EP0143491B1 - Detergent composition - Google Patents
Detergent composition Download PDFInfo
- Publication number
- EP0143491B1 EP0143491B1 EP84201655A EP84201655A EP0143491B1 EP 0143491 B1 EP0143491 B1 EP 0143491B1 EP 84201655 A EP84201655 A EP 84201655A EP 84201655 A EP84201655 A EP 84201655A EP 0143491 B1 EP0143491 B1 EP 0143491B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- dye
- peracid
- bleaching
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000003599 detergent Substances 0.000 title claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- 239000004744 fabric Substances 0.000 claims abstract description 36
- -1 peracid compound Chemical class 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 22
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 16
- 150000004967 organic peroxy acids Chemical class 0.000 claims abstract description 9
- 239000003352 sequestering agent Substances 0.000 claims abstract description 7
- 239000007844 bleaching agent Substances 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 238000004061 bleaching Methods 0.000 abstract description 35
- 238000012546 transfer Methods 0.000 abstract description 20
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 82
- 239000000243 solution Substances 0.000 description 29
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 12
- 229910001428 transition metal ion Inorganic materials 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- KXEMXOYVVPLGSD-UHFFFAOYSA-N benzene-1,3-dicarboperoxoic acid Chemical compound OOC(=O)C1=CC=CC(C(=O)OO)=C1 KXEMXOYVVPLGSD-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000010668 complexation reaction Methods 0.000 description 5
- 239000008233 hard water Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UFUQRRYHIHJMPB-DUCFOALUSA-L Sirius red 4B Chemical compound [Na+].[Na+].OS(=O)(=O)c1cc2cc(NC(=O)c3ccccc3)ccc2c([O-])c1\N=N\c1ccc(cc1)\N=N\c1ccc(cc1)S([O-])(=O)=O UFUQRRYHIHJMPB-DUCFOALUSA-L 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229960001922 sodium perborate Drugs 0.000 description 4
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008364 bulk solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 1
- MDBGGTQNNUOQRC-UHFFFAOYSA-N Allidochlor Chemical compound ClCC(=O)N(CC=C)CC=C MDBGGTQNNUOQRC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- PGZPBNJYTNQMAX-UHFFFAOYSA-N dimethylazanium;methyl sulfate Chemical compound C[NH2+]C.COS([O-])(=O)=O PGZPBNJYTNQMAX-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- IILQHMMTOSAJAR-UHFFFAOYSA-L disodium;2-(carboxylatomethoxy)acetate Chemical compound [Na+].[Na+].[O-]C(=O)COCC([O-])=O IILQHMMTOSAJAR-UHFFFAOYSA-L 0.000 description 1
- LCZPIYCNOWJWPQ-UHFFFAOYSA-I disodium;chromium(3+);1-[(2-oxidonaphthalen-1-yl)diazenyl]-4-sulfonaphthalen-2-olate;3-oxido-4-[(2-oxidonaphthalen-1-yl)diazenyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].[Cr+3].C12=CC=CC=C2C(S(=O)(=O)O)=CC([O-])=C1N=NC1=C([O-])C=CC2=CC=CC=C12.C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3[O-])=C([O-])C=C(S([O-])(=O)=O)C2=C1 LCZPIYCNOWJWPQ-UHFFFAOYSA-I 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005453 pelletization Methods 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
- 239000002304 perfume Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 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
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
Definitions
- This invention relates to fabric-washing detergent compositions which are especially designed for the washing of coloured or mixed coloured and white fabric loadings.
- Hitherto fabric-washing detergent compositions of two types were available, i.e. (1) washing products of a non-bleaching type for coloured fabrics, which, although safe for the fabric dyes themselves, are not effective to prevent the tendency of some coloured fabrics to release into the wash liquor dyes which are then transferred during the washing process onto other fabrics being washed therewith; and (2) a bleach-containing fabric-washing product type which can inhibit dye transfer to a certain extent but at the same time will cause bleaching and fading of the colours of the fabrics.
- washing products of a non-bleaching type for coloured fabrics which, although safe for the fabric dyes themselves, are not effective to prevent the tendency of some coloured fabrics to release into the wash liquor dyes which are then transferred during the washing process onto other fabrics being washed therewith
- a bleach-containing fabric-washing product type which can inhibit dye transfer to a certain extent but at the same time will cause bleaching and fading of the colours of the fabrics.
- dye-transfer-inhibiting compositions which comprise a peroxygen compound, e.g. an organic peroxyacid, combined with rather complex aldehyde or ketone compounds as bleach activator.
- a peroxygen compound e.g. an organic peroxyacid
- aldehyde or ketone compounds rather complex aldehyde or ketone compounds
- compositions having dye-transfer inhibitory effects are disclosed in European Patent 0024367 (based on the activation of organic peracids with bromide ions) and European Patent Application 0024368 (based on a system comprising an organic peracid precursor and a bromide activator). Still, the main drawback of these compositions is that they too exert a rather strong direct fabric bleaching, tending to cause fading of the coloured fabrics.
- European Patent Application 0058444 describes washing compositions useful for the reduction of dye transfer in fabric washing at lower temperatures, comprising a bleach system consisting essentially of an organic peracid or an organic peracid precursor in conjunction with a water-soluble iodide salt.
- a bleach system consisting essentially of an organic peracid or an organic peracid precursor in conjunction with a water-soluble iodide salt.
- iodide catalyst There are some snags in the use of iodide catalyst, i.e. 1) the risk of staining due to iodine formation and 2) the effect of direct fabric dye bleaching.
- Heavy metals including copper have been proposed as catalyst for enhancing the decomposition or bleaching performance of peroxygen bleaching agents e.g. in EP-A-72166.
- transition metal ions can catalyse dye bleaching in solution by oxygen bleaches. So hydrogen peroxide or hydrogen peroxide adducts, inorganic persalt/bleach activator systems and peroxyacids per se can all be activated by copper ions. However, it has been found that copper-catalysed peracid bleach systems were much more effective than copper-catalysed hydrogen peroxide systems (e.g. sodium perborate).
- transition-metal-catalysed dye bleaching has only been achieved with transition metal ions which are easily capable of one-electron radox processes leading to the formation of reactive radicals.
- transition metal ions which are easily capable of one-electron radox processes leading to the formation of reactive radicals.
