Polymers 0.000 title claims abstract description 82
- 239000003599 detergent Substances 0.000 title claims abstract description 48
- 238000012546 transfer Methods 0.000 title claims abstract description 30
- 230000002401 inhibitory effect Effects 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 82
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 75
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 66
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004744 fabric Substances 0.000 claims abstract description 50
- BOZBBKZCBLPUSG-UHFFFAOYSA-N 2-prop-1-enyl-1h-imidazole Chemical compound CC=CC1=NC=CN1 BOZBBKZCBLPUSG-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 125000000129 anionic group Chemical group 0.000 claims abstract description 29
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002689 soil Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- XWRBMHSLXKNRJX-UHFFFAOYSA-N 2-ethenyl-1-oxidopyridin-1-ium Chemical compound [O-][N+]1=CC=CC=C1C=C XWRBMHSLXKNRJX-UHFFFAOYSA-N 0.000 claims abstract description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 6
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims abstract description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract 4
- 229960004275 glycolic acid Drugs 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 7
- YEYMTOQDNGGXRS-UHFFFAOYSA-N 5-ethenyl-2H-1,3-oxazol-2-id-4-one Chemical compound C(=C)C1C(N=[C-]O1)=O YEYMTOQDNGGXRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 150000002334 glycols Chemical class 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004902 Softening Agent Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000000116 mitigating effect Effects 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 65
- 229920000642 polymer Polymers 0.000 description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000007844 bleaching agent Substances 0.000 description 21
- -1 sulpho groups Chemical group 0.000 description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
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- 238000012360 testing method Methods 0.000 description 11
- 108091005804 Peptidases Proteins 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 230000005764 inhibitory process Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 229940088598 enzyme Drugs 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 102000035195 Peptidases Human genes 0.000 description 7
- 239000004365 Protease Substances 0.000 description 7
- 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
- 239000000843 powder Substances 0.000 description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 5
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 4
- 101100468275 Caenorhabditis elegans rep-1 gene Proteins 0.000 description 4
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 4
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 150000004965 peroxy acids Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 4
- 229940045872 sodium percarbonate Drugs 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
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- 239000004367 Lipase Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 3
- YIQKLZYTHXTDDT-UHFFFAOYSA-H Sirius red F3B Chemical compound C1=CC(=CC=C1N=NC2=CC(=C(C=C2)N=NC3=C(C=C4C=C(C=CC4=C3[O-])NC(=O)NC5=CC6=CC(=C(C(=C6C=C5)[O-])N=NC7=C(C=C(C=C7)N=NC8=CC=C(C=C8)S(=O)(=O)[O-])S(=O)(=O)[O-])S(=O)(=O)O)S(=O)(=O)O)S(=O)(=O)[O-])S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] YIQKLZYTHXTDDT-UHFFFAOYSA-H 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
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- 102000013142 Amylases Human genes 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
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- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 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 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000002366 lipolytic effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- 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
- C11D3/3792—Amine oxide containing polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A detergent composition comprising a copolymer and at least one component selected from surface active agents and fabric softening compounds, the copolymer comprising at least one dye binding monomer and at least one anionic or nonionic monomer, with the proviso that the copolymer is not poly(1-vinylpyrrolidone-co-acrylic acid). Also a method of mitigating dye transfer in a detergent composition in the presence of typically encountered soils is provided. A dye binding copolymer comprising at least one anionic monomer selected from acrylic acid, methacrylic acid, vinyl sulphonic acid, itaconic acid, octanoic acid, hexanoic, hydroxy acetic acid or mixtures thereof or at least one nonionic monomer selected from polyethylene glycols and at least one dye binding monomer selected from vinyl imidazole, methyl vinyl imidazole, vinyl pyridine-N-oxide, vinyl pyrrolidone and mixtures thereof is also disclosed.
Description
DETERGENT COMPOSITIONS AND COPOLYMERS FOR INHIBITING DYE TRANSFER
Technical Field The present invention relates to a detergent composition and to a process for inhibiting dye transfer between fabrics during washing. In particular, the invention relates to detergent compositions containing novel dye-transfer inhibition copolymers.
Backaround of the Invention There is a tendency during the laundering of fabrics for coloured fabrics to release dye into the wash solution. This is a most persistent and troublesome problem as this released dye can then be transferred onto other fabrics. Afabric treatment composition comprising an agent which could prevent the transfer of dye would therefore prove useful.
EP462 806 (Unilever) discloses a domestic treatment of a fabric with a cationic dye fixing agent to reduce the amount of dye released from the fabric. Suitable cationic dye fixing agents include the dimethyldiallyl ammonium chloride polymer.
Surfactant-containing dye transfer inhibiting compositions are disclosed in EP 0 587 550 (Procter and Gamble). The dye transfer inhibition agent is a polymer selected from polyamine N-oxide containing polymers.
EP O 327 927 (Procter and Gamble) describes a granular detergent additive comprising water-soluble polymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidine and cationic compounds.
Detergent compositions comprising a N-vinylimidazole N-vinylpyrolidone copolymer are disclosed in EP 0 635 566 and EPo 635 565 (Procter and Gamble).
DE 42 24 762A (BASF AG) discloses the use of nitrogen-containing polymers as dye-transfer inhibitors in textile washing, the polymers contain a carbonyl or ester group with the esters being neutral in the co-polymer.
EP-A-0-631-008 (Ciba-Geigy AG) relates to an after-washing process for a dyeing operation in which a polyvinyl pyrrolidone homo or co-polymer, and, a water softener are used in the absence of a surfactant. The copolymer can contain comonomers such as those containing carboxyl groups, sulpho groups, phosphorous based groups or other ethylenically unsaturated monomers. Such non-surfactant dyeing after washing processes and compositions used in them are outside the scope of the present invention.
EP-0-100-890-A (BASF AG) discloses co-polymers obtained by the radical copolymerisation of monomers of C3-C2o alkyl ester of (meth)acrylic acid N-containing neutrally reacting water-soluble compounds, compounds containing cationic groups and olefinically unsaturated Cj-CS carboxylic acids. The polymers are used in hair treatment compositions.
.. __._... .. . _ . _.__-.
r ~. ~-.-..~._.~.... . ..
' CA 02277484 1999-07-09 Document #: 344111 WO 95/27759 discloses ink compositions comprising network forming or cross-linked polymers or resins, where the polymers may include a dye-binding copolymer.
EP 687 694 (BASF) discloses a process for the preparation of polymers base on vinyl imidazoles. The process relates to vinyl imidazole co-polymers and homopolymers.
WO 91 00302 (GAF) discloses terpolymers which are insoluble in heptane and which are produced form a reaction mixture of a vinyl lactam, a polymersible carboxylic acid and a hydrophobic monomer.
WO 95/00611 discloses floor cleaners comprising a copolymer of vinyl pyrrolidone and acrylic acid, dimethylaminoethyl methacrylate, vinyl acetate or methaminopropyl trimethyl ammonium chloride. The copolymers are used as shine boosters.
We have found that whilst these polymers of the prior art when used for dye transfer mitigation can be effective in preventing dye transfer under model conditions, in the presence of soil under normal laundering conditions they become ineffective, and can even lead to additional dye transfer.
Compositions of the present invention are directed towards overcoming this problem by using co-polymers which even in the presence of soil, retain their dye transfer inhibition properties.
Definition of the Invention Accordingly the present invention provides a fabric wash detergent composition comprising a co-polymer and at least one .'C::.,~~1~'~ ~~ c I~I=wcP
component selected from surface active agents and fabric softening compounds, the co-polymer comprising at least one dye binding monomer selected from vinyl azalactam monomers, vinyl azalactone monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, with the proviso that the co-polymer is not poly(1-vinylpyrrolidone-co-acrylic acid).
Of particular interest are dye binding co-polymers of poly(vinylpyrrolidone-co-polyvinylimidazole-co-acrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-polyvinylimidazole-co-methacrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-polymethylvinylimidazole-co-acrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-polymethylvinylimidazole-co-methacrylic acid).
The invention also relates to use of a co-polymer comprising at least one dye binding monomer selected from vinyl azalactone, vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof, and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, in a laundry treatment composition to mitigate dye transfer between fabrics.
The present invention further provides use of a co-polymer comprising at least one dye binding monomer selected from vinyl azalactone monomers, vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof, and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, to prevent redeposition of soil in fabric washing conditions.
r~ ~~, -» .~.-T
~; '.~~i:. :'~...,.._.... .-;'yes C3757 ' S -In particular co-polymers as defined above comprising 1-10% by weight acrylic acid or methacrylic acid monomers are of use.
The teen dye-binding monomer as used herein is used in relation to monomers which have a dye-binding capability when in their polymerised form i.e. the co-polymer comprising the polymerised dye-binding monomers has dye binding characteristics resulting from said monomer.
More specifically in the context of the present invention a dye binding monomer is defined as a monomer the homopolymer (mwt of 40,000-100,000) of which binds dye in water at pH at a temperature from 5°C to 60°C, preferably at a temperature of 20°C. However, with this proviso the dye binding homopolymer can bind dye under other conditions.
Detailed Description of the Invention The copolymers of the invention at least one dye binding monomer and at least one anionic or nonionic monomer.
Preferred polymers include vinyl pyrrolidone (VP), vinyl imidazole (VI), methyl vinyl imidazole (MeVI), vinyl pyridine, vinyl pyridine-N-oxide (VPy-N-0), vinyl oxazolidone.
i ;: :. ._ ~. -i ~ w ,~.- ,; ;._ r Especially preferred are vinyl imidazole, methyl vinyl imidazole (meVI) and vinyl pyridine-N-oxide, used alone or in combination with vinyl pyrrolidone and combinations thereof.
Any anionic monomer is suitable for use with the invention.
However it is preferred if the anionic moiety is based on a carboxy, sulphonate, sulphate, phosphate or phosponate containing material, especially preferred are short chain, polyTnerisable group carboxy containing material having at least one double bond. Preferred anionic monomers are itaconic acid, aconitic acid, mesaconic acid, citraconic acid, acrylic acid (AA), methacrylic acid (MA), octanoic acid, hexanoic acid, vinyl acetic acid, vinyl benzoic acid, vinyl sulphonic acid, vinyl benzene sulphonic acid, vinyl phosphoric acid and hydroxy acrylic oracetic acid. Especially preferred are AA, MA and vinyl sulphonic acid Examples of preferred copolymers are described below.
i ) ~~_ ~ ~~~~~y ( ii~~
CO~bI COibl N~ O
p R~ ~~~.Rn N ~N
~( CA~1 PAY( ~) ~CH~-~~CH~.CH-~-~CH=.CH~ "~"Ctl:_CRn~CHz.CH~
x r (iii) ~~ N ( Z O (iv) ~iM y ~W R"
N H
Poh(MIWwPI i O
~h( cNPY-~1 M ~ H) l~l~', K', IdH, CAS Carboxylic acid. X,Z,Z is the polmerisation number so . R = H, A1 mwt is achieved.
kyl; ~g Clip, CsH~, ate; n ~ t-4 inaependentaly of each other Y
For (ii) it is preferred that R' is H so that the polymer is poly(acrylic acid/VI/VP). It is possible that VI may have R' as CH3 i.e. be methyl vinyl imidazole which is another preferred co-polymer. This applies for each of (i)-(iii) above.