- Table I only copper and possibly cobalt gave catalysis of peracetic acid for dye bleaching, whereas all the other metals including chromium and zinc are inactive.
- transition metal ions are well known to interact with peroxide compounds as in Route B above, thus inducing decomposition to radicals or radical species which are known to have high oxidation potential and are capable of oxidizing most unsaturated molecules, no other transition metals are as effective for dye transfer inhibition as copper.
- Cupric ion being the smallest divalent transition metal ion, with the highest charge density, most readily forms stable complexes.
- Cobalt III and chromium III complexes of dyes are also very stable, but apparently they are kinetically inert and, in contrast to copper, severe conditions are generally necessary to introduce cobalt III and chromium III into dye structures.
- manganese which is known to be very useful for catalysing stain bleaching, especially with hydrogen peroxide bleaches in the presence of a carbonate, has proved to be ineffective for dye transfer inhibition. Experiments have even shown that under practical conditions manganese can inhibit the catalytic effect of copper, and so the presence of manganese ions in the system of the invention should preferably be avoided.
- the invention provides a fabric washing detergent composition especially designed for washing mixed coloured fabrics comprising a surfactant, a detergency builder, a bleaching agent and a heavy metal compound, characterized in that it comprises as the bleaching agent an organic peracid or a peracid salt in an amount of 0.5 to 25% by weight and a hydrogen peroxide adduct in a molar ratio to said peracid or peracid salt of from 1:100 to 2:1, and as the heavy metal compound a Copper compound in an amount of from 0.002 to 2.5% by weight of Copper(11)-ion, said composition having a solution pH (5 g/I) of 7 to 11 and being free of a sequestrant which complexes more strongly with Copper than EDTA.
- cupric ion concentration The influence of cupric ion concentration on an experiment of dye transfer inhibition is shown in the following Table 11 for the peracid bleaches monopersulphate, diperisophthalic acid and magnesium monoperphthalate, with and without sodium perborate.
- the detergent base used in the experiments had the following composition:
- CI Direct Red 81 (0.002 g/I), peracid (4.6x10 -4 g. atoms of active oxygen), pH stat. at 40°C.
- the diperisophthalic acid used was a commercial product "Suprox®”; monopersulphate used was a commercial product "Oxone®”; and the peracetic acid used was pretreated with catalase to remove H 2 0 2 .
- the apparatus consists of a Beckman @ DB spectrophotometer fitted with a 1 cm silica flow cell, a water bath to maintain the temperature of the bulk liquor and a pH stat to control the pH.
- the cell is connected to the solution with small-bore silicon rubber tubing and the liquor is circulated by a Watson Marlow O flow inducer. This is fitted on the return tube from the cell to the bulk solution to prevent accidental flooding of the cell compartment.
- the silicon rubber tubes enter the cell compartment of the spectrophotometer through small holes in the lid. The small amount of light which must enter here does not affect readings in the visible range.
- the flow cell The flow cell
- the silica flow cell has a path length of 1 cm. Its stopper has a glass entry tube almost reaching the bottom of the cell and set to one side out of the light path. A short exit tube takes the solution from the top of the cell through the pump and back to the bulk solution.
- a 0.04% w/v stock solution of dye was diluted with demineralised water to give 250 ml of 0.004% solution. This was poured into a 600 ml beaker set in the water bath preheated to 40°C and the pH was adjusted. The solution was then pumped through the cell at a rate of 40 ml per minute. This gives a good flow through the cell without turbulence causing bubbles. The per cent transmission at ⁇ max for the dye was monitored on the recorder.
- a further 250 ml of demineralised water containing 1.137x10- 4 moles of peracid was warmed to 40°C and the pH adjusted. This was added to the dye solution and the change in % transmission was recorded for one hour. During this time, the solution was stirred constantly and, at various time intervals, 50 ml aliquots were taken for titration with M/200 sodium thiosulphate.
- Bleaches were compared at equal active oxygen concentrations.
- the dye solution was scanned from 700 nm to 400 nm to find the maximum absorption wavelength. Then an absorption (at ⁇ max) vs concentration (% w/v) graph was plotted and the slope calculated.
- Test fabrics with different dye types are used. One 17.5 cm x 17.5 cm square of dyed test cloth was used in each wash.
- the sets of test cloths were washed in the Terg-0-Tometer for 30 minutes at a constant 40°C and 100 rpm.
- the product concentration was 0.4% w/v in 18° hard water with a liquor to cloth ratio of 50: 1.
- Each set of cloths was rinsed separately with three 600 ml portions of cold 18° hard water.
- the sets of cloths from each pot were put into separate 600 ml portions of cold 18° hard water.
- the rinses were then continued, each set of cloths being rinsed three times in 600 ml portions of cold 18° hard water.
- the reflectance of the cloths was measured at the maximum absorbance wavelength of the dye using a Beckmann @ DB-GD grating spectrophotometer fitted with a diffuse reflectance attachment. Barium sulphate was used to standardise the instrument and as a reference when measuring the cloths.
- composition of the invention should contain at least 0.002% by weight of copper, i.e. equivalent to about 0.1 ppm in solution, should have a 5 g/l solution pH of from 7 to 11, and should contain a hydrogen peroxide adduct at molar ratios to peracid which can be as low as 1:100 up to 2:1, most preferably from 1:25 to 1:1.
- the upper limit of the copper concentration can be set at 2.5% by weight based on the total composition.
- any copper(II) salt can be used in the practice of the invention, for example copper sulphate, copper carbonate, copper chloride, copper phosphate etc.
- sequestration of copper by strong sequestrants should be minimized so as to favour dye/copper interaction and the production of radicals from the bleach, but on the other hand excessive bleach decomposition must be avoided during storage of the powder.
- a relatively weak sequestrant such as ethylene diamine tetra-acetate (EDTA) can be tolerated in the present invention at levels usually below 0.2% by weight, preferably up to about 0.1% by weight, based on the total composition.
- the level of sequestrant tolerated will depend on the level of copper added.
- a higher level of copper in the formulation is required.
- a preferred level of copper in such formulations will in general be at least about 0.02% by weight.
- stain chromophores on fabrics which are generally quinonoid in character, are unlikely to behave very differently to dyes in bleaching reactions.
- Dyes of different types e.g. azo, quinonoid and indigoid, have all been found to respond to transition metal ion catalysis in solution.
- dyes can be bleached in solution (i.e. a homogeneous reaction)
- the bleach in order to bleach dye on the cloth, the bleach must transfer from the solution phase into (or onto) the substrate phase.
- a surprising feature of the present invention is that generally no positive catalysis of dye or stain bleaching on the fabric is observed from copper added to the wash solution.
- the effect of copper in solution is likely to deplete the concentration of transferable bleach species (bleach anion ROO- and especially undissociated ROOH) in solution and thus to reduce the amount of bleach available to undergo phase transition into the dye or stain on the fabric, thus reducing direct fabric bleaching.
- transferable bleach species bleach anion ROO- and especially undissociated ROOH
- the organic peracids which can be used in the present invention are known in the art. They can be either aliphatic or aromatic and have the general formula: wherein R is an alkylene group containing from 1-16 carbon atoms or an arylene group containing from 6-8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution, for example: wherein M is hydrogen or a water-soluble salt-forming cation.
- aliphatic peracids are peracetic acid, monoperazelaic acid, diperazalaic acid, diperadipic acid, diperoxy dodecanoic acid and decyl butane diperoxic acid.
- aromatic peracids are monoperoxy phthalic acid, perbenzoic acid, m-chloro-perbenzoic , acid, diperisophthalic acid or mixtures thereof.
- peracid salts examples include magnesium monoperphthalate, potassium monopersulphate, and peroxymonophosphate. Mixtures of peracids may be useful in practice.
- the amount of peracid compound in the composition of the invention will be in the range of from 0.5 to 25% by weight, preferably from 1 to 15% by weight.
- the washing composition of the instant invention contains a surfactant.
- the surfactant can be anionic, nonionic, cationic, ampholytic or zwitterionic in nature, or can be mixtures thereof. Anionics/nonionics and cationics/nonionics are typical basic surfactant mixtures. These surfactants can be used at levels from 5% to 50% of the composition by weight, preferably at levels of 10% to 35% by weight.
- Typical anionic non-soap surfactants are the alkylbenzene sulphonates having from 8-16 carbon atoms in the alkyl group, e.g. sodium dodecyl benzene sulphonate; the aliphatic sulphonates, e.g.
- C 8 ⁇ C 18 alkane sulphonates the olefin sulphonates having from 10-20 carbon atoms, obtained by reacting an alpha-olefin with gaseous diluted sulphur trioxide and hydrolysing the resulting product; the alkyl sulphates, such as tallow alcohol sulphate; and further the sulphation products of ethoxylated and/or propoxylated fatty alcohols, alkyl phenols with 8-15 carbon atoms in the alkyl group, and fatty acid amides having 1-8 moles of ethylene oxide or propylene oxide groups.
- Other anionic surfactants usable in the present invention are the alkali metal soaps (e.g. of C S -C 22 fatty acids).
- Typical nonionic surfactants are the condensation products of alkyl phenols having 5-15 carbon atoms in the alkyl group with ethylene oxide, e.g. the reaction product of nonyl phenol with 6-30 ethylene oxide units; the condensation products of higher fatty alcohols, such as tridecyl alcohol and secondary C 10 -C 15 alcohols, with ethylene oxide, known under the trade-name of "Tergitols" @ , supplied by Union Carbide; the condensation products of fatty acid amine with 8-15 ethylene oxide units and the condensation products of polypropylene glycol with ethylene oxide.
- Typical cationic surfactants include the conventional quaternary ammonium compounds and the C 10 ⁇ C 25 alkyl imidazolinium salts.
- Preferred quaternary ammonium compounds are the di(C 16 ⁇ C 20 alkyl)di(C 1 -C 4 alkyl) ammonium salts such as ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methylsulphate; dihydrogenated tallow dimethyl ammonium chloride or methyl sulphate; dioctadecyl dimethyl ammonium chloride; dicoconut alkyl dimethyl ammonium chloride.
- Also suitable are the single long chained quaternary ammonium compounds wherein the long chain is a C, o -C 22 alkyl or alkenyl group.
- a preferred member of the class of C 10 ⁇ C 25 alkyl imidazolinium salts believed to be the 1-methyl-2-tallow-3-(2-tallow amide ethyl) imidazolinium chloride, is sold under the trade-name of Varisoft® 455 or 457 (Ashland Chemical Company) or Stemoquat @ M 5040/H (Chemische Werke Rewo).
- the washing composition of the invention will also include one or more detergency builders and generally also alkaline materials. Usually the total amount of detergency builders in a detergent composition of the invention will be from 5 to 70% by weight of the detergent composition. Many detergency builders are known, and those skilled in the art of formulating fabric-washing detergent compositions will be familiar with these materials.
- detergency builders are sodium triphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium carbonate; sodium silicate; sodium oxydiacetate; sodium salts of long-chain dicarboxylic acids, for instance straight-chain (C io to C 20 ) succinic acids and malonic acids; sodium salts of alpha-sulphonated long-chain monocarboxylic acids; sodium salts of polycarboxylic acids, i.e.
- acids derived from the (co)polymerisation of unsaturated carboxylic acids and unsaturated carboxy acid anhydrides such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid, and the anhydrides of these acids, and also from the copolymerisation of the above acids and anhydrides with minor amounts of other monomers, such as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and styrene; and modified starches such as starches oxidized, for example using sodium hypochlorite, in which some anhydroglucose units have been opened to give dicarboxyl units.
- Another class of suitable builders is the insoluble aluminosilicates as described in British Patents 1 429 143, 1 470 250 and 1 529 454, e.g. zeolite A.
- a detergent composition of the invention may contain any of the conventional detergent composition ingredients in any of the amounts in which such conventional ingredients are usually employed therein.
- additional ingredients are lather boosters, such as coconut mono-ethanolamide and palm-kernel mono-ethanolamide; lather controllers, inorganic salts, such as sodium sulphate and magnesium sulphate; anti-redeposition agents, such as sodium carboxymethylcellulose; and, usually present only in minor amounts, perfumes, colorants, fluorescers, corrosion inhibitors and germicides.
- the washing composition of the present invention can suitably be used in relatively short washes as well as in relatively longer soak-washings under room temperature conditions up to 60°C for coloured fabrics, with a minimal risk of dye transfer and without the risk of serious direct fabric bleaching.