The weight ratio of anionic or nonionic monomertsa to the dye - binding monomers) within the co-polymer is preferably from 1:200 to 1:1, more preferably 1:15J to 1:2, most preferably 1:100 to 1:3.
It may be desirable to include additional monomers in these dye binding polymer. Examples of these additional monomers include vinyl alcohol, vinyl acetate, vinyl styrene, acrylamide, methyl methacrylate, hydroxyethyl acrylate/methacrylate, IEG
acrylate/methacrylate, glycidyl acrylate/methacrylate. The addition of these third monomers can cause changes in the properties of these polymers such as solubility, compatibility with liquid products and redeposition performance or sequestration ability. However, such further monomers may be .. _. , -. . ' ._. ~... .
';, '. : ,_ included if the properties of the co-polymers are not adversely affected.
Additional monomers may also be present for cost minimalisation) as a cross-linking moiety or to impart biodegradability. However, non-crosslinked co-polymers are preferred. The co-polymers of the present invention most preferably retain the anionic ar nonionic nature of the monomers within the co-polymer.
It is preferred if the co-polymer has an average molecular weight range from 2,000 to 200,000 more preferably from 5,000 to 100.000, most If the detergent composition is in liquid forth it is preferred if the co-polymer has a molecular weight range from 5,000 to 30,000. If the detergent composition is granular the preferred molecular weight is from 10,000 to 50,000.
The detergent compositions may comprise 0.001-5% w/w of the copolymer, preferably 0.1-3%, e.g. 0.1-2%, such as 0.1-1%.
In the context of the present invention the most preferred co-polymers are selected from the group consisting of:
a) co-polymers of PVP/PVI/AA, PVP/PVI/MA especially where the ratio of PVI/PVP is from 2:1 to 0.2:1, most preferably 1:1 to 0.3:1 b) co-polymers of PVI/AA, PVI/MA and:
c) co-polymers of PVPy-N-O/AA, PVPy-N-0/MA.
d) co-polymers of PVP/MePVI/AA, PVP/MePVI/MA especially where the weight ratio of PVP:PVI/MePVI is from 90:10 to 10:90, especially 75:25 to 25:75, e.g. 50:50.
_9 Co-polymers comprising at least one dye-binding monomer selected from VI, MeVI and VP where the anionic monomer is AA are especially preferred.
The ratio of VP/meVI or VI when two dye binding monomers are used together is preferably in the weight ratio range stated above in a) or d) .
It is also advantageous, especially for VP/meVI co-polymers if the anionic monomer, which is preferably AA or MA represents 1-10% w/w of the copolymer, especially 2-8%, most especially 2.5%-7% w/w. Excellent results for both the mitigation of dye transfer and anti-redeposition have been obtained with VP/meVI
co-polymers containing around 3% MA or AA, particularly when the ratio of the VP/meVI is within the range 90:10 to 10:90, preferably 75:25 to 25:75 e.g. 50:50.
In addition to dye transfer inhibition properties the compositions of the invention also exhibit excellent redeposition of soil properties. This is especially advantageous for the co-polymers of VP, with VI or MeVI, and AA or. MA.
The compositions of the invention comprise a component selected from surface active agents and fabric softening compounds. Typically at least one of the two aforementioned components will be present dependent upon the application.
The compositions of. the present invention are preferably laundry compositions, especially main wash compositions or rinse-added softening compositions.
The main wash compositions may include a fabric softening agent.
Surface Active Compounds The detergent compositions of the invention may contain a surface-active compound (surfactant) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof. Many suitable surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I
and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
It is preferred if the compositions of the invention contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of CR-CiS. It is preferred if the level of alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt%
to 15 wt%.
The detergent compositions of the invention may contain other anionic surfactants in amounts additional to the percentages quoted above. Suitable anionic surfactants are well-known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly Cg-C,5 primary alkyl r T _.__ ._...__... T ._..____m_._~..
sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred.
The compositions of the invention may also contain nonionic surfactant. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the cec,,) aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C,o-C,5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
It is preferred if the level of nonionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
The choice of surface-active compound (surfactant), and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions) different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wts surfactant e.g. 2-60a, preferably 15-40°s most preferably 5-35%.
Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
Fabric Softening Compounds Any conventional fabric softening compound may be used in the compositions of the present invention. The softening compounds may be cationic or nonionic. If the fabric softening compound is to be employed in a main wash detergent composition the compound will typically be nonionic.
The fabric softening compound is suitably a substantially water insoluble quaternary ammonium material comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to CZO or, more preferably, a compound comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C14.
Preferably the fabric softening compound has two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16. Most preferably at least 50~ of the long chain alkyl or alkenyl groups have a chain length of Cle or above It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
___._.~._..__.__...r.__~__.......
The fabric softening compounds used in the compositions of the invention are preferably compounds that provide excellent softening, and characterised by a chain melting L beta to L
alpha transition temperature greater than 25°C, preferably greater than 35°C, most preferably greater than 45°C. This L
beta to L alpha transition can be measured by DSC as defined in " Handbook of Lipid Bilayers, D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337).
Substantially insoluble fabric softening compounds in the context of this invention are defined as fabric softening compounds having a solubility less than 1 x10 3 wt % in deminerailised water at 20°C. Preferably the fabric softening compounds have a solubility less than 1 x10-' wt %. Most preferably the fabric softening compounds have a solubility less than 1 x10 8 to 1 x10 6.
Preferred fabric softening compounds are quaternary ammonium compounds. It is especially preferred if the fabric softening compound is a water insoluble quaternary ammonium material which comprises a compound having two C12-le alkyl or alkenyl groups connected to the molecule via at least one ester link.
It is preferred if the quaternary ammonium material has two ester links present. An especially preferred ester-linked quaternary ammonium material can be represented by the formula;
Rt R1 N (CHZ) ~-T-Rz (CHZ) n-T_R2 i wherein each R1 group is independently selected from C1_4 alkyl, hydroxyalkyl or C2_4 alkenyl groups; and wherein each R2 group is independently selected from CB_28 alkyl or alkenyl groups;
O O
T is -O-C- or -C-O-; and N is an integer from 0-5.
Di (tallowowyloxyethyl) dimethyl ammonium chloride is especially preferred.
A second preferred type of quaternary ammonium material can be represented by the formula;
(R~ ) 3N - (CHz) n CH
CHZOOCRz wherein Rl ( n and RZ are as defined above .
It is advantageous if the quaternary ammonium material is biologically biodegradable.
Preferred materials of this class such as 1,2 bis (hardened tallowoyloxy) -3- trimethylamQnonium propane chloride and their method of preparation are, for example, described in US 4 137 180 (lever Brothers). Preferably these materials comprise small amounts of the corresponding monoester as described in US
4 137 180 for example 1- hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.
Lecithins are also suitable softening compounds.
_..__.~s..~_~__~.__..__....
DeterQencv Builders The detergent compositions of the invention will generally also contain one or more detergency builders if they are for use in the main wash of a laundering process. The total amount of detergency builder in the compositions will typically suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates) for example, zeolites as disclosed in GH 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 5148 (Hoechst). Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
The detergent compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
0 . 8 -1 . 5 NazO . A1203 . 0 . 8 - 6 S i02 These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg Ca0/g.
The preferred sodium aluminosilicates contain 1.5-3.5 Si02 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the cocrnnercially available zeolite ~A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite M,~P>as described and claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33) preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite M~ having a silicon to aluminium ratio not exceeding 1.07.more preferably about 1.00. The calcium binding capacity of zeolite MAPis generally at least 150 mg Ca0 per g of anhydrous material.
Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, ._ _~_.-.~._-..,..
and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates,dipicolinates,hydroxyethyiiminodiacet ates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Bleach Components Detergent compositions according to the invention may also suitably contain a bleach system..Fabric washing compositions may desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt%, preferably from 0.5 to 25 wt%.
The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 0.1 to 8 wt%, preferably from 0.5 to 5 wt%.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernoanoic acid precursors. Especially preferred bleach precursors suitable for use in the present invention are N,N,N',N.-tetracetyl ethylenediamine (TAED) and sodium noanoyloxybenzene sulphonate (SNOBS). The novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP
402971A (Unilever), and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) are also of interest.
The bleach system can be either supplemented with or replaced by a peroxyacid. Examples of such peracids can be found in US 4 686 063 and US 5 397 501 (Unilever).
a preferred example is the imido peroxycarboxylic class of peracids described in EP A 325 288, EP A 349 940, DE 382 3172 r _._~._ __T..._~_w _. _ .__._.._ ~.
and EP 325 289. A particularly preferred example is phtalimido peroxy caproic acid (PAP). Such peracids are suitably present at 0.1 - 12% preferably 0.5 - 10%.
A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), the polyphosphonates such as bequest (Trade Mark) and non-phosphate stabilisers such as EDDS
(ethylene diamine di-succinic acid). These Bleach stabilisers are also useful for stain removal especially in products containing low levels of bleaching species or no bleaching species.
An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
The Enzyme The detergent compositions according to the invention may also contain an enzyme.
Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
Preferred proteolytic enzymes (proteases) are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.
Examples of suitable proteolytic enzymes are the stabilisins which are obtained from particular strains of B. subtilis B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark). The preparation of these and analogous enzymes is described in GB 1 243 785. Other commercial proteases are Kazusase (Trade Mark) (obtainable from Showa-Denko of Japan), Optimase (Trade Mark) (from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark) (obtainable from Pfizer of U.S..a. >.
Detergency enzymes are commonly employed in granular forth in amounts of from about 0.1 to about 3.0 wt%.
Other ingredients The compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scone of the invention.
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
Other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes;
coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive.
It is advantageous if soil release polymers are present as they enhance the dye transfer inhibition. Particularly preferred are soil release polymers based disclosed in WO 95/32997 A (Rhone Poulenc)), EP 219 048 (BASF)) GB 2 208 515 (Colgate), EP 253 567 (P-.G) The detergent composition when diluted in the wash liquor (during a typical wash cycle) will typically give a pH of the wash liquor from 7 to 10.5 for a main wash detergent.
The detergent components of the present invention may be incorporated in detergent compositions of all physical types, for example, powders, liquids, gels and solid bars.
Detergent compositions of the invention may be prepared by any suitable method.
Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/1, more preferably at least 500 g/1.
Especially preferred compositions have bulk densities of at least 650 g/litre, more preferably at least 700 g/litre.
Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a hiqh-speed mixer/granulator may advantageously be used.
Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever) .
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in compact form which means ___..~. ..._~. T ~..-.... T
it will contain a lower level of water compared to a conventional liquid detergent.
Examples The invention will now be illustrated by the following non-limiting examples. In the examples all percentages are expressed by weight. Further modifications within the scope of the present invention will be obvious to the skilled man.
Comparative Examples are designated by letters, while Examples of the invention are designated by numbers.
Preparation of Polymers The co-polymers of this invention can be produced by radical polymerisation of the appropriate monomers with or without a crosslinking agent. The polymerisation can be conducted in bulk, in solution (aqueous or organic media) also employing emulsion or suspension polymerisation techniques. Depending on the monomer reactivity ratios and their concentration, the co-polymers will have random or block nature.
Example 1 Co-polymerisation of Vinylimidazole & Acrylic Acid (95:5) 1-Vinylimidazole 47g (0.5 mol) Acrylic Acid 1.8g(25 mol) 1,4-Dioxane 250 ml 4,4-Azobis(4-cyanovaleric)acid(ACVA) 0.148 The radical polymerisation of 1-Vinylimidazole (0.5 mol) and Acrylic Acid was carried out under nitrogen. After degassing for 30 minutes, the reaction mixture was heated to 70°C and ACVA (0.5 mol) was added. The polymerisation reaction was stirred overnight under a nitrogen atmosphere until the reaction mixture turned cloudy.
The bulk of the dioxane was removed and sodium hydroxide solution was added to neutralise the acrylic acid. The remaining dioxane/water was removed, the sample was redissolved in water and freeze dried.
NMR Analysis indicate that the co-polymer contains between 4-80 of acrylic acid monomer. GPC Molecular weights against polyethylene glycol standards are: Mn 40970, Mw 137900, D3.366.
....___.._ ..... _T_._.. _. ~_....___. . ...
Example 2 Co-Polymerisation of Vinylimidazole & Acrylic Acid (50:50) 1-Vinylimidazole 18.88 (0.2 mol) Acrylic Acid 14.4g (0.2 mol) 1,4-Dioxane 300 ml 4,4-Azobis(4-cyanovaleric)acid(ACVA) 0.5g The polymerisation was carried out as example 1, but with different monomer ratios. After the polymerisation completed, sodium hydroxide solution was added to the stirred reaction product and the polymer precipitated out. The polymer was redissolved in water and freeze dried or precipitated out using methanol (three times).
NMR spectrum shows that the copolymer contains about 75 acrylic acid monomer.
Example 3 Co-Polymerlsation of Vinylimidazole ~ Acrylic Acid (80:20) 1-Vinylimidazole 25.8g (0.274 mol) Acrylic Acid 3.95g(55 mol) 1,4-Dioxane 250 ml 4,4-Azobis(4-cyanovaleric) acid (ACVA) 0.2g The polymerisation was carried out as example 1, but with different monomer ratios. After the polymerisation completed, sodium hydroxide solution was added to the stirred reaction product and the polymer precipitated out. The polymer was redissolved in water and freeze dried or precipitated out using methanol (three times).
NMR analysis indicate that the co-polymer contains about 18 of acrylic acid monomer.
Dye Transfer Performance Conditions: Shakerbath, 40°C, 30 rains, 100 rpm lOOmls solution made with 26.4°FH water lg/1 total surfactant (combinations of LAS and E07) 0.522g/1 NaC03 0.87g/1 STP
lOuM Direct Red 80 dye 13x13cm white mercerised cotton 0.0435q/1 polymer After washing, the cloths were rinsed and tumble dried.
Their reflectances were measured on a ICS Texicon Spectraflash 500, and the results are given in Table 1 below as delta E values, calculated from the reflectance values.
The delta E values shown in the table are differences between washed and unwashed cotton. A high value of delta E
corresponds to more dye transfer than a low value.
Table 1 Example Dye Tranater Ratio of L71.9 : E07 inhibition agent polymer 100:0 90:10 75:25 60:10 0:100 None 41.63 41.63 42.51 41.72 38.77 pVp 41.26 40.06 37.41 26.6 23.82 r PVP/AA (95:51 40.89 pVI 36.55 32.87 25.36 21.55 17.08 q PVI/AA(94:6) 36.03 32.23 26.75 23.68 17.25 pVI/p,p, 37.76 37.03 29.52 25.77 24.41 (83:17) In addition to the above it was found that a simple ~esr.
using soiled fabrics predicts negative interactions between the formulation, dye transfer polymer and soil, but it does not predict positive benefits. It can therefore be used as a gross negative test to distinguish polymers which can give a negative in machine tests (worse than the control in the model test), from those Which will either have no effect, or . f.. ... _. .,.,....~.................. T ....
have benefits in the machine tests (equal to or better than the control) at the higher anionic ratios.
White cotton monitors were washed together with a piece of dyed test cloth and a piece of soiled test cloth for 30 mins at 40°C in a solution containing lg/1 active (80:20 LAS/NI), STP and NaC03 made with Prenton water (26.4°FH). Polymer was added at 0.0218g/1. The delta E values were calculated from the reflectance values of the white monitors and the results compared to the control (no polymer present).
Table 2 Example Dye Traaater Delta 8 Inhibition Polymer g None 10.19 g pVP 13.18 G PVP/PVI 12.42 PVI 14.04 PVP/AA (95:5) 13.27 6 PVI/AA (94.:6) 9.45 The results for PVP, PVI and PVP/PVI are significantly worse than the control, and this correlates with the relatively poor Performance of PVP and PVP/PVI in the washing machine.
In accordance with the invention the inclusion of anionic monomers in the co-polymer of PVI has significantly reduced its tendency to interact with soil, whilst not affecting its ability to bind dyes in solution.
Redeposition performance The redeposition performance of the polymers of the invention was investigated by evaluating their ability to prevent the transfer of iron oxide forth prestained fabric on to clean cotton monitor cloths. (0.5 mls of a 1% dispersion of iron (III) oxide was pipetted onto each monitor cloth and allowed to dry overnight).
Experiments were conducted in a tergotometer at 60rpm, 4oC, lOmin using demineralised water.
The reflectance of the monitor cloths was measured as in Example 1 and delta E values calculated.
The formulation was:
lg/1 nonionic surfactant (E07) 0.87g/L STP
0.522g/L sodium carbonate 0.1305g/L g co-polymer (absent for the control) Table 3 Example Dye Tanefer Delta E
Inhibition Polymer None 5.06 PVI 3.79 7 PVI/AA (83:17) 2.84 g PVI/AA(94:6) 3.19 There is thus a clear benefit for pvI/~ polymers.
Example 5 - Dye solubilisation Without wishing to be bound by theory, it is desirable for the polymers of the invention to have lower solubilising capacities compared to the homopolymers of the dye scavenging monomers. Orange OT, a sparingly water soluble dye from Aldrich, was purified by recrystalising twice from a .. _. .. __.. . _. .__...~..~_-.____.. _ . _ r..~~......N _ .
water/ethanol mixture. This purified dye was then dissolved in acetone (lOmg/ml).
30u1 (=0.3mg dye) of this solution was added to a vial containing water. The other components were then added: 0.25g/1 active (a combination of LAS and non-ionic), 0.522g/1 Na2C03) 0.87g/1 STP and 0.1088g/1 polymer (absent for the control). The total solution was lOmls made with demin water. The vials containing the solutions were then shaken for 24 hours at 30°C.
They were then centrifuged at 13,000 rpm for 10 mins to separate out the undissolved dye. The absorbance of the solutions was measured on a Perkin-Blmer Lambda 16 spectrophotometer at 492nm. In the table below Dye solubilised refers to the increase in absorbance of solutions (492nm) due to additional dye solubilised compared to the control without polymer.
Table 4 gxam~le Dye Traneter Dye Solubiliaed Inhibition Polymer 50/50 LAS/E07 pVI 0.031 9 PVI/AA (99:6) 0.021 PVI/AA (83:17) 0.003 The results clearly show that the incorporation of anionic groups in the polymer has depressed the ability of the polymer-surfactant complexes to solubilise the water insoluble dye.
Examples 11 and 12 A liquid detergent composition was prepared having the following composition.
Table 5 Wt. $
Ingredient Example 11 Example 12 Alkyl Sulphate - 10 Linear Alkyl Benzene 10 -Sulphonate Alkyl ethoxy sulphate Fatty alcohol ethoxylate 7E0 6 6 Sodium Citrate 2H,0 4 4 Propylene glycol Sorbitol 4.5 4.5 Na tetra-borate 5H20 3 3 Enzyme to 2$ to 2$
Soil release polymer to 2$ to 2$
PVI/AA 94:6 0.1 to 1 0.1 to 1 water/minors to 100 to 100 i r _.. _.... ~_... T ._ ._~..._~.. ... _ . .
Example 13 Table 6 The following powdered compositions were prepared.
NaLAS 7.1 NI 7E0 4.7 NI 3E0 3.5 Soap 0.3 Fatty Acid 0.3 STPP 27.1 SCMC 0.2 Na silicate 7.1 CP5 polymer 1.2 Sulphate 16.5 Soil release polymer 0.4 PVI/AA polymer 0.1-1 EAG 1.28 Carbonate 12.00 Bicarbonate 6.00 0.18 Protease Lipase/Amylase 0.30 Clay 0 to 10$
Cationic surfactant 0 to 2$
Perfume 0.17 Salts/water to 100 ' Table 7 Na PAS 11.5 NI 7E0 6.3 Soap 2.0 Zeolite A24 24.1 SCMC 0.6 Na Citrate 10.6 Carbonate 23.0 Soil release polymer 0.8 EpG 3.7 PVI/AA 94.6 copolymer 0.1 to 1 Fluorescer EDTMP 0.4 Percarbonate CP5 type polymer 0.9 Protease Lipase 0.1 Perfume 0.4 water/salts to 100 The formulations of Tables 5,6 and 7 had excellent cleaning and detergency performances with outstanding colour: care performance on coloured fabrics and mixed loads of coloured and white fabrics.