- washing compositions of the invention are preferably particulate, either as flowable powders or aggregates.
- They can be prepared using any of the conventional manufacturing techniques commonly used or proposed for the t preparation of particulate detergent compositions, such as dry-mixing, or slurry-making followed by spray-drying or spray-cooling and subsequent dry-dosing of sensitive ingredients, e.g. the solid organic peroxyacid compound and the inorganic peroxyhydrate salt.
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Abstract
Description
- This invention relates to fabric-washing detergent compositions which are especially designed for the washing of coloured or mixed coloured and white fabric loadings.
- Hitherto fabric-washing detergent compositions of two types were available, i.e. (1) washing products of a non-bleaching type for coloured fabrics, which, although safe for the fabric dyes themselves, are not effective to prevent the tendency of some coloured fabrics to release into the wash liquor dyes which are then transferred during the washing process onto other fabrics being washed therewith; and (2) a bleach-containing fabric-washing product type which can inhibit dye transfer to a certain extent but at the same time will cause bleaching and fading of the colours of the fabrics. Hence, heretofore there has been no good way to combat the problem of dye transfer other than by mechanically sorting the fabrics to partition fabrics with dark and light shades for separate laundering.
- With the fashion of moving towards more coloured clothing and textile materials, especially multi-coloureds, the problem of dye transfer has become more acute. Many attempts have been made to resolve this problem, but so far without much success.
- For example, in GB-A-1 368 400 dye-transfer-inhibiting compositions were proposed which comprise a peroxygen compound, e.g. an organic peroxyacid, combined with rather complex aldehyde or ketone compounds as bleach activator. These compositions have several drawbacks in that not only do they use rather expensive complex organic chemical compounds, i.e. aldehydes and ketones, but also in that they are not very effective.
- Other compositions having dye-transfer inhibitory effects are disclosed in European Patent 0024367 (based on the activation of organic peracids with bromide ions) and European Patent Application 0024368 (based on a system comprising an organic peracid precursor and a bromide activator). Still, the main drawback of these compositions is that they too exert a rather strong direct fabric bleaching, tending to cause fading of the coloured fabrics.
- European Patent Application 0058444 describes washing compositions useful for the reduction of dye transfer in fabric washing at lower temperatures, comprising a bleach system consisting essentially of an organic peracid or an organic peracid precursor in conjunction with a water-soluble iodide salt. There are some snags in the use of iodide catalyst, i.e. 1) the risk of staining due to iodine formation and 2) the effect of direct fabric dye bleaching.
- It is an object of the present invention to provide an improved fabric-washing detergent composition which is suitable for the washing of mixed coloured fabrics, including mixed loads of coloured and white fabrics, without the above drawbacks.
- It is another object of the invention to provide a system that is effective for dye bleaching in solution, i.e. minimising dye transfer, but is non-effective or substantially non-effective with respect to direct fabric dye bleaching.
- It has now been found that these and other objects which may be apparent hereinafter can be achieved by using a system comprising a peroxyacid or a peroxyacid salt together with a hydrogen peroxide adduct, and a copper (11) catalyst in the absence of a sequestrant which complexes more strongly with copper than EDTA.
- Heavy metals including copper have been proposed as catalyst for enhancing the decomposition or bleaching performance of peroxygen bleaching agents e.g. in EP-A-72166. EP-A-25600 and FR-A-1 515 237. These documents do not disclose compositions comprising a peracid or a peracid salt together with a hydrogen peroxides adduct.
- Internal work has shown that transition metal ions can catalyse dye bleaching in solution by oxygen bleaches. So hydrogen peroxide or hydrogen peroxide adducts, inorganic persalt/bleach activator systems and peroxyacids per se can all be activated by copper ions. However, it has been found that copper-catalysed peracid bleach systems were much more effective than copper-catalysed hydrogen peroxide systems (e.g. sodium perborate).
- The effect of added transition metal ions on the bleaching of a Direct dye in solution by peracetic acid was investigated under the following test conditions:
- Conditions: Peracetic acid (4.6x 10-4 moles/I) was added to a solution of CI Direct Red 81 (0.002% w/w) and the dye concentration measured at the wavelength of maximum absorption*. The experiments were repeated with added transition metal compounds (CUS04, MnS04, CoCl2, FeCl3, NiS04, ZnS04, Ti(S04)2 as appropriate). The experiments were made at
pH 9 and at 40°C. -
- Mechanistically it is very important to recognise that transition-metal-catalysed dye bleaching has only been achieved with transition metal ions which are easily capable of one-electron radox processes leading to the formation of reactive radicals. However, as is shown in Table I, only copper and possibly cobalt gave catalysis of peracetic acid for dye bleaching, whereas all the other metals including chromium and zinc are inactive.
- Without wishing to be bound to any theory, the mechanism of dye bleaching with oxidizing bleaches can be envisaged in general terms to progress via interactions of two distinct types:
- Metaln+ +dye→Metaln+dye→Dye Metal"+bleach->oxidized dye (+Bleach)
-
- It has also been found that although transition metal ions are well known to interact with peroxide compounds as in Route B above, thus inducing decomposition to radicals or radical species which are known to have high oxidation potential and are capable of oxidizing most unsaturated molecules, no other transition metals are as effective for dye transfer inhibition as copper.
- A possible explanation therefor may be the less well known mechanism of transition metal ions to complex strongly with many dyes as in Route A above. This route to the interaction of transition metal with bleach, which is only after its interaction with dye, seems to be followed by copper. There seems also to be little doubt that, when it occurs, complexation of transition metal ion and dye will aid dye bleaching, because metal-catalysed bleach decomposition can thus take place in the vicinity of the dye via a dye-metal bleach complex. Thus the ease with which copper forms such complexes compared with other transition metal ions may be one reason why copper has proved to be generally the most useful transition metal ion for dye bleaching in solution. Cupric ion, being the smallest divalent transition metal ion, with the highest charge density, most readily forms stable complexes. Cobalt III and chromium III complexes of dyes are also very stable, but apparently they are kinetically inert and, in contrast to copper, severe conditions are generally necessary to introduce cobalt III and chromium III into dye structures.
- In fact, copper is not the most powerful decomposer of bleach molecules. It is known that cobalt is much more effective in this respect, so the amount of free radicals or radical-like intermediates formed from oxygen bleaches is likely to be higher in the case of cobalt. The experimental observation that cobalt is less useful for bleaching dyes than copper may be attributed to the fact that for cobalt many of these radicals lead to useless bleach decomposition, whereas for copper they are more likely to be produced in the vicinity of the dye molecules.
- Also manganese, which is known to be very useful for catalysing stain bleaching, especially with hydrogen peroxide bleaches in the presence of a carbonate, has proved to be ineffective for dye transfer inhibition. Experiments have even shown that under practical conditions manganese can inhibit the catalytic effect of copper, and so the presence of manganese ions in the system of the invention should preferably be avoided.
- Some experiments have also been carried out by Applicants to determine whether strong metal-dye complexation is absolutely essential for good copper catalysis of dye bleaching in solution. From observations of the UV/visible spectra it is clear that CI Direct Red 81 and
CI Acid Orange 7 dyes complex with copper. On adding copper sulphate to Cl Acid Orange 52, an azo dye without orthohydroxy groups, there is, however, little change in the UV/visible spectrum, suggesting that the binding of this dye with copper is very weak. There is, however, a definite increase in the rate of dye bleaching when copper is added to a solution containing this dye and sodium monopersulfate (a peroxyacid salt) bleach, just as is obtained with the dyes which complex more strongly with copper. - Also when the complexation site of a bis ortho-ortho' dihydroxy azo dye was blocked with chromium, a metal which does not activate dye bleaching, as in CI Acid Blue 161, then, although there is no detectable change in the visible absorption spectrum on addition of copper to the dye alone, this addition in the presence of a monopersulfate bleach produces a considerable increase in the rate of dye bleaching. Thus these experiments indicated that copper complexation with dyes is not a necessary criterion for copper-catalysed dye bleaching and it must be concluded that, although the ability of copper to strongly complex with dyes under wash conditions plays a role in its generally found higher catalytic activity compared with other transition metal ions, copper catalysis still occurs even when the metal-dye complexation is weak or non-existent.
- There is much evidence that copper-catalysed dye bleaching is intimately connected with the decomposition of bleach in solution. Increase in concentration of copper generally increases the rate of dye bleaching as well as the decomposition of bleach. Characteristically, it has been observed that the transition-metal-catalysed decomposition of a peroxide often exhibits an induction period which is reduced by higher levels of copper ions. Many experiments made with copper-catalysed dye bleaching similarly exhibit induction periods which are reduced by increasing the concentration of copper ions.
- Thus, although this reduction in induction period is accompanied by an increased decomposition rate of bleach, acceleration of dye bleaching to avoid dye transfer can be effected by:
- (a) increase in concentration of the bleach and copper (II) ions; and furthermore by other means which increase the rate of radical production, viz:
- (b) increase in the pH of the bleach liquor; and
- (c) addition of a suitable reducing agent, e.g. hydrogen peroxide added as solid hydrogen peroxide adduct such as sodium perborate or percarbonate, which liberates hydrogen peroxide in solution.
- Accordingly the invention provides a fabric washing detergent composition especially designed for washing mixed coloured fabrics comprising a surfactant, a detergency builder, a bleaching agent and a heavy metal compound, characterized in that it comprises as the bleaching agent an organic peracid or a peracid salt in an amount of 0.5 to 25% by weight and a hydrogen peroxide adduct in a molar ratio to said peracid or peracid salt of from 1:100 to 2:1, and as the heavy metal compound a Copper compound in an amount of from 0.002 to 2.5% by weight of Copper(11)-ion, said composition having a solution pH (5 g/I) of 7 to 11 and being free of a sequestrant which complexes more strongly with Copper than EDTA.
- The influence of cupric ion concentration on an experiment of dye transfer inhibition is shown in the following Table 11 for the peracid bleaches monopersulphate, diperisophthalic acid and magnesium monoperphthalate, with and without sodium perborate.
-
- The influence of pH on dye transfer inhibition with copper-catalysed monopersulfate bleach systems is shown in Table III.
- The influence of increasing pH on the rate of copper-catalysed bleaching of CI Direct Red 81 with various peracids, i.e. I (diperisophthalic acid), II (monopersulphate) and III (peracetic acid) is shown in Fig. 1.
- The dye concentration in g/I (vertical axis) was set out against pH (horizontal axis) under the following experimental conditions:
- CI Direct Red 81 (0.002 g/I), peracid (4.6x10-4 g. atoms of active oxygen), pH stat. at 40°C. The diperisophthalic acid used was a commercial product "Suprox®"; monopersulphate used was a commercial product "Oxone®"; and the peracetic acid used was pretreated with catalase to remove
H 202. -
- The above Tables II and III also show the influence of adding perborate (sodium perborate) to monopersulphate, diperisophthalic acid or magnesium monoperphthalate on the dye-transfer problem.
- It can be seen that, in general, the addition of perborate gave a considerable enhancement of the dye transfer reduction. A molar ratio of peracid:perborate of 2:1 was found to be the optimum. Higher levels of perborate will tend to a reduced enhancement and sometimes even a reduced effect.
- The dye bleaching in solution and tergotometer dye transfer experiments were carried out by the following methods:
- The apparatus consists of a Beckman@ DB spectrophotometer fitted with a 1 cm silica flow cell, a water bath to maintain the temperature of the bulk liquor and a pH stat to control the pH. The cell is connected to the solution with small-bore silicon rubber tubing and the liquor is circulated by a Watson MarlowO flow inducer. This is fitted on the return tube from the cell to the bulk solution to prevent accidental flooding of the cell compartment. The silicon rubber tubes enter the cell compartment of the spectrophotometer through small holes in the lid. The small amount of light which must enter here does not affect readings in the visible range.
- The silica flow cell has a path length of 1 cm. Its stopper has a glass entry tube almost reaching the bottom of the cell and set to one side out of the light path. A short exit tube takes the solution from the top of the cell through the pump and back to the bulk solution.
- A 0.04% w/v stock solution of dye was diluted with demineralised water to give 250 ml of 0.004% solution. This was poured into a 600 ml beaker set in the water bath preheated to 40°C and the pH was adjusted. The solution was then pumped through the cell at a rate of 40 ml per minute. This gives a good flow through the cell without turbulence causing bubbles. The per cent transmission at λ max for the dye was monitored on the recorder.