_ _ ___~.. _ . T_ Example (14)~ Anti redeposition results for a copolymer of MeVI/VP/AA.
The anti-redeposition properties of co-polymers comprising 50/50 MeVI/PVP dye-binding monomers and between 1 and 10% AA
was tested following the method used above under the heading "Redeposition Performance". The tests were repeated to check the accuracy (Rep 1 and Rep 2). This time carbon black, not an iron compound, was used. Tests A, B and C below refer to the formulation in which the anti-redeposition properties of the polymer was tested.
The control was the formulation in the absence of polymer. The MeVI/PVP/AA polymers were prepared following the method of Example 1. The method of EP-100-890 may also be used to produce the polymers.
Tergotometer, 40°C, 10 mins, 60 rpm.
Liquor: cloth 25:1 (270 mls:l0.8g) Demin water 4 13x13 cm white mercerised cotton pieces 1 g/1 synperonic A7 (Syn A7) 0.87 g/1 zeolite A24 (MAP) 1.5 mls 1% dispersion of carbon black in 1 g/1 synperonic A7 The water and carbon black dispersion were placed in the tergo pot and agitated. The active and zeolite were then added followed by the cloth. They were washed for 10 mins and then rinsed twice in demin. They were then spun and tumble dried and their reflectance values measured as above.
A) 1 g~Syn A7, 0.522 g/1 NazC03, 0.87 s/1 zeolite 5.56 mls/1, 1°s carbon black suspension, 25:1 liquor: cloth Polymer Delta E value of white monitor Rep Rep 2 Control 1.4 1.26 MeVI/VP 50:50 1.32 1.14 MeVI/VP/AA 50:50:3 1.14 0.84 MeVI/VP 50:50:5 1.34 0.95 MeVI/VP/AA 50:50:7 0.98 0.71 MeVI/VP/AA 50:50:10 1.08 0.59 B) 1 g/1 Syn A7, 0.522 g/1 Na2C03) no builder Polymer Delta E value of white monitor Rep 1 Rep 2 Control 6.81 5.09 MeVI/VP 50:50 2.42 2.08 MeVI/VP/AA 50:50:1 2.47 2.07 MeVI/VP/AA 50:50:3 0.96 1.25 C) 1 Q/1 Syn A7, 0.522 q/1 NaZC03) no builder Polymer Delta E value of white monitor Rep 1 Control 7.54 MeVI/VP 50:50 5.65 MeVI/VP/AA 50:50:1 5.96 MeVI/VP/AA 50:50:3 0.36 Tests A, B and C all show the benefits for anti-redeposition achieved by the MeVI/VP/AA co-polymers. In particular the 3%
and 7% AA exhibit excellent results. The anti-redeposition effect is achieved over a range of wash concentrations and both in the presence and absence of builder.
~..__~ _.____.~.__ ~ i (ii) Rede~,osition Screen The 50/50 MeVI/VP/AA co-polymers abpve were also tested as below.
Shakerbath, 40°C 30 mins, 100 rpm.
100 mls wash solution prepared with Prenton water (26.4°F).
150 mls HDPE bottles.
1 6x6cm Direct Red 80 test cloth.
2 1Ox10cm WFK10D test cloths.
1 13x13 cm white mercerised cotton.
1 g/1 80:20 LAS:NI tPetrelab 550:Synperonic A7) 0.522 g/1 Na2C03 0.87 g/1 STP
0.0218 g/1 polymer (=0.5% on formulation) The cloths, water, active and then polymer were placed in the poly bottle and then shaken for 30 mins. When the wash was complete the cloths were rinsed twice, spun dried and then tumbled. The reflectance values were measured on an ICS
texicon Spectraflash 500 using the flash 500 programme. These were converted to Delta E values using the 40ptspec programme.
Each wash was carried out in triplicate to minimise any experimental variation.
WO 98/30664 PCT/EP97l07327 Polymer E values of white monitors Rep 1 Rep 2 Rep 3 Average Control 14.81 12.66 10.23 12.57 MeVI/VP 15.74 14.88 15.18 15.27 50:50 MeVI/VP/AA 14.21 11.98 15.22 13.80 50:50:3 MeVI/VP/AA 10.96 12.96 13.63 12.52 50:50:5 MeVI/VP/AA 13.06 10.71 13.83 12.53 50:50:7 MeVI/VP/AA 8.94 13.99 12.83 11.92 50:50:10 The above table shows the good results for the anti-redeposition properties of the co-polymers.
Example 15~ MeVI/VP with AA in the presence of anionic and nonionic surfactants dye transfer performance.
MeVI/VP/AA polymers of varying MeVI/VP ratios and AA
concentrations were tested in a surfactant active system of varying anionic/nonionic ratios (LAS: N1 ratio).
Conditions: Shakerbath) 40°C, 30 mins, 100 rpm.
100 mls solution made with 26.4°F water in 150 HI7PE
bottle.
1 g/1 total active (combination of LAS and nonionic) 0.52 g/1 NaC03 0.87 g/1 STP
uM Direct Red 80 dye 0.0435 g/1 polymer 13x13cm piece white mercerised cotton sheeting.
I T
The dye transfer performance was tested as detailed above under the heading "Dye Transfer Performance".
Polymer Delta E values of white monitors LAS:NI ratio 100:0 90:10 75:25 60:40 0:100 Control 39.8 41.18 40.11 40 39.44 MeVI/VP/AA 39.6 38.8 32.5 22.6 9.4 50:50:1 MeVI/VP/AA 38.9 37.52 30.75 21.88 15.73 50:50:3 MeVI/VP/AA 38.28 38.13 32.35 25.43 22.91 33:66:3 MeVI/VP/AA 38.32 36.23 32.22 29.05 29.73 25:75:3 The MeVI/VP/AA polymers containing 3% AA were found to give higher 0E values and hence better performance across the range of anionic: nonionic (NI) ratios. In the predominantly nonionic surfactant systems particularly good results were obtained.
ExamQle 16~ MeVI/VP with nonionic monomers.
The dye transfer performance when PEG nonionic monomers were used was tested as for Example 15.
Polymer Delta E values of white monitors LAS:NI ratio 100:0 90:10 75:25 60:40 0:100 Control 40.54 40.33 41.10 40.06 38.4 MeVI/VP/PEG (MW 40.35 38.13 34.77 25.67 7.85 300)50:50:5 MeVI/VP/PEG (MW 39.73 38.14 34.10 24.60 9.76 6000) 50:50:5 The two examples showed good results for dye transfer performance especially in the presence of larger ratios of nonionic surfactant ratios.
Example 17~ VI copolymers with other anionic monomers.
The dye transfer performance of co-polymers of VI with either octanioic acid or hexanoic acid monomers was tested using the method of Example 15 and following the method detailed under the heading "Dye Transfer Performance". The control contained no co-polymer.
Polymer Delta values white monitors E of LAS:NI
ratio 100:0 90:10 75:25 60:40 0:100 Control 41.31 41.84 41.39 41.37 40.92 PVI/Octanoic 32.06 29.43 22.34 15.52 8.67 (94.4:5.6) PVI/Hexanoic 34.61 28.89 23.23 16.09 9.12 (92:8) Again the copolymers showed good dye-transfer inhibition performance especially in the presence of predominantly nonionic surfactant.
.._._.~._ ... __. ~
Example 18~ MeVI/VP with AA (50:50 with 3% AA) in a fabric softening composition.
The following fabric softening composition was prepared.
w/w Di-hardened tallow 5.7 6 dimethyl ammonium chloride Varisoft 460 18 di(hardened 13.5 tallowoyloxy)ethyl dimethyl ammonium chloride Fatty acid 2 Perfume 0.3 0.7 1.0 Co-polymer 0.25 0.5 0.75 water added balance balance balance Example 19~ Granular Main Wash Detergent Compositions Comprising the Copolymer Hand Wash Top Loading Front Loading %w/w %w/w %w/w NaLas 28 22 7 Soap 0 2 4 Carbonate 15 15 15 Zeolite 0 0 0 Sulphate 15.8 5.8 21.2 Silicate 8 8 8 Enzyme 0.6 1.0 0.6 Fluorescer 0.2 0.2 0.2 Co-polymer 0.5 0.75 0.25 The VP/MeVI/AA (50:50 with 3% AA) was included in various washing compositions as above.
Technical Field The present invention relates to a detergent composition and to a process for inhibiting dye transfer between fabrics during washing. In particular, the invention relates to detergent compositions containing novel dye-transfer inhibition copolymers.
Backaround of the Invention There is a tendency during the laundering of fabrics for coloured fabrics to release dye into the wash solution. This is a most persistent and troublesome problem as this released dye can then be transferred onto other fabrics. Afabric treatment composition comprising an agent which could prevent the transfer of dye would therefore prove useful.
EP462 806 (Unilever) discloses a domestic treatment of a fabric with a cationic dye fixing agent to reduce the amount of dye released from the fabric. Suitable cationic dye fixing agents include the dimethyldiallyl ammonium chloride polymer.
Surfactant-containing dye transfer inhibiting compositions are disclosed in EP 0 587 550 (Procter and Gamble). The dye transfer inhibition agent is a polymer selected from polyamine N-oxide containing polymers.
EP O 327 927 (Procter and Gamble) describes a granular detergent additive comprising water-soluble polymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidine and cationic compounds.
Detergent compositions comprising a N-vinylimidazole N-vinylpyrolidone copolymer are disclosed in EP 0 635 566 and EPo 635 565 (Procter and Gamble).
DE 42 24 762A (BASF AG) discloses the use of nitrogen-containing polymers as dye-transfer inhibitors in textile washing, the polymers contain a carbonyl or ester group with the esters being neutral in the co-polymer.
EP-A-0-631-008 (Ciba-Geigy AG) relates to an after-washing process for a dyeing operation in which a polyvinyl pyrrolidone homo or co-polymer, and, a water softener are used in the absence of a surfactant. The copolymer can contain comonomers such as those containing carboxyl groups, sulpho groups, phosphorous based groups or other ethylenically unsaturated monomers. Such non-surfactant dyeing after washing processes and compositions used in them are outside the scope of the present invention.
EP-0-100-890-A (BASF AG) discloses co-polymers obtained by the radical copolymerisation of monomers of C3-C2o alkyl ester of (meth)acrylic acid N-containing neutrally reacting water-soluble compounds, compounds containing cationic groups and olefinically unsaturated Cj-CS carboxylic acids. The polymers are used in hair treatment compositions.
.. __._... .. . _ . _.__-.
r ~. ~-.-..~._.~.... . ..
' CA 02277484 1999-07-09 Document #: 344111 WO 95/27759 discloses ink compositions comprising network forming or cross-linked polymers or resins, where the polymers may include a dye-binding copolymer.
EP 687 694 (BASF) discloses a process for the preparation of polymers base on vinyl imidazoles. The process relates to vinyl imidazole co-polymers and homopolymers.
WO 91 00302 (GAF) discloses terpolymers which are insoluble in heptane and which are produced form a reaction mixture of a vinyl lactam, a polymersible carboxylic acid and a hydrophobic monomer.
WO 95/00611 discloses floor cleaners comprising a copolymer of vinyl pyrrolidone and acrylic acid, dimethylaminoethyl methacrylate, vinyl acetate or methaminopropyl trimethyl ammonium chloride. The copolymers are used as shine boosters.
We have found that whilst these polymers of the prior art when used for dye transfer mitigation can be effective in preventing dye transfer under model conditions, in the presence of soil under normal laundering conditions they become ineffective, and can even lead to additional dye transfer.
Compositions of the present invention are directed towards overcoming this problem by using co-polymers which even in the presence of soil, retain their dye transfer inhibition properties.
Definition of the Invention Accordingly the present invention provides a fabric wash detergent composition comprising a co-polymer and at least one .'C::.,~~1~'~ ~~ c I~I=wcP
component selected from surface active agents and fabric softening compounds, the co-polymer comprising at least one dye binding monomer selected from vinyl azalactam monomers, vinyl azalactone monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, with the proviso that the co-polymer is not poly(1-vinylpyrrolidone-co-acrylic acid).
Of particular interest are dye binding co-polymers of poly(vinylpyrrolidone-co-polyvinylimidazole-co-acrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-polyvinylimidazole-co-methacrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-polymethylvinylimidazole-co-acrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-polymethylvinylimidazole-co-methacrylic acid).
The invention also relates to use of a co-polymer comprising at least one dye binding monomer selected from vinyl azalactone, vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof, and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, in a laundry treatment composition to mitigate dye transfer between fabrics.
The present invention further provides use of a co-polymer comprising at least one dye binding monomer selected from vinyl azalactone monomers, vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof, and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, to prevent redeposition of soil in fabric washing conditions.
r~ ~~, -» .~.-T
~; '.~~i:. :'~...,.._.... .-;'yes C3757 ' S -In particular co-polymers as defined above comprising 1-10% by weight acrylic acid or methacrylic acid monomers are of use.
The teen dye-binding monomer as used herein is used in relation to monomers which have a dye-binding capability when in their polymerised form i.e. the co-polymer comprising the polymerised dye-binding monomers has dye binding characteristics resulting from said monomer.
More specifically in the context of the present invention a dye binding monomer is defined as a monomer the homopolymer (mwt of 40,000-100,000) of which binds dye in water at pH at a temperature from 5°C to 60°C, preferably at a temperature of 20°C. However, with this proviso the dye binding homopolymer can bind dye under other conditions.
Detailed Description of the Invention The copolymers of the invention at least one dye binding monomer and at least one anionic or nonionic monomer.
Preferred polymers include vinyl pyrrolidone (VP), vinyl imidazole (VI), methyl vinyl imidazole (MeVI), vinyl pyridine, vinyl pyridine-N-oxide (VPy-N-0), vinyl oxazolidone.
i ;: :. ._ ~. -i ~ w ,~.- ,; ;._ r Especially preferred are vinyl imidazole, methyl vinyl imidazole (meVI) and vinyl pyridine-N-oxide, used alone or in combination with vinyl pyrrolidone and combinations thereof.
Any anionic monomer is suitable for use with the invention.
However it is preferred if the anionic moiety is based on a carboxy, sulphonate, sulphate, phosphate or phosponate containing material, especially preferred are short chain, polyTnerisable group carboxy containing material having at least one double bond. Preferred anionic monomers are itaconic acid, aconitic acid, mesaconic acid, citraconic acid, acrylic acid (AA), methacrylic acid (MA), octanoic acid, hexanoic acid, vinyl acetic acid, vinyl benzoic acid, vinyl sulphonic acid, vinyl benzene sulphonic acid, vinyl phosphoric acid and hydroxy acrylic oracetic acid. Especially preferred are AA, MA and vinyl sulphonic acid Examples of preferred copolymers are described below.
i ) ~~_ ~ ~~~~~y ( ii~~
CO~bI COibl N~ O
p R~ ~~~.Rn N ~N
~( CA~1 PAY( ~) ~CH~-~~CH~.CH-~-~CH=.CH~ "~"Ctl:_CRn~CHz.CH~
x r (iii) ~~ N ( Z O (iv) ~iM y ~W R"
N H
Poh(MIWwPI i O
~h( cNPY-~1 M ~ H) l~l~', K', IdH, CAS Carboxylic acid. X,Z,Z is the polmerisation number so . R = H, A1 mwt is achieved.
kyl; ~g Clip, CsH~, ate; n ~ t-4 inaependentaly of each other Y
For (ii) it is preferred that R' is H so that the polymer is poly(acrylic acid/VI/VP). It is possible that VI may have R' as CH3 i.e. be methyl vinyl imidazole which is another preferred co-polymer. This applies for each of (i)-(iii) above.
The weight ratio of anionic or nonionic monomertsa to the dye - binding monomers) within the co-polymer is preferably from 1:200 to 1:1, more preferably 1:15J to 1:2, most preferably 1:100 to 1:3.
It may be desirable to include additional monomers in these dye binding polymer. Examples of these additional monomers include vinyl alcohol, vinyl acetate, vinyl styrene, acrylamide, methyl methacrylate, hydroxyethyl acrylate/methacrylate, IEG
acrylate/methacrylate, glycidyl acrylate/methacrylate. The addition of these third monomers can cause changes in the properties of these polymers such as solubility, compatibility with liquid products and redeposition performance or sequestration ability. However, such further monomers may be .. _. , -. . ' ._. ~... .
';, '. : ,_ included if the properties of the co-polymers are not adversely affected.
Additional monomers may also be present for cost minimalisation) as a cross-linking moiety or to impart biodegradability. However, non-crosslinked co-polymers are preferred. The co-polymers of the present invention most preferably retain the anionic ar nonionic nature of the monomers within the co-polymer.
It is preferred if the co-polymer has an average molecular weight range from 2,000 to 200,000 more preferably from 5,000 to 100.000, most If the detergent composition is in liquid forth it is preferred if the co-polymer has a molecular weight range from 5,000 to 30,000. If the detergent composition is granular the preferred molecular weight is from 10,000 to 50,000.
The detergent compositions may comprise 0.001-5% w/w of the copolymer, preferably 0.1-3%, e.g. 0.1-2%, such as 0.1-1%.
In the context of the present invention the most preferred co-polymers are selected from the group consisting of:
a) co-polymers of PVP/PVI/AA, PVP/PVI/MA especially where the ratio of PVI/PVP is from 2:1 to 0.2:1, most preferably 1:1 to 0.3:1 b) co-polymers of PVI/AA, PVI/MA and:
c) co-polymers of PVPy-N-O/AA, PVPy-N-0/MA.
d) co-polymers of PVP/MePVI/AA, PVP/MePVI/MA especially where the weight ratio of PVP:PVI/MePVI is from 90:10 to 10:90, especially 75:25 to 25:75, e.g. 50:50.
_9 Co-polymers comprising at least one dye-binding monomer selected from VI, MeVI and VP where the anionic monomer is AA are especially preferred.
The ratio of VP/meVI or VI when two dye binding monomers are used together is preferably in the weight ratio range stated above in a) or d) .
It is also advantageous, especially for VP/meVI co-polymers if the anionic monomer, which is preferably AA or MA represents 1-10% w/w of the copolymer, especially 2-8%, most especially 2.5%-7% w/w. Excellent results for both the mitigation of dye transfer and anti-redeposition have been obtained with VP/meVI
co-polymers containing around 3% MA or AA, particularly when the ratio of the VP/meVI is within the range 90:10 to 10:90, preferably 75:25 to 25:75 e.g. 50:50.
In addition to dye transfer inhibition properties the compositions of the invention also exhibit excellent redeposition of soil properties. This is especially advantageous for the co-polymers of VP, with VI or MeVI, and AA or. MA.
The compositions of the invention comprise a component selected from surface active agents and fabric softening compounds. Typically at least one of the two aforementioned components will be present dependent upon the application.
The compositions of. the present invention are preferably laundry compositions, especially main wash compositions or rinse-added softening compositions.
The main wash compositions may include a fabric softening agent.
Surface Active Compounds The detergent compositions of the invention may contain a surface-active compound (surfactant) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof. Many suitable surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I
and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
It is preferred if the compositions of the invention contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of CR-CiS. It is preferred if the level of alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt%
to 15 wt%.
The detergent compositions of the invention may contain other anionic surfactants in amounts additional to the percentages quoted above. Suitable anionic surfactants are well-known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly Cg-C,5 primary alkyl r T _.__ ._...__... T ._..____m_._~..
sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred.
The compositions of the invention may also contain nonionic surfactant. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the cec,,) aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C,o-C,5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
It is preferred if the level of nonionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
The choice of surface-active compound (surfactant), and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions) different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wts surfactant e.g. 2-60a, preferably 15-40°s most preferably 5-35%.
Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
Fabric Softening Compounds Any conventional fabric softening compound may be used in the compositions of the present invention. The softening compounds may be cationic or nonionic. If the fabric softening compound is to be employed in a main wash detergent composition the compound will typically be nonionic.
The fabric softening compound is suitably a substantially water insoluble quaternary ammonium material comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to CZO or, more preferably, a compound comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C14.
Preferably the fabric softening compound has two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16. Most preferably at least 50~ of the long chain alkyl or alkenyl groups have a chain length of Cle or above It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
___._.~._..__.__...r.__~__.......
The fabric softening compounds used in the compositions of the invention are preferably compounds that provide excellent softening, and characterised by a chain melting L beta to L
alpha transition temperature greater than 25°C, preferably greater than 35°C, most preferably greater than 45°C. This L
beta to L alpha transition can be measured by DSC as defined in " Handbook of Lipid Bilayers, D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337).
Substantially insoluble fabric softening compounds in the context of this invention are defined as fabric softening compounds having a solubility less than 1 x10 3 wt % in deminerailised water at 20°C. Preferably the fabric softening compounds have a solubility less than 1 x10-' wt %. Most preferably the fabric softening compounds have a solubility less than 1 x10 8 to 1 x10 6.