- A further 250 ml of demineralised water containing 1.137x10-4 moles of peracid was warmed to 40°C and the pH adjusted. This was added to the dye solution and the change in % transmission was recorded for one hour. During this time, the solution was stirred constantly and, at various time intervals, 50 ml aliquots were taken for titration with M/200 sodium thiosulphate.
- When reagents such as electrolytes, surfactants or bleaching aids were to be used, they were added as the first dye solution was prepared.
- Bleaches were compared at equal active oxygen concentrations.
- The dye solution was scanned from 700 nm to 400 nm to find the maximum absorption wavelength. Then an absorption (at λ max) vs concentration (% w/v) graph was plotted and the slope calculated.
-
- Slope=the slope of the absorption vs concentration graph.
- Test fabrics with different dye types are used. One 17.5 cm x 17.5 cm square of dyed test cloth was used in each wash.
- The fabrics for dye pick-up where white mercerised, desized cotton shirting and white bulked nylon 66, both non-fluorescent. One 12 cm x 12 cm square of each of these was put into the wash, regardless of the dye type, to keep the liquor to cloth ratio the same.
- The sets of test cloths were washed in the Terg-0-Tometer for 30 minutes at a constant 40°C and 100 rpm. The product concentration was 0.4% w/v in 18° hard water with a liquor to cloth ratio of 50: 1. Each set of cloths was rinsed separately with three 600 ml portions of cold 18° hard water.
- 450 ml portions of 18° hard water were poured into the Tergo pots and allowed to warm up to 40°C. The pre-weighed constituents were then added. One dyed test fabric and one each of the clean cotton and nylon test cloths were added and washed for 30 min. at 100 rpm.
- At the end of the wash, the sets of cloths from each pot were put into separate 600 ml portions of cold 18° hard water. The rinses were then continued, each set of cloths being rinsed three times in 600 ml portions of cold 18° hard water.
- After rinsing, the cloths were separated, padded on paper towelling to remove excess moisture and dried in a cabinet at 60°C.
- The reflectance of the cloths was measured at the maximum absorbance wavelength of the dye using a Beckmann@ DB-GD grating spectrophotometer fitted with a diffuse reflectance attachment. Barium sulphate was used to standardise the instrument and as a reference when measuring the cloths.
- From the above experimental results it can be said that the composition of the invention should contain at least 0.002% by weight of copper, i.e. equivalent to about 0.1 ppm in solution, should have a 5 g/l solution pH of from 7 to 11, and should contain a hydrogen peroxide adduct at molar ratios to peracid which can be as low as 1:100 up to 2:1, most preferably from 1:25 to 1:1.
- For practical reasons, the upper limit of the copper concentration can be set at 2.5% by weight based on the total composition.
- As the source of copper, any copper(II) salt can be used in the practice of the invention, for example copper sulphate, copper carbonate, copper chloride, copper phosphate etc.
- As already elucidated before, sequestration of copper by strong sequestrants should be minimized so as to favour dye/copper interaction and the production of radicals from the bleach, but on the other hand excessive bleach decomposition must be avoided during storage of the powder. Hence the presence of very minor amounts of a relatively weak sequestrant such as ethylene diamine tetra-acetate (EDTA) can be tolerated in the present invention at levels usually below 0.2% by weight, preferably up to about 0.1% by weight, based on the total composition. The level of sequestrant tolerated will depend on the level of copper added.
- In practice, where the invention is used in a normal phosphate-built detergent composition, a higher level of copper in the formulation is required. Hence a preferred level of copper in such formulations will in general be at least about 0.02% by weight.
- From theoretical considerations, stain chromophores on fabrics, which are generally quinonoid in character, are unlikely to behave very differently to dyes in bleaching reactions. Dyes of different types, e.g. azo, quinonoid and indigoid, have all been found to respond to transition metal ion catalysis in solution. However, whereas dyes can be bleached in solution (i.e. a homogeneous reaction), in order to bleach dye on the cloth, the bleach must transfer from the solution phase into (or onto) the substrate phase. A surprising feature of the present invention is that generally no positive catalysis of dye or stain bleaching on the fabric is observed from copper added to the wash solution. The effect of copper in solution is likely to deplete the concentration of transferable bleach species (bleach anion ROO- and especially undissociated ROOH) in solution and thus to reduce the amount of bleach available to undergo phase transition into the dye or stain on the fabric, thus reducing direct fabric bleaching.
- The organic peracids which can be used in the present invention are known in the art. They can be either aliphatic or aromatic and have the general formula:
- Examples of aliphatic peracids are peracetic acid, monoperazelaic acid, diperazalaic acid, diperadipic acid, diperoxy dodecanoic acid and decyl butane diperoxic acid.
- Examples of aromatic peracids are monoperoxy phthalic acid, perbenzoic acid, m-chloro-perbenzoic , acid, diperisophthalic acid or mixtures thereof.
- Examples of peracid salts as meant here include magnesium monoperphthalate, potassium monopersulphate, and peroxymonophosphate. Mixtures of peracids may be useful in practice.
- The amount of peracid compound in the composition of the invention will be in the range of from 0.5 to 25% by weight, preferably from 1 to 15% by weight.
- The washing composition of the instant invention contains a surfactant. The surfactant can be anionic, nonionic, cationic, ampholytic or zwitterionic in nature, or can be mixtures thereof. Anionics/nonionics and cationics/nonionics are typical basic surfactant mixtures. These surfactants can be used at levels from 5% to 50% of the composition by weight, preferably at levels of 10% to 35% by weight.
- Typical anionic non-soap surfactants are the alkylbenzene sulphonates having from 8-16 carbon atoms in the alkyl group, e.g. sodium dodecyl benzene sulphonate; the aliphatic sulphonates, e.g. C8―C18 alkane sulphonates; the olefin sulphonates having from 10-20 carbon atoms, obtained by reacting an alpha-olefin with gaseous diluted sulphur trioxide and hydrolysing the resulting product; the alkyl sulphates, such as tallow alcohol sulphate; and further the sulphation products of ethoxylated and/or propoxylated fatty alcohols, alkyl phenols with 8-15 carbon atoms in the alkyl group, and fatty acid amides having 1-8 moles of ethylene oxide or propylene oxide groups. Other anionic surfactants usable in the present invention are the alkali metal soaps (e.g. of CS-C22 fatty acids).