Preferred fabric softening compounds are quaternary ammonium compounds. It is especially preferred if the fabric softening compound is a water insoluble quaternary ammonium material which comprises a compound having two C12-le alkyl or alkenyl groups connected to the molecule via at least one ester link.
It is preferred if the quaternary ammonium material has two ester links present. An especially preferred ester-linked quaternary ammonium material can be represented by the formula;
Rt R1 N (CHZ) ~-T-Rz (CHZ) n-T_R2 i wherein each R1 group is independently selected from C1_4 alkyl, hydroxyalkyl or C2_4 alkenyl groups; and wherein each R2 group is independently selected from CB_28 alkyl or alkenyl groups;
O O
T is -O-C- or -C-O-; and N is an integer from 0-5.
Di (tallowowyloxyethyl) dimethyl ammonium chloride is especially preferred.
A second preferred type of quaternary ammonium material can be represented by the formula;
(R~ ) 3N - (CHz) n CH
CHZOOCRz wherein Rl ( n and RZ are as defined above .
It is advantageous if the quaternary ammonium material is biologically biodegradable.
Preferred materials of this class such as 1,2 bis (hardened tallowoyloxy) -3- trimethylamQnonium propane chloride and their method of preparation are, for example, described in US 4 137 180 (lever Brothers). Preferably these materials comprise small amounts of the corresponding monoester as described in US
4 137 180 for example 1- hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.
Lecithins are also suitable softening compounds.
_..__.~s..~_~__~.__..__....
DeterQencv Builders The detergent compositions of the invention will generally also contain one or more detergency builders if they are for use in the main wash of a laundering process. The total amount of detergency builder in the compositions will typically suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates) for example, zeolites as disclosed in GH 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 5148 (Hoechst). Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
The detergent compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
0 . 8 -1 . 5 NazO . A1203 . 0 . 8 - 6 S i02 These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg Ca0/g.
The preferred sodium aluminosilicates contain 1.5-3.5 Si02 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the cocrnnercially available zeolite ~A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite M,~P>as described and claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33) preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite M~ having a silicon to aluminium ratio not exceeding 1.07.more preferably about 1.00. The calcium binding capacity of zeolite MAPis generally at least 150 mg Ca0 per g of anhydrous material.
Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, ._ _~_.-.~._-..,..
and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates,dipicolinates,hydroxyethyiiminodiacet ates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Bleach Components Detergent compositions according to the invention may also suitably contain a bleach system..Fabric washing compositions may desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt%, preferably from 0.5 to 25 wt%.
The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 0.1 to 8 wt%, preferably from 0.5 to 5 wt%.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernoanoic acid precursors. Especially preferred bleach precursors suitable for use in the present invention are N,N,N',N.-tetracetyl ethylenediamine (TAED) and sodium noanoyloxybenzene sulphonate (SNOBS). The novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP
402971A (Unilever), and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) are also of interest.
The bleach system can be either supplemented with or replaced by a peroxyacid. Examples of such peracids can be found in US 4 686 063 and US 5 397 501 (Unilever).
a preferred example is the imido peroxycarboxylic class of peracids described in EP A 325 288, EP A 349 940, DE 382 3172 r _._~._ __T..._~_w _. _ .__._.._ ~.
and EP 325 289. A particularly preferred example is phtalimido peroxy caproic acid (PAP). Such peracids are suitably present at 0.1 - 12% preferably 0.5 - 10%.
A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), the polyphosphonates such as bequest (Trade Mark) and non-phosphate stabilisers such as EDDS
(ethylene diamine di-succinic acid). These Bleach stabilisers are also useful for stain removal especially in products containing low levels of bleaching species or no bleaching species.
An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
The Enzyme The detergent compositions according to the invention may also contain an enzyme.
Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
Preferred proteolytic enzymes (proteases) are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.
Examples of suitable proteolytic enzymes are the stabilisins which are obtained from particular strains of B. subtilis B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark). The preparation of these and analogous enzymes is described in GB 1 243 785. Other commercial proteases are Kazusase (Trade Mark) (obtainable from Showa-Denko of Japan), Optimase (Trade Mark) (from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark) (obtainable from Pfizer of U.S..a. >.
Detergency enzymes are commonly employed in granular forth in amounts of from about 0.1 to about 3.0 wt%.
Other ingredients The compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scone of the invention.
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
Other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes;
coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive.
It is advantageous if soil release polymers are present as they enhance the dye transfer inhibition. Particularly preferred are soil release polymers based disclosed in WO 95/32997 A (Rhone Poulenc)), EP 219 048 (BASF)) GB 2 208 515 (Colgate), EP 253 567 (P-.G) The detergent composition when diluted in the wash liquor (during a typical wash cycle) will typically give a pH of the wash liquor from 7 to 10.5 for a main wash detergent.
The detergent components of the present invention may be incorporated in detergent compositions of all physical types, for example, powders, liquids, gels and solid bars.
Detergent compositions of the invention may be prepared by any suitable method.
Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/1, more preferably at least 500 g/1.
Especially preferred compositions have bulk densities of at least 650 g/litre, more preferably at least 700 g/litre.
Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a hiqh-speed mixer/granulator may advantageously be used.
Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever) .
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in compact form which means ___..~. ..._~. T ~..-.... T
it will contain a lower level of water compared to a conventional liquid detergent.
Examples The invention will now be illustrated by the following non-limiting examples. In the examples all percentages are expressed by weight. Further modifications within the scope of the present invention will be obvious to the skilled man.
Comparative Examples are designated by letters, while Examples of the invention are designated by numbers.
Preparation of Polymers The co-polymers of this invention can be produced by radical polymerisation of the appropriate monomers with or without a crosslinking agent. The polymerisation can be conducted in bulk, in solution (aqueous or organic media) also employing emulsion or suspension polymerisation techniques. Depending on the monomer reactivity ratios and their concentration, the co-polymers will have random or block nature.
Example 1 Co-polymerisation of Vinylimidazole & Acrylic Acid (95:5) 1-Vinylimidazole 47g (0.5 mol) Acrylic Acid 1.8g(25 mol) 1,4-Dioxane 250 ml 4,4-Azobis(4-cyanovaleric)acid(ACVA) 0.148 The radical polymerisation of 1-Vinylimidazole (0.5 mol) and Acrylic Acid was carried out under nitrogen. After degassing for 30 minutes, the reaction mixture was heated to 70°C and ACVA (0.5 mol) was added. The polymerisation reaction was stirred overnight under a nitrogen atmosphere until the reaction mixture turned cloudy.
The bulk of the dioxane was removed and sodium hydroxide solution was added to neutralise the acrylic acid. The remaining dioxane/water was removed, the sample was redissolved in water and freeze dried.
NMR Analysis indicate that the co-polymer contains between 4-80 of acrylic acid monomer. GPC Molecular weights against polyethylene glycol standards are: Mn 40970, Mw 137900, D3.366.
....___.._ ..... _T_._.. _. ~_....___. . ...
Example 2 Co-Polymerisation of Vinylimidazole & Acrylic Acid (50:50) 1-Vinylimidazole 18.88 (0.2 mol) Acrylic Acid 14.4g (0.2 mol) 1,4-Dioxane 300 ml 4,4-Azobis(4-cyanovaleric)acid(ACVA) 0.5g The polymerisation was carried out as example 1, but with different monomer ratios. After the polymerisation completed, sodium hydroxide solution was added to the stirred reaction product and the polymer precipitated out. The polymer was redissolved in water and freeze dried or precipitated out using methanol (three times).
NMR spectrum shows that the copolymer contains about 75 acrylic acid monomer.
Example 3 Co-Polymerlsation of Vinylimidazole ~ Acrylic Acid (80:20) 1-Vinylimidazole 25.8g (0.274 mol) Acrylic Acid 3.95g(55 mol) 1,4-Dioxane 250 ml 4,4-Azobis(4-cyanovaleric) acid (ACVA) 0.2g The polymerisation was carried out as example 1, but with different monomer ratios. After the polymerisation completed, sodium hydroxide solution was added to the stirred reaction product and the polymer precipitated out. The polymer was redissolved in water and freeze dried or precipitated out using methanol (three times).
NMR analysis indicate that the co-polymer contains about 18 of acrylic acid monomer.
Dye Transfer Performance Conditions: Shakerbath, 40°C, 30 rains, 100 rpm lOOmls solution made with 26.4°FH water lg/1 total surfactant (combinations of LAS and E07) 0.522g/1 NaC03 0.87g/1 STP
lOuM Direct Red 80 dye 13x13cm white mercerised cotton 0.0435q/1 polymer After washing, the cloths were rinsed and tumble dried.
Their reflectances were measured on a ICS Texicon Spectraflash 500, and the results are given in Table 1 below as delta E values, calculated from the reflectance values.
The delta E values shown in the table are differences between washed and unwashed cotton. A high value of delta E
corresponds to more dye transfer than a low value.
Table 1 Example Dye Tranater Ratio of L71.9 : E07 inhibition agent polymer 100:0 90:10 75:25 60:10 0:100 None 41.63 41.63 42.51 41.72 38.77 pVp 41.26 40.06 37.41 26.6 23.82 r PVP/AA (95:51 40.89 pVI 36.55 32.87 25.36 21.55 17.08 q PVI/AA(94:6) 36.03 32.23 26.75 23.68 17.25 pVI/p,p, 37.76 37.03 29.52 25.77 24.41 (83:17) In addition to the above it was found that a simple ~esr.
using soiled fabrics predicts negative interactions between the formulation, dye transfer polymer and soil, but it does not predict positive benefits. It can therefore be used as a gross negative test to distinguish polymers which can give a negative in machine tests (worse than the control in the model test), from those Which will either have no effect, or . f.. ... _. .,.,....~.................. T ....
have benefits in the machine tests (equal to or better than the control) at the higher anionic ratios.
White cotton monitors were washed together with a piece of dyed test cloth and a piece of soiled test cloth for 30 mins at 40°C in a solution containing lg/1 active (80:20 LAS/NI), STP and NaC03 made with Prenton water (26.4°FH). Polymer was added at 0.0218g/1. The delta E values were calculated from the reflectance values of the white monitors and the results compared to the control (no polymer present).
Table 2 Example Dye Traaater Delta 8 Inhibition Polymer g None 10.19 g pVP 13.18 G PVP/PVI 12.42 PVI 14.04 PVP/AA (95:5) 13.27 6 PVI/AA (94.:6) 9.45 The results for PVP, PVI and PVP/PVI are significantly worse than the control, and this correlates with the relatively poor Performance of PVP and PVP/PVI in the washing machine.