- Typical nonionic surfactants are the condensation products of alkyl phenols having 5-15 carbon atoms in the alkyl group with ethylene oxide, e.g. the reaction product of nonyl phenol with 6-30 ethylene oxide units; the condensation products of higher fatty alcohols, such as tridecyl alcohol and secondary C10-C15 alcohols, with ethylene oxide, known under the trade-name of "Tergitols"@, supplied by Union Carbide; the condensation products of fatty acid amine with 8-15 ethylene oxide units and the condensation products of polypropylene glycol with ethylene oxide.
- Typical cationic surfactants include the conventional quaternary ammonium compounds and the C10―C25 alkyl imidazolinium salts. Preferred quaternary ammonium compounds are the di(C16―C20 alkyl)di(C1-C4 alkyl) ammonium salts such as ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methylsulphate; dihydrogenated tallow dimethyl ammonium chloride or methyl sulphate; dioctadecyl dimethyl ammonium chloride; dicoconut alkyl dimethyl ammonium chloride. Also suitable are the single long chained quaternary ammonium compounds wherein the long chain is a C,o-C22 alkyl or alkenyl group.
- A preferred member of the class of C10―C25 alkyl imidazolinium salts, believed to be the 1-methyl-2-tallow-3-(2-tallow amide ethyl) imidazolinium chloride, is sold under the trade-name of Varisoft® 455 or 457 (Ashland Chemical Company) or Stemoquat@ M 5040/H (Chemische Werke Rewo).
- A typical listing of the classes and species of surfactants useful in this invention appears in the books "Surface Active Agents", Vol. I, by Schwartz & Perry (Interscience Publishers 1949) and "Surface Active Agents and Detergents", Vol II, by Schwartz, Perry & Berch (Interscience 1958).
- The washing composition of the invention will also include one or more detergency builders and generally also alkaline materials. Usually the total amount of detergency builders in a detergent composition of the invention will be from 5 to 70% by weight of the detergent composition. Many detergency builders are known, and those skilled in the art of formulating fabric-washing detergent compositions will be familiar with these materials. Examples of known detergency builders are sodium triphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium carbonate; sodium silicate; sodium oxydiacetate; sodium salts of long-chain dicarboxylic acids, for instance straight-chain (Cio to C20) succinic acids and malonic acids; sodium salts of alpha-sulphonated long-chain monocarboxylic acids; sodium salts of polycarboxylic acids, i.e. acids derived from the (co)polymerisation of unsaturated carboxylic acids and unsaturated carboxy acid anhydrides, such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid, and the anhydrides of these acids, and also from the copolymerisation of the above acids and anhydrides with minor amounts of other monomers, such as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and styrene; and modified starches such as starches oxidized, for example using sodium hypochlorite, in which some anhydroglucose units have been opened to give dicarboxyl units. Another class of suitable builders is the insoluble aluminosilicates as described in British Patents 1 429 143, 1 470 250 and 1 529 454, e.g. zeolite A.
- Further, a detergent composition of the invention may contain any of the conventional detergent composition ingredients in any of the amounts in which such conventional ingredients are usually employed therein. Examples of these additional ingredients are lather boosters, such as coconut mono-ethanolamide and palm-kernel mono-ethanolamide; lather controllers, inorganic salts, such as sodium sulphate and magnesium sulphate; anti-redeposition agents, such as sodium carboxymethylcellulose; and, usually present only in minor amounts, perfumes, colorants, fluorescers, corrosion inhibitors and germicides.
- The washing composition of the present invention can suitably be used in relatively short washes as well as in relatively longer soak-washings under room temperature conditions up to 60°C for coloured fabrics, with a minimal risk of dye transfer and without the risk of serious direct fabric bleaching.
- The washing compositions of the invention are preferably particulate, either as flowable powders or aggregates.
- They can be prepared using any of the conventional manufacturing techniques commonly used or proposed for thetpreparation of particulate detergent compositions, such as dry-mixing, or slurry-making followed by spray-drying or spray-cooling and subsequent dry-dosing of sensitive ingredients, e.g. the solid organic peroxyacid compound and the inorganic peroxyhydrate salt.
- Other conventional techniques for taking precautions to improve storage stability or to minimize undue and undesirable interactions during storage between the bleaching agents and copper or other components of the detergent compositions, such as noodling, granulation, pelletizing and coating of any of the compounds may be utilized as and when necessary.
Claims (4)
Priority Applications (1)
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AT84201655T ATE41672T1 (en) | 1983-11-23 | 1984-11-15 | DETERGENT COMPOSITION. |
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GB838331278A GB8331278D0 (en) | 1983-11-23 | 1983-11-23 | Detergent composition |
GB8331278 | 1983-11-23 |
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EP0143491A2 EP0143491A2 (en) | 1985-06-05 |
EP0143491A3 EP0143491A3 (en) | 1985-10-30 |
EP0143491B1 true EP0143491B1 (en) | 1989-03-22 |
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EP84201655A Expired EP0143491B1 (en) | 1983-11-23 | 1984-11-15 | Detergent composition |
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JP (1) | JPS60138000A (en) |
AT (1) | ATE41672T1 (en) |
AU (1) | AU550759B2 (en) |
BR (1) | BR8405950A (en) |
CA (1) | CA1234456A (en) |
DE (1) | DE3477397D1 (en) |
DK (1) | DK556184A (en) |
FI (1) | FI844531L (en) |
GB (2) | GB8331278D0 (en) |
GR (1) | GR80988B (en) |
IN (1) | IN161099B (en) |
NO (1) | NO163964C (en) |
PH (1) | PH20525A (en) |
PT (1) | PT79540A (en) |
TR (1) | TR22429A (en) |
YU (1) | YU196684A (en) |
ZA (1) | ZA849117B (en) |
Families Citing this family (12)
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GB8508010D0 (en) * | 1985-03-27 | 1985-05-01 | Unilever Plc | Liquid bleaching compositions |
ES2008833A6 (en) * | 1988-10-25 | 1989-08-01 | Camp Jabones | Textile bleaching compositions effective at low temperatures. |
US5288746A (en) * | 1992-12-21 | 1994-02-22 | The Procter & Gamble Company | Liquid laundry detergents containing stabilized glucose/glucose oxidase as H2 O2 generation system |
JP2941430B2 (en) * | 1994-04-07 | 1999-08-25 | ザ、プロクター、エンド、ギャンブル、カンパニー | Bleaching composition containing a metal-containing bleaching catalyst |
US5686014A (en) * | 1994-04-07 | 1997-11-11 | The Procter & Gamble Company | Bleach compositions comprising manganese-containing bleach catalysts |
WO1995027774A1 (en) * | 1994-04-07 | 1995-10-19 | The Procter & Gamble Company | Bleach compositions comprising metal-containing bleach catalysts and antioxidants |
US5968881A (en) * | 1995-02-02 | 1999-10-19 | The Procter & Gamble Company | Phosphate built automatic dishwashing compositions comprising catalysts |
WO1996023861A1 (en) * | 1995-02-02 | 1996-08-08 | The Procter & Gamble Company | Automatic dishwashing compositions comprising cobalt (iii) catalysts |
DE69608541T2 (en) * | 1995-02-02 | 2001-01-18 | The Procter & Gamble Company, Cincinnati | MACHINE DISHWASHER COMPOSITIONS WITH COBALT CHELATE CATALYSTS |
ES2158312T3 (en) * | 1995-06-16 | 2001-09-01 | Procter & Gamble | WHITENING COMPOSITIONS THAT INCLUDE COBALT CATALYSTS. |
CN1192774A (en) * | 1995-06-16 | 1998-09-09 | 普罗格特-甘布尔公司 | Automatic dishwashing compositions comprising cobalt catalysts |
US5703034A (en) * | 1995-10-30 | 1997-12-30 | The Procter & Gamble Company | Bleach catalyst particles |
Citations (1)
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EP0025608A2 (en) * | 1979-09-18 | 1981-03-25 | Süd-Chemie Ag | Catalyst for the controlled decomposition of peroxide compounds, its preparation and use; washing or bleaching agent and process for producing a washing or bleaching agent that contains peroxide compounds |
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NL266614A (en) * | 1960-07-07 | |||
BE614629A (en) * | 1961-03-24 | |||
FR1515237A (en) * | 1967-01-20 | 1968-03-01 | Colgate Palmolive Co | Cleaning composition with enhanced bleaching effect |
FR2253823B1 (en) * | 1973-12-11 | 1977-06-10 | Colgate Palmolive Co | |
DD141844B1 (en) * | 1978-12-28 | 1982-04-28 | Rudolf Opitz | BLEACH |
GR76237B (en) * | 1981-08-08 | 1984-08-04 | Procter & Gamble |
-
1983
- 1983-11-23 GB GB838331278A patent/GB8331278D0/en active Pending
-
1984
- 1984-11-15 AT AT84201655T patent/ATE41672T1/en not_active IP Right Cessation
- 1984-11-15 EP EP84201655A patent/EP0143491B1/en not_active Expired
- 1984-11-15 DE DE8484201655T patent/DE3477397D1/en not_active Expired
- 1984-11-19 FI FI844531A patent/FI844531L/en not_active Application Discontinuation
- 1984-11-20 GR GR80988A patent/GR80988B/en unknown
- 1984-11-20 AU AU35697/84A patent/AU550759B2/en not_active Ceased
- 1984-11-21 CA CA000468356A patent/CA1234456A/en not_active Expired
- 1984-11-21 TR TR8845/84A patent/TR22429A/en unknown
- 1984-11-22 GB GB08429496A patent/GB2150944B/en not_active Expired
- 1984-11-22 YU YU01966/84A patent/YU196684A/en unknown
- 1984-11-22 NO NO844648A patent/NO163964C/en unknown
- 1984-11-22 JP JP59247882A patent/JPS60138000A/en active Granted
- 1984-11-22 DK DK556184A patent/DK556184A/en not_active Application Discontinuation
- 1984-11-22 ZA ZA849117A patent/ZA849117B/en unknown
- 1984-11-22 BR BR8405950A patent/BR8405950A/en not_active IP Right Cessation
- 1984-11-22 PH PH31476A patent/PH20525A/en unknown
- 1984-11-23 PT PT79540A patent/PT79540A/en unknown
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---|---|---|---|---|
EP0025608A2 (en) * | 1979-09-18 | 1981-03-25 | Süd-Chemie Ag | Catalyst for the controlled decomposition of peroxide compounds, its preparation and use; washing or bleaching agent and process for producing a washing or bleaching agent that contains peroxide compounds |
Non-Patent Citations (1)
Title |
---|
Lindner's Tenside-Textilhilfsmittel-Waschrohstoffe, vol. I, pp. 462-466 (1964) * |
Also Published As
Publication number | Publication date |
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GB8331278D0 (en) | 1983-12-29 |
YU196684A (en) | 1986-12-31 |
CA1234456A (en) | 1988-03-29 |
JPH0352519B2 (en) | 1991-08-12 |
PT79540A (en) | 1984-12-01 |
NO844648L (en) | 1985-05-24 |
ATE41672T1 (en) | 1989-04-15 |
BR8405950A (en) | 1985-09-10 |
GB2150944A (en) | 1985-07-10 |
EP0143491A2 (en) | 1985-06-05 |
NO163964C (en) | 1990-08-15 |
FI844531A0 (en) | 1984-11-19 |
AU550759B2 (en) | 1986-04-10 |
IN161099B (en) | 1987-10-03 |
GR80988B (en) | 1985-02-27 |
AU3569784A (en) | 1985-05-30 |
DK556184A (en) | 1985-05-24 |
JPS60138000A (en) | 1985-07-22 |
TR22429A (en) | 1987-06-02 |
DK556184D0 (en) | 1984-11-22 |
EP0143491A3 (en) | 1985-10-30 |
PH20525A (en) | 1987-02-04 |
GB2150944B (en) | 1987-12-02 |
GB8429496D0 (en) | 1985-01-03 |
NO163964B (en) | 1990-05-07 |
DE3477397D1 (en) | 1989-04-27 |
FI844531L (en) | 1985-05-24 |
ZA849117B (en) | 1986-07-30 |
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