In accordance with the invention the inclusion of anionic monomers in the co-polymer of PVI has significantly reduced its tendency to interact with soil, whilst not affecting its ability to bind dyes in solution.
Redeposition performance The redeposition performance of the polymers of the invention was investigated by evaluating their ability to prevent the transfer of iron oxide forth prestained fabric on to clean cotton monitor cloths. (0.5 mls of a 1% dispersion of iron (III) oxide was pipetted onto each monitor cloth and allowed to dry overnight).
Experiments were conducted in a tergotometer at 60rpm, 4oC, lOmin using demineralised water.
The reflectance of the monitor cloths was measured as in Example 1 and delta E values calculated.
The formulation was:
lg/1 nonionic surfactant (E07) 0.87g/L STP
0.522g/L sodium carbonate 0.1305g/L g co-polymer (absent for the control) Table 3 Example Dye Tanefer Delta E
Inhibition Polymer None 5.06 PVI 3.79 7 PVI/AA (83:17) 2.84 g PVI/AA(94:6) 3.19 There is thus a clear benefit for pvI/~ polymers.
Example 5 - Dye solubilisation Without wishing to be bound by theory, it is desirable for the polymers of the invention to have lower solubilising capacities compared to the homopolymers of the dye scavenging monomers. Orange OT, a sparingly water soluble dye from Aldrich, was purified by recrystalising twice from a .. _. .. __.. . _. .__...~..~_-.____.. _ . _ r..~~......N _ .
water/ethanol mixture. This purified dye was then dissolved in acetone (lOmg/ml).
30u1 (=0.3mg dye) of this solution was added to a vial containing water. The other components were then added: 0.25g/1 active (a combination of LAS and non-ionic), 0.522g/1 Na2C03) 0.87g/1 STP and 0.1088g/1 polymer (absent for the control). The total solution was lOmls made with demin water. The vials containing the solutions were then shaken for 24 hours at 30°C.
They were then centrifuged at 13,000 rpm for 10 mins to separate out the undissolved dye. The absorbance of the solutions was measured on a Perkin-Blmer Lambda 16 spectrophotometer at 492nm. In the table below Dye solubilised refers to the increase in absorbance of solutions (492nm) due to additional dye solubilised compared to the control without polymer.
Table 4 gxam~le Dye Traneter Dye Solubiliaed Inhibition Polymer 50/50 LAS/E07 pVI 0.031 9 PVI/AA (99:6) 0.021 PVI/AA (83:17) 0.003 The results clearly show that the incorporation of anionic groups in the polymer has depressed the ability of the polymer-surfactant complexes to solubilise the water insoluble dye.
Examples 11 and 12 A liquid detergent composition was prepared having the following composition.
Table 5 Wt. $
Ingredient Example 11 Example 12 Alkyl Sulphate - 10 Linear Alkyl Benzene 10 -Sulphonate Alkyl ethoxy sulphate Fatty alcohol ethoxylate 7E0 6 6 Sodium Citrate 2H,0 4 4 Propylene glycol Sorbitol 4.5 4.5 Na tetra-borate 5H20 3 3 Enzyme to 2$ to 2$
Soil release polymer to 2$ to 2$
PVI/AA 94:6 0.1 to 1 0.1 to 1 water/minors to 100 to 100 i r _.. _.... ~_... T ._ ._~..._~.. ... _ . .
Example 13 Table 6 The following powdered compositions were prepared.
NaLAS 7.1 NI 7E0 4.7 NI 3E0 3.5 Soap 0.3 Fatty Acid 0.3 STPP 27.1 SCMC 0.2 Na silicate 7.1 CP5 polymer 1.2 Sulphate 16.5 Soil release polymer 0.4 PVI/AA polymer 0.1-1 EAG 1.28 Carbonate 12.00 Bicarbonate 6.00 0.18 Protease Lipase/Amylase 0.30 Clay 0 to 10$
Cationic surfactant 0 to 2$
Perfume 0.17 Salts/water to 100 ' Table 7 Na PAS 11.5 NI 7E0 6.3 Soap 2.0 Zeolite A24 24.1 SCMC 0.6 Na Citrate 10.6 Carbonate 23.0 Soil release polymer 0.8 EpG 3.7 PVI/AA 94.6 copolymer 0.1 to 1 Fluorescer EDTMP 0.4 Percarbonate CP5 type polymer 0.9 Protease Lipase 0.1 Perfume 0.4 water/salts to 100 The formulations of Tables 5,6 and 7 had excellent cleaning and detergency performances with outstanding colour: care performance on coloured fabrics and mixed loads of coloured and white fabrics.
_ _ ___~.. _ . T_ Example (14)~ Anti redeposition results for a copolymer of MeVI/VP/AA.
The anti-redeposition properties of co-polymers comprising 50/50 MeVI/PVP dye-binding monomers and between 1 and 10% AA
was tested following the method used above under the heading "Redeposition Performance". The tests were repeated to check the accuracy (Rep 1 and Rep 2). This time carbon black, not an iron compound, was used. Tests A, B and C below refer to the formulation in which the anti-redeposition properties of the polymer was tested.
The control was the formulation in the absence of polymer. The MeVI/PVP/AA polymers were prepared following the method of Example 1. The method of EP-100-890 may also be used to produce the polymers.
Tergotometer, 40°C, 10 mins, 60 rpm.
Liquor: cloth 25:1 (270 mls:l0.8g) Demin water 4 13x13 cm white mercerised cotton pieces 1 g/1 synperonic A7 (Syn A7) 0.87 g/1 zeolite A24 (MAP) 1.5 mls 1% dispersion of carbon black in 1 g/1 synperonic A7 The water and carbon black dispersion were placed in the tergo pot and agitated. The active and zeolite were then added followed by the cloth. They were washed for 10 mins and then rinsed twice in demin. They were then spun and tumble dried and their reflectance values measured as above.
A) 1 g~Syn A7, 0.522 g/1 NazC03, 0.87 s/1 zeolite 5.56 mls/1, 1°s carbon black suspension, 25:1 liquor: cloth Polymer Delta E value of white monitor Rep Rep 2 Control 1.4 1.26 MeVI/VP 50:50 1.32 1.14 MeVI/VP/AA 50:50:3 1.14 0.84 MeVI/VP 50:50:5 1.34 0.95 MeVI/VP/AA 50:50:7 0.98 0.71 MeVI/VP/AA 50:50:10 1.08 0.59 B) 1 g/1 Syn A7, 0.522 g/1 Na2C03) no builder Polymer Delta E value of white monitor Rep 1 Rep 2 Control 6.81 5.09 MeVI/VP 50:50 2.42 2.08 MeVI/VP/AA 50:50:1 2.47 2.07 MeVI/VP/AA 50:50:3 0.96 1.25 C) 1 Q/1 Syn A7, 0.522 q/1 NaZC03) no builder Polymer Delta E value of white monitor Rep 1 Control 7.54 MeVI/VP 50:50 5.65 MeVI/VP/AA 50:50:1 5.96 MeVI/VP/AA 50:50:3 0.36 Tests A, B and C all show the benefits for anti-redeposition achieved by the MeVI/VP/AA co-polymers. In particular the 3%
and 7% AA exhibit excellent results. The anti-redeposition effect is achieved over a range of wash concentrations and both in the presence and absence of builder.
~..__~ _.____.~.__ ~ i (ii) Rede~,osition Screen The 50/50 MeVI/VP/AA co-polymers abpve were also tested as below.
Shakerbath, 40°C 30 mins, 100 rpm.
100 mls wash solution prepared with Prenton water (26.4°F).
150 mls HDPE bottles.
1 6x6cm Direct Red 80 test cloth.
2 1Ox10cm WFK10D test cloths.
1 13x13 cm white mercerised cotton.
1 g/1 80:20 LAS:NI tPetrelab 550:Synperonic A7) 0.522 g/1 Na2C03 0.87 g/1 STP
0.0218 g/1 polymer (=0.5% on formulation) The cloths, water, active and then polymer were placed in the poly bottle and then shaken for 30 mins. When the wash was complete the cloths were rinsed twice, spun dried and then tumbled. The reflectance values were measured on an ICS
texicon Spectraflash 500 using the flash 500 programme. These were converted to Delta E values using the 40ptspec programme.
Each wash was carried out in triplicate to minimise any experimental variation.
WO 98/30664 PCT/EP97l07327 Polymer E values of white monitors Rep 1 Rep 2 Rep 3 Average Control 14.81 12.66 10.23 12.57 MeVI/VP 15.74 14.88 15.18 15.27 50:50 MeVI/VP/AA 14.21 11.98 15.22 13.80 50:50:3 MeVI/VP/AA 10.96 12.96 13.63 12.52 50:50:5 MeVI/VP/AA 13.06 10.71 13.83 12.53 50:50:7 MeVI/VP/AA 8.94 13.99 12.83 11.92 50:50:10 The above table shows the good results for the anti-redeposition properties of the co-polymers.
Example 15~ MeVI/VP with AA in the presence of anionic and nonionic surfactants dye transfer performance.
MeVI/VP/AA polymers of varying MeVI/VP ratios and AA
concentrations were tested in a surfactant active system of varying anionic/nonionic ratios (LAS: N1 ratio).
Conditions: Shakerbath) 40°C, 30 mins, 100 rpm.
100 mls solution made with 26.4°F water in 150 HI7PE
bottle.
1 g/1 total active (combination of LAS and nonionic) 0.52 g/1 NaC03 0.87 g/1 STP
uM Direct Red 80 dye 0.0435 g/1 polymer 13x13cm piece white mercerised cotton sheeting.
I T
The dye transfer performance was tested as detailed above under the heading "Dye Transfer Performance".
Polymer Delta E values of white monitors LAS:NI ratio 100:0 90:10 75:25 60:40 0:100 Control 39.8 41.18 40.11 40 39.44 MeVI/VP/AA 39.6 38.8 32.5 22.6 9.4 50:50:1 MeVI/VP/AA 38.9 37.52 30.75 21.88 15.73 50:50:3 MeVI/VP/AA 38.28 38.13 32.35 25.43 22.91 33:66:3 MeVI/VP/AA 38.32 36.23 32.22 29.05 29.73 25:75:3 The MeVI/VP/AA polymers containing 3% AA were found to give higher 0E values and hence better performance across the range of anionic: nonionic (NI) ratios. In the predominantly nonionic surfactant systems particularly good results were obtained.
ExamQle 16~ MeVI/VP with nonionic monomers.
The dye transfer performance when PEG nonionic monomers were used was tested as for Example 15.
Polymer Delta E values of white monitors LAS:NI ratio 100:0 90:10 75:25 60:40 0:100 Control 40.54 40.33 41.10 40.06 38.4 MeVI/VP/PEG (MW 40.35 38.13 34.77 25.67 7.85 300)50:50:5 MeVI/VP/PEG (MW 39.73 38.14 34.10 24.60 9.76 6000) 50:50:5 The two examples showed good results for dye transfer performance especially in the presence of larger ratios of nonionic surfactant ratios.
Example 17~ VI copolymers with other anionic monomers.
The dye transfer performance of co-polymers of VI with either octanioic acid or hexanoic acid monomers was tested using the method of Example 15 and following the method detailed under the heading "Dye Transfer Performance". The control contained no co-polymer.
Polymer Delta values white monitors E of LAS:NI
ratio 100:0 90:10 75:25 60:40 0:100 Control 41.31 41.84 41.39 41.37 40.92 PVI/Octanoic 32.06 29.43 22.34 15.52 8.67 (94.4:5.6) PVI/Hexanoic 34.61 28.89 23.23 16.09 9.12 (92:8) Again the copolymers showed good dye-transfer inhibition performance especially in the presence of predominantly nonionic surfactant.
.._._.~._ ... __. ~
Example 18~ MeVI/VP with AA (50:50 with 3% AA) in a fabric softening composition.
The following fabric softening composition was prepared.
w/w Di-hardened tallow 5.7 6 dimethyl ammonium chloride Varisoft 460 18 di(hardened 13.5 tallowoyloxy)ethyl dimethyl ammonium chloride Fatty acid 2 Perfume 0.3 0.7 1.0 Co-polymer 0.25 0.5 0.75 water added balance balance balance Example 19~ Granular Main Wash Detergent Compositions Comprising the Copolymer Hand Wash Top Loading Front Loading %w/w %w/w %w/w NaLas 28 22 7 Soap 0 2 4 Carbonate 15 15 15 Zeolite 0 0 0 Sulphate 15.8 5.8 21.2 Silicate 8 8 8 Enzyme 0.6 1.0 0.6 Fluorescer 0.2 0.2 0.2 Co-polymer 0.5 0.75 0.25 The VP/MeVI/AA (50:50 with 3% AA) was included in various washing compositions as above.
Claims (13)
1. A fabric wash detergent composition comprising a co-polymer and at least one component selected from surface active agents and fabric softening compounds, the co-polymer comprising at least one dye binding monomer selected from vinyl azalactam monomers, vinyl azalactone monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, with the proviso that the co-polymer is not poly(1-vinylpyrrolidone-co-acrylic acid).
2. A detergent composition according to claim 1 in which the anionic monomer of the copolymer is derived from acrylic acid, methacrylic acid, vinyl sulphonic acid, octanoic acid, hexanoic acid, itaconic acid, hydroxy acetic acid or mixtures thereof.
3. A detergent composition according to any preceding claim in which the dye binding monomer comprises at least one monomer selected from vinyl imidazole, methyl vinyl imidazole, vinyl pyridine-N-oxide, N-vinyl pyrrolidone and mixtures thereof.
4. A detergent composition according to any preceding claim in which the dye binding monomer comprises at least one dye binding monomer(s) selected from vinyl imidazole, methyl vinyl imidazole and N-vinylpyrrolidone and the anionic monomer is acrylic acid.
5. A detergent composition according to any preceding claim in which the co-polymer is a co-polymer of poly(N-vinylpyrrolidone-co-polyvinylimidazole-co-acrylic acid) or a co-polymer of poly(N-vinylpyrrolidone-co-polyvinylimidazole-co-methacrylic acid) or poly(N-vinylpyrrolidone-co-polymethylvinylimidazole-co-acrylic acid) or poly(N-vinylpyrrolidone-co-poly methyl vinyl imidazole-co-acrylic acid).
6. A detergent composition according to claim 5 wherein the copolymer comprises 1-10% w/w acrylic acid or methacrylic acid and the weight ratio of N-vinyl pyrrolidone to vinylimidazole or methylvinylimidazole is within the range 90:10 to 10:90.
7. A detergent composition according to any preceding claim in which the molecular weight of the co-polymer is from 5,000 to 70,000.
8. A detergent composition according to any preceding claim in which the ratio of monomer selected from anionic monomers and polyethylene glycols to the dye binding monomer within the co-polymer is from 1:100 to 1:3.
9. A detergent composition according to any preceding claim that comprises at least 2% w/w surfactant active agents and/or fabric softening agents.
10. A detergent composition according to any preceding claim wherein the surface active agent comprises a nonionic and/or anionic surfactant.
11. A detergent composition according to any preceding claim that further comprises a builder.
12. Use of a co-polymer comprising at least one dye binding monomer selected from vinyl azalactone monomers, vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof, and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, in a laundry treatment composition to mitigate dye transfer between fabrics.
13. Use of a co-polymer comprising at least one dye binding monomer selected from vinyl azalactone monomers, vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof, and at least one monomer selected from anionic monomers and ethylenically unsaturated polyethylene glycol derivatives, to prevent redeposition of soil in fabric washing conditions.
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EP97300122.5 | 1997-01-10 | ||
EP97300122 | 1997-01-10 | ||
PCT/EP1997/007327 WO1998030664A1 (en) | 1997-01-10 | 1997-12-24 | Detergent compositions and copolymers for inhibiting dye transfer |
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EP (1) | EP0964905A1 (en) |
CN (1) | CN1255157A (en) |
AR (1) | AR011388A1 (en) |
AU (1) | AU5764798A (en) |
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CA (1) | CA2277484A1 (en) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7119058B2 (en) | 2001-11-16 | 2006-10-10 | Basf Aktiengesellschaft | Graft polymers comprising side chains containing cyclic N-vinylamides |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9820552D0 (en) * | 1998-09-21 | 1998-11-11 | Unilever Plc | Fabric conditioning compositions |
DE102004020544A1 (en) | 2004-04-27 | 2005-11-24 | Basf Ag | Copolymers with N-heterocyclic groups and their use as additives in detergents |
US20120032093A1 (en) * | 2010-08-03 | 2012-02-09 | Kemira Chemicals Inc. | Tagged scale inhibitor compositions and methods of inhibiting scale |
EP3421583A1 (en) | 2017-06-26 | 2019-01-02 | Basf Se | Use of cationic vinylcarboxamide/vinylamine copolymers as a color care agent for laundering formulations |
CN109776739B (en) * | 2018-12-29 | 2021-09-14 | 广州星业科技股份有限公司 | Macromolecular anti-cross-color builder |
AU2020227836B2 (en) | 2019-02-28 | 2022-09-22 | Ecolab Usa Inc. | Hardness additives and block detergents containing hardness additives to improve edge hardening |
CN111848868B (en) * | 2020-07-16 | 2022-05-13 | 重庆市化工研究院有限公司 | Copolymer and preparation method and application thereof |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4368146A (en) * | 1979-01-12 | 1983-01-11 | Lever Brothers Company | Light duty hand dishwashing liquid detergent composition |
DE3227334A1 (en) * | 1982-07-22 | 1984-01-26 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATE AND THEIR USE IN HAIR TREATMENT PRODUCTS |
US5015708A (en) * | 1989-06-26 | 1991-05-14 | Gaf Chemicals Corporation | Precipitation polymerization of terpolymers of a vinyl lactam, a polymerizable carboxylic acid and a hydrophobic monomer in an aliphatic hydrocarbon solvent |
DE4224762A1 (en) * | 1992-07-27 | 1994-02-03 | Basf Ag | Polymers for use as dye-transfer inhibitors in textile washing - contain 2-pyrrolidone deriv. units and are prepd by reacting monomer with ethylenically unsatd comonomers e.g. (meth)acrylamide. |
EP0631008B1 (en) * | 1993-05-24 | 1999-08-18 | Ciba SC Holding AG | Process for the washing of printings or dyeings on cellulose containing textile materials |
US5409639A (en) * | 1993-06-25 | 1995-04-25 | Verona Inc. | Hardwood floor cleaner composition |
US5973025A (en) * | 1994-04-12 | 1999-10-26 | Sri International | Aqueous ink compositions containing a binder of a neutralized acidic resin |
DE4421178A1 (en) * | 1994-06-17 | 1995-12-21 | Basf Ag | Process for the preparation of polymers based on 1-vinylimidazoles |
DE19519339A1 (en) * | 1995-05-26 | 1996-11-28 | Basf Ag | Water-soluble copolymers containing copolymerized crosslinkers, process for their preparation and their use |
DE19646437A1 (en) * | 1996-11-11 | 1998-05-14 | Basf Ag | Use of quaternized vinylimidazole units containing polymers as a color-fixing and dye transfer-inhibiting additive to laundry after-treatment agents and to detergents |
-
1997
- 1997-12-24 ID IDW990659D patent/ID23930A/en unknown
- 1997-12-24 HU HU0001073A patent/HUP0001073A3/en unknown
- 1997-12-24 CA CA002277484A patent/CA2277484A1/en not_active Abandoned
- 1997-12-24 WO PCT/EP1997/007327 patent/WO1998030664A1/en not_active Application Discontinuation
- 1997-12-24 PL PL97334474A patent/PL334474A1/en unknown
- 1997-12-24 BR BR9714275-1A patent/BR9714275A/en not_active Application Discontinuation
- 1997-12-24 CN CN97182011A patent/CN1255157A/en active Pending
- 1997-12-24 AU AU57647/98A patent/AU5764798A/en not_active Abandoned
- 1997-12-24 EP EP97953933A patent/EP0964905A1/en not_active Withdrawn
-
1998
- 1998-01-09 AR ARP980100101A patent/AR011388A1/en unknown
- 1998-01-09 ZA ZA9800173A patent/ZA98173B/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7119058B2 (en) | 2001-11-16 | 2006-10-10 | Basf Aktiengesellschaft | Graft polymers comprising side chains containing cyclic N-vinylamides |
Also Published As
Publication number | Publication date |
---|---|
CN1255157A (en) | 2000-05-31 |
EP0964905A1 (en) | 1999-12-22 |
PL334474A1 (en) | 2000-02-28 |
HU0001073B (en) | 2000-09-28 |
AR011388A1 (en) | 2000-08-16 |
WO1998030664A1 (en) | 1998-07-16 |
ID23930A (en) | 2000-06-02 |
BR9714275A (en) | 2000-04-18 |
HUP0001073A3 (en) | 2003-02-28 |
AU5764798A (en) | 1998-08-03 |
ZA98173B (en) | 1999-07-09 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |