WO2010069957A1 - Laundry detergent composition - Google Patents
Laundry detergent composition Download PDFInfo
- Publication number
- WO2010069957A1 WO2010069957A1 PCT/EP2009/067193 EP2009067193W WO2010069957A1 WO 2010069957 A1 WO2010069957 A1 WO 2010069957A1 EP 2009067193 W EP2009067193 W EP 2009067193W WO 2010069957 A1 WO2010069957 A1 WO 2010069957A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition according
- composition
- surfactant
- hydroxamate
- anionic
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 239000003599 detergent Substances 0.000 title claims description 53
- 239000004094 surface-active agent Substances 0.000 claims abstract description 48
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 23
- 125000000129 anionic group Chemical group 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 17
- 239000002689 soil Substances 0.000 claims description 38
- 239000004927 clay Substances 0.000 claims description 33
- 239000004744 fabric Substances 0.000 claims description 33
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 229920000742 Cotton Polymers 0.000 claims description 13
- 239000004753 textile Substances 0.000 claims description 12
- 239000003752 hydrotrope Substances 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000000344 soap Substances 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 238000009472 formulation Methods 0.000 description 28
- -1 alkali metal salt Chemical class 0.000 description 25
- 239000007844 bleaching agent Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 244000025254 Cannabis sativa Species 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 239000002280 amphoteric surfactant Substances 0.000 description 8
- 229940088598 enzyme Drugs 0.000 description 8
- 238000004900 laundering Methods 0.000 description 8
- 239000002888 zwitterionic surfactant Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000008233 hard water Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000008234 soft water Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003352 sequestering agent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- 239000004115 Sodium Silicate Substances 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
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- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229940094506 lauryl betaine Drugs 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 108010020132 microbial serine proteinases Proteins 0.000 description 2
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 230000002829 reductive effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 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 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
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- 150000003890 succinate salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
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- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- KKMIHKCGXQMFEU-UHFFFAOYSA-N 2-[dimethyl(tetradecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O KKMIHKCGXQMFEU-UHFFFAOYSA-N 0.000 description 1
- AMRBZKOCOOPYNY-QXMHVHEDSA-N 2-[dimethyl-[(z)-octadec-9-enyl]azaniumyl]acetate Chemical compound CCCCCCCC\C=C/CCCCCCCC[N+](C)(C)CC([O-])=O AMRBZKOCOOPYNY-QXMHVHEDSA-N 0.000 description 1
- OBMBUODDCOAJQP-UHFFFAOYSA-N 2-chloro-4-phenylquinoline Chemical compound C=12C=CC=CC2=NC(Cl)=CC=1C1=CC=CC=C1 OBMBUODDCOAJQP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
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- 238000002036 drum drying Methods 0.000 description 1
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- 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
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HUPYBBFSQOFVSZ-UHFFFAOYSA-N methioninehydroxamic acid Chemical compound CSCCC(N)C(=O)NO HUPYBBFSQOFVSZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WKGHJBXTMFXUNA-UHFFFAOYSA-N n,n,n',n'-tetrahexadecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCC)CCN(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC WKGHJBXTMFXUNA-UHFFFAOYSA-N 0.000 description 1
- JLXAQYGJCVUJLE-UHFFFAOYSA-N n-hydroxynonanamide Chemical compound CCCCCCCCC(=O)NO JLXAQYGJCVUJLE-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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- 235000020030 perry Nutrition 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
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- QYSPLQLAKJAUJT-UHFFFAOYSA-N piroxicam Chemical compound OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 QYSPLQLAKJAUJT-UHFFFAOYSA-N 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 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
- 239000011780 sodium chloride Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019794 sodium silicate Nutrition 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
- ODBPOHVSVJZQRX-UHFFFAOYSA-M sodium;[2-[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methyl-hydroxyphosphinate Chemical compound [Na+].OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)([O-])=O ODBPOHVSVJZQRX-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical compound CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 229940124024 weight reducing agent Drugs 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
-
- 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
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
Definitions
- the present invention relates to the use of hydroxamic acid and its corresponding salts in laundry detergent compositions with low levels of zeolite and phosphate builder, leading to improved detergency and stain removal.
- Improvement of stain removal is one of the constant goals of the detergents industry, as this may lead to savings on the use of chemicals in detergent compositions, or may lead to washing at lower temperature, and/or for shorter times, and therewith saving energy. Therefore there is still an interest to improve the detergency effect, especially the primary detergency effect of laundry detergent compositions on textile stains, for example particulate stains, such as stains comprising soils or clay, or plant based stains, such as grass. Especially particulate stains are difficult to remove during the laundering process.
- Hydroxamic acids are a class of chemical compounds in which a hydroxylamine is inserted into a carboxylic acid.
- the general structure of a hydroxamic acid is the following: o
- R 1 is an organic residue, for example alkyl or alkylene groups.
- the hydroxamic acid may be present as its corresponding alkali metal salt, or hydroxamate.
- hydroxamates may conveniently be formed from the corresponding hydroxamic acid by substitution of the acid hydrogen atom by a cation: fl LOH ft ⁇ , ®
- L + is a monovalent cation such as for example the alkali metals (e.g. potassium, sodium), or ammonium or a substituted ammonium.
- Hydroxamic acids and hydroxamates are known to be useful as metal chelators. They have also been used in detergent compositions in order to improve bleaching performance, as well as use as a builder substance.
- EP 388 389 A2 discloses bleach free under built liquid detergent compositions containing hydroxamic acids and their derivatives which assist in the removal of bleachable wine stains from fabrics during laundering.
- Hydroxamic acids as in formula 1 are disclosed, wherein R 1 represents an optionally substituted straight- or branched chain C5-C 21 alkyl or C5-C 21 alkenyl group or an optionally-substituted phenyl group, and R 2 represents hydrogen, or an optionally substituted d-C 6 alkyl group, or an optionally-substituted phenyl group.
- R 1 represents an optionally substituted straight- or branched chain C5-C 21 alkyl or C5-C 21 alkenyl group or an optionally-substituted phenyl group
- R 2 represents hydrogen, or an optionally substituted d-C 6 alkyl group, or an optionally-substituted phenyl group.
- One of the examples shows an improved bleaching performance when a hydro
- the examples use C 12 linear, C 12 branched, C 1 3 branched and C 1 8 hydroxamates in detergent formulations comprising mixtures of anionic surfactant and nonionic surfactant.
- examples I, Il and IV there is an excess of nonionic surfactant of at least 1.25 to 1 and in example III there is 100% anionic surfactant.
- the liquids also contain at least 6 wt% ethanol, which assists in solubilising the long chain hydroxamates.
- EP 384 912 A2 discloses the use of hydroxamic acids and their derivatives as stabilizers for peroxygen bleach compounds in built, mainly granular, detergent compositions. Fully formulated detergent powder examples with 20 wt% zeolite used C 12 , Ci 3 and C 12 branched hydroxamates. Ci 8 was also used. US 4,874,539 discloses polymeric carboxy hydroxamic acids useful as detergent additives, especially as metal ion chelating agents, and also leading to improved tea stain removal from a test cloth, as compared to a detergent powder without a metal ion chelating agent.
- US 4,863,636 discloses liquid detergent compositions comprising one or more detersive surfactants and one or more of N-hydroxyimide or carboxy hydroxamic acid detergent additives. These compounds serve as active metal ion chelants, leading to improved stain removal.
- WO 97/48786 discloses a multicomponent system for use with detergent substances, containing an oxidation catalyst, a suitable oxidant, at least one mediator that has been selected from the group of, among others, hydroxamic acids and hydroxamic acid derivatives, a co-mediator, and optionally a low quantity of at least one free amine of each inserted mediator. This system leads to improved bleach function of the detergent, and less consumption of a mediator.
- GB 1317445 discloses detergent compositions comprising an alkali-metal salt of a hydroxamic acid. The function of this salt is to prevent the corrosion of copper and copper alloys that is utilised in the construction of the washing machines.
- Laundry detergents need to be able to remove everyday dirt and stains that are commonly found in a wash load.
- One type of clay that is particularly resistant to removal by surfactants alone is red clay, such as red pottery clay or Red Georgia clay. This is a particulate soil stain.
- the present invention provides a laundry detergent composition comprising a) 0.5 to 20, preferably 0.5 to 6, wt% hydroxamic acid or its corresponding hydroxamate of the structure:
- R 2 is a straight or branched C 4 -C 2 O alkyl, or a straight or branched substituted C 4 -C 20 alkyl, or a straight or branched C 4 -C 20 alkenyl, or a straight or branched substituted C 4 -C 20 alkenyl, or an alkyl ether group CH 3 (CH 2 ) n (EO) m wherein n is from 2 to 20 and m is from 1 to 12, or a substituted alkyl ether group CH 3 (CH 2 ) n (EO) m wherein n is from 2 to 20 and m is from 1 to 12, and the types of substitution include one or more of -NH 2 , -OH, -S-, -O-, -COOH, and
- R 2 is selected from hydrogen and a moiety that forms part of a cyclic structure with a branched R 1 group
- a detersive surfactant system at a concentration from 3 to 80 wt%; the detersive surfactant system comprising
- the ratio of (i) to (ii) lies in the range 1 :1.1 to 19:1 and the weight ratio of a) to b) lies in the range 1 :5 to 1 :15 c) optionally, other ingredients to 100 wt%, provided that zeolite and phosphate builders are present at less than 5 wt% and ethanol is present at a level of less than 5 wt%.
- references to a number of carbon atoms include mixed chain length materials provided that some of the hydroxamate material falls within the ranges specified and the ratios and amounts are determined by excluding any material falling outside of the specified range.
- Such concentrated formulations comprise at least 20 wt% of the detersive surfactant system, preferably at least 30 wt% and more preferably over 40 wt%.
- the preferred hydroxamates are those where R 2 is Hydrogen and R 1 is Cs to Ci 4 alkyl, preferably normal alkyl, most preferably saturated.
- the detergent composition is preferably used in an aqueous wash liquor, but may comprise one or more solvents suitable for use for domestic laundry purposes.
- the improved stain removal occurs during the main wash of the laundry process, i.e. preferably the laundry detergent composition in which the hydroxamates are used is a main wash product.
- the wash liquor is preferably free of formate salts. Furthermore, it is preferably free from bleach, especially peroxygen bleach.
- the composition may comprise from 1 to 15 wt% soap.
- the preferred soaps are made from saturated fatty acids.
- Especially preferred compositions comprise at least 0.5 wt% of soil release polymer. This improves the multiwash performance of the detergent system for the removal of the clay.
- Inclusion of at least 0.5 wt% anti redeposition polymer is also beneficial due to the very high efficiency of primary detergency soil removal meaning that there is an increased level of soil in the wash liquor, which must then be prevented from redeposition onto the same or a different piece of fabric.
- the preferred ratio of hydroxamate to detersive surfactant system for optimum particulate red clay soil removal lies in the range 1 :7 to 1 :13. An even more preferred range of ratios being 1 :9 to 1 :11 parts by weight.
- the preferred ratio of anionic to nonionic surfactant for particulate red clay soil removal is at least 1 :1 , more preferably at least 3:2. Preferably, it is at most 9:1. So a most preferred range is 1 :1 to 9:1 , or 3:2 to 9:1.
- compositions are particularly suitable for use on particulate stains such as soils and clays, especially red clay, and also surprisingly grass.
- the invention also extends to the use of 0.5 to 20 wt% hydroxamic acid or its corresponding hydroxamate of the structure: o
- R 1 is a C 8 normal alkyl group
- R 2 is a hydrogen atom
- the composition further comprises a detersive surfactant system comprising anionic surfactant and nonionic surfactant at a concentration from 3 to 80 wt%; and optionally other ingredients to 100 wt%.
- the hydroxamate may be incorporated within the laundry detergent compositions in any suitable fashion within the knowledge of a person of ordinary skill in the art.
- the stained fabric is treated with the laundry detergent composition comprising hydroxamate according to the invention and the primary detergency is the measured stain removal by the laundry composition on the stain.
- This is a separate process to so-called soil release using a polymer, which is treatment of fabric with a polymer (through a wash or other such treatment), with subsequent staining of the fabric, the soil release polymer having the effect of the easier removal of the stain.
- the textile/fabric substrates used can be any typical textile/fabric substrate, such as cotton (woven, knitted & denim), polyester (woven, knitted & micro fibre), nylon, silk, polycotton (polyester/cotton blends), polyester elastane, cotton elastane, viscose rayon, acrylic or wool.
- Particularly suitable textile/fabric substrates are cotton, polycotton and polyester substrates.
- Particulate stains are stains comprising for example dirt, soil, clay, mud or soot. They are predominately solid in nature and come into contact with fabrics in the course of their regular use.
- R 1 is an alkyl ether group CH 3 (CH 2 ) n (EO) m wherein n is from 2 to 20 and m is from 1 to 12 then the alkyl moiety terminates this side group.
- R 1 is chosen from the group consisting of C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , Cio, Cii, or Ci 2 or Ci 4 normal alkyl group, most preferably R 1 is at least a C 8-I4 normal alkyl group. When the C 8 material is used this is called octyl hydroxamic acid.
- the potassium salt is particularly useful.
- hydroxamic acids whilst less preferred, are suitable for use in the present invention.
- suitable compounds include, but are not limited to, the following compounds:
- Such hydroxamic acids are commercially available.
- the hydroxamate acts by binding to metal ions that are present in the soil on the fabric. This binding action, which is, in effect, the known sequestrant property of the hydroxamate is not, in itself, of any use to remove the soil from the fabric.
- the key is the "tail" of the hydroxamate i.e. the group R 1 minus any branching that folds back onto the amate Nitrogen via group R 2 .
- the tail is selected to have an affinity for the surfactant system.
- the soil removal ability of an already optimised surfactant system is further enhanced by the use of the hydroxamate as it, in effect, labels the difficult to remove particulate material (clay) as "soil” for removal by the surfactant system acting on the hydroxamate molecules now fixed to the particulates via their binding to the metal ions embedded in the clay type particulates.
- the detersive surfactants will adhere to the hydroxamate, leading overall to more surfactants interacting with the fabric, leading to better soil release.
- the hydroxamic acids act as a linker molecule facilitating the removal and suspension of the particulate soil from the fabric into a wash liquor and thus boosting the primary detergency.
- This enhancing of the primary detergency of surfactant systems is especially relevant when using concentrated liquid detergent compositions, as the pH during the laundering process is relatively low (pH 7.5-8) as compared to traditional laundering processes with particulate detergent compositions (pH 9-10.5).
- the lower pH during the laundering process with liquid detergent compositions may lead to reduced soil release, as the surface charges of the soils are less negative as compared to the higher pH during the conventional well built and buffered laundering processes, achieved with conventional zeolite or phosphate built powder products.
- This surface charge of the soil may lead to increased repellence of the surfactants by the soil, possibly leading to reduced release of the soil.
- the hydroxamates are used in liquid detergent compositions, and more preferred the detersive surfactant concentration in said liquid detergent compositions is from 20 to 80 wt%.
- the hydroxamates have a higher affinity for transition metals, like iron, than for alkaline earth metals like calcium and magnesium, therefore the hydroxamic acid primarily acts to improve the removal of soil on fabric, especially particulate soils, and not additionally as a builder for calcium and magnesium. This selectively is especially beneficial if the laundering composition is underbuilt; especially when it comprises less than 5 wt% zeolite or phosphate builder.
- the laundry detergent composition in which the hydroxamate is used comprises a detersive surfactant system at a concentration from 3 to 80 wt%.
- a detersive surfactant system we mean that the surfactants therein provide a detersive, i.e. cleaning effect to textile fabrics treated as part of a laundering process.
- Other surfactants which are not detersive surfactants, can be used as part of the composition.
- the detersive surfactant is present at a level of from 5 to 60 wt%, more preferably from 10 to 50 wt%. Even more preferably, the detersive surfactant system comprises at least 20, or 30 or even 40 wt% of the composition.
- any surfactant may be used as detersive surfactants, including anionic, nonionic, cationic, and amphoteric or zwitterionic surfactants, or combinations of these, provided that there is anionic and nonionic surfactant present in the range of ratios specified above.
- Cationic surfactant may optionally be present as part of the detersive surfactant.
- Anionic surfactant is present at a level of from 0.1 to 50 wt%, preferably from 1 to 40 wt%, more preferably from 1.5 to 25 wt%.
- Nonionic surfactant is incorporated at a level of from 0.1 to 50 wt%, preferably from 1 to 40 wt%, more preferably from 1.5 to 25 wt%.
- the ratio of anionic surfactant to nonionic surfactant is from 19:1 to 1 :1.1 , more preferably from 9:1 to 1 :1.
- nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described in 'Surface Active Agents' Vol. 1 , by Schwartz & Perry, lnterscience 1949, Vol. 2 by Schwartz, Perry & Berch, lnterscience 1958, in the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company or in Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
- 'nonionic surfactant' shall be defined as amphiphilic molecules with a molecular weight of less than about 10,000, unless otherwise noted, which are substantially free of any functional groups that exhibit a net charge at the normal wash pH of 6-11.
- nonionic surfactant may be used, although preferred materials are further discussed below.
- fatty acid alkoxylates especially ethoxylates, having an alkyl chain of from C 8 -C 35 , preferably C 8 -C 30 , more preferably Ci 0 -C 24 , especially Ci 0 -Ci 8 carbon atoms, for example, the Neodol range from Shell (The Hague, The Netherlands); ethylene oxide/propylene oxide block polymers which may have molecular weight from 1 ,000 to 30,000, for example, Pluronic (trademark) from BASF (Ludwigshafen, Germany); and alkylphenol ethoxylates, for example Triton X-100, available from Dow Chemical (Midland, Mich., USA).
- nonionic surfactants should also be considered within the scope of this invention. These include condensates of alkanolamines with fatty acids, such as cocamide DEA, polyol-fatty acid esters, such as the Span series available from Uniqema (Gouda, The Netherlands), ethoxylated polyol-fatty acid esters, such as the Tween series available from Uniqema (Gouda, The Netherlands), alkylpolyglucosides, such as the APG line available from Cognis (D ⁇ sseldorf, Germany) and n-alkylpyrrolidones, such as the Surfadone series of products marketed by ISP (Wayne, N. J., USA). Furthermore, nonionic surfactants not specifically mentioned above, but within the definition, may also be used.
- the more preferred nonionic surfactants are the fatty acid ethoxylates with an average degree of ethoxylation of 7, alkoxylates with one propylene oxide and multiple ethylene oxide units, seed oil based surfactant, such as Ecosurf SA7 or SA9 available from Dow Chemical, APGs, and branched alcohol Guerbet nonionics.
- Anionic surfactant 'Anionic surfactants' are defined herein as amphiphilic molecules comprising one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH of between 6 and 11.
- Preferred anionic surfactants are the alkali metal salts of organic sulphur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals.
- anionic surfactant hereinafter described can be used, such as alkyl ether sulphates, soaps, fatty acid ester sulphonates, alkyl benzene sulphonates, sulphosuccinate esters, primary alkyl sulphates, olefin sulphonates, paraffin sulphonates and organic phosphate; preferred anionic surfactants are the alkali and alkaline earth metal salts of fatty acid carboxylates, fatty alcohol sulphates, preferably primary alkyl sulfates, more preferably they are ethoxylated, for example alkyl ether sulphates; alkylbenzene sulphonates, alkyl ester fatty acid sulphonates, especially methyl ester fatty acid sulphonates and mixtures thereof.
- cationic, amphoteric surfactants and/or zwitterionic surfactants may be present in the laundry detergent compositions in which the hydroxamate is used as cosurfactant according to the invention.
- Preferred cationic surfactants are quaternary ammonium salts of the general formula R 1 R 2 RsR 4 N + X " , for example where Ri is a Ci 2 -Ci 4 alkyl group, R 2 and R 3 are methyl groups, R 4 is a 2-hydroxyethyl group, and X " is a chloride ion.
- This material is available commercially as Praepagen (Trade Mark) HY from Clariant GmbH, in the form of a 40% by weight aqueous solution.
- the laundry detergent composition in which the hydroxamate is used according to the invention further comprises an amphoteric or zwitterionic surfactant.
- Amphoteric surfactants are molecules that contain both acidic and basic groups and will exist as zwitterions at the normal wash pH of between 6 and 11.
- an amphoteric or zwitterionic surfactant is present at a level of from 0.1 to 20% by weight, more preferably from 0.25 to 15% by weight, even more preferably from 0.5 to 10% by weight.
- Suitable zwitterionic surfactants are exemplified as those which can be broadly described as derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds with one long chain group having about 8 to about 18 carbon atoms and at least one water solubilizing radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate.
- a general formula for these compounds is:
- R 1 contains an alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms, from 0 to 10 ethylene-oxy groups or from 0 to 2 glyceryl units;
- Y is a nitrogen, sulphur or phosphorous atom;
- R 2 is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms;
- x is 1 when Y is a sulphur atom and 2 when Y is a nitrogen or phosphorous atom;
- R 3 is an alkyl or hydroxyalkyl group with 1 to 5 carbon atoms and Z is radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate.
- Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide.
- Preferred zwitterionic surfactants are betaines, and especially amidobetaines.
- Preferred betaines are C 8 to Ci 8 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co-surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition.
- Other betaines that may be employed are sulfatobetaines, such as 3-(dodecyldimethylammonium)-1- propane sulfate; and 2-(cocodimethylammonium)-1 -ethane sulfate.
- Sulfobetaines such as: 3-(dodecyldimethyl-ammonium)-2-hydroxy-1 -propane sulfonate; 3-(tetradecyl- dimethylammonium)-1 -propane sulfonate; 3-(Ci 2 -Ci 4 alkyl- amidopropyldimethylammonium)-2-hydroxy-1 -propane sulfonate; and 3- (cocodimethylammonium)-i -propane sulfonate.
- Carboxybetaines such as (dodecyldimethylammonium) acetate (also known as lauryl betaine); (tetradecyldimethylammonium) acetate (also known as myristyl betaine); (cocodimethylammonium) acetate (also known as coconut betaine); (oleyldimethylammonium) acetate (also known as oleyl betaine); (dodecyloxymethyldimethylammonium) acetate; and (cocoamido- propyldimethylammonium) acetate (also known as cocoamido-propyl betaine or CAPB).
- (dodecyldimethylammonium) acetate also known as lauryl betaine
- tetradecyldimethylammonium) acetate also known as myristyl betaine
- (cocodimethylammonium) acetate also known as coconut betaine
- the sulfoniumbetaines such as: (dodecyldimethylsulfonium) acetate; and 3- (cocodimethyl-sulfonium)-i -propane sulfonate.
- the phosphoniumbetaines such as 4-(trimethylphosphonium)-1-hexadecane sulfonate; 3-(dodecyldimethylphosphonium)-1 -propanesulfonate; and 2-(dodecyldimethylphosphonium)-1 -ethane sulfate.
- the laundry detergent compositions preferably comprise carboxybetaines or sulphobetaines as amphoteric or zwitterionic surfactants, or mixtures thereof. Especially preferred is lauryl betaine.
- the betaines and hydroxamates may provide even further enhanced particulate soil removal when used together in the compositions according to the invention.
- the laundry detergent compositions in which the hydroxamate is used preferably comprise low levels of detergency builder, based on the weight of the total composition.
- the amounts of the inorganic builders zeolite and phosphate are less than 5 wt%. These builders are considered to be harmful to the environment when used in large quantities. Furthermore they need to be used at high levels to have a significant building effect and this is inconsistent with the modern concentrated highly weight efficient laundry detergent formulations.
- the builder is selected from the group of alkali and alkaline earth metal carbonates (e.g. sodium carbonate), silicates (e.g. layered silicate), and organic builders such as citrates (e.g. sodium citrate), succinates, sulphamates and malonates, and any combination of these.
- alkali and alkaline earth metal carbonates e.g. sodium carbonate
- silicates e.g. layered silicate
- organic builders such as citrates (e.g. sodium citrate), succinates, sulphamates and malonates, and any combination of these.
- organic builders are preferred. They may be used at levels of 1 wt% or more, up to, say, 50 wt%.
- Organic builders that may be present include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
- polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
- polyaspartates monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alky
- Organic builders may be used in minor amounts Especially preferred organic builders are citrates, suitably used in amounts of from 1 to 30 wt%, preferably from 1.5 to 10 wt%; and acry ⁇ c 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.
- the formulation may include one or more optional ingredients to enhance performance and properties. While it is not necessary for these elements to be present in order to practice this invention, the use of such materials is often very helpful in rendering the formulation acceptable for consumer use.
- optional components include, but are not limited to: hydrotropes, fluorescent whitening agents, photobleaches, fibre lubricants, reducing agents, enzymes, enzyme stabilising agents (such as borates and polyols), powder finishing agents, defoamers, bleaches, bleach catalysts, soil release agents, especially soil release polymers for cotton or polyester or both, antiredeposition agents, especially antiredeposition polymers, dye transfer inhibitors, buffers, colorants, fragrances, pro-fragrances, rheology modifiers, anti- ashing polymers, preservatives, insect repellents, soil repellents, water-resistance agents, suspending agents, aesthetic agents, structuring agents, sanitisers, solvents, including aqueous and non-aqueous solvents, fabric finishing agents, dye fixatives, wrinkle- reducing agents, fabric conditioning agents and deodorizers.
- hydrotropes such as borates and polyols
- powder finishing agents such as borates and polyols
- optional ingredients may include, but are not limited to, any one or more of the following: soap, peroxyacid and persalt bleaches, bleach activators, sequestrants, cellulose ethers and esters, other antiredeposition agents, sodium sulphate, sodium silicate, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, proteases, lipases, cellulases, amylases, other detergent enzymes, citric acid, soil release polymers, fabric conditioning compounds, coloured speckles, and perfume.
- the laundry detergent composition may suitably contain a bleach system based on 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.
- 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 5 to 35% by weight, preferably from 10 to 25% by weight.
- 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 1 to 8% by weight, preferably from 2 to 5% by weight.
- Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
- An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
- TAED N,N,N',N'-tetracetyl ethylenediamine
- peroxybenzoic acid precursors in particular, N,N,N-trimethylammonium toluoyloxy benzene sulphonate.
- a bleach stabiliser may also be present.
- Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
- EDTA ethylenediamine tetraacetate
- Dequest Trade Mark
- the composition it is preferred for the composition to contain no bleach and to rely on the improved clay stain removal derived from the novel hydroxamate and surfactant combination. This is particularly the case for liquid compositions.
- the detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
- detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
- Antiredeposition agents for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present.
- compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
- soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
- soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
- soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyviny
- a product according to the invention may take any suitable form, such as a solid, liquid or paste composition, for example as particulates (powders, granules), tablets or bars.
- the product is in a concentrated liquid with a surfactant concentration of at least 30wt%.
- Such compositions require the presence of hydrotropes to solubilise the ingredients. Ethanol is preferably avoided.
- Preferred hydrotropes are propylene glycol and glycerol. Based on this teaching the skilled person will be able to select other hydrotropes that avoid the use of highly volatile solvents like ethanol without the need for inventive activity.
- the detergent composition is in particulate form.
- the ratio of anionic to nonionic surfactant in the detersive surfactant system is then preferably at least 3:2, preferably at least 7:2.
- Powders of low to moderate bulk density may be prepared by spray-drying slurry, and optionally post dosing (dry-mixing) further ingredients.
- Routes available for powder manufacture include spray drying, drum drying, fluid bed drying, and scraped film drying devices such as the wiped film evaporator.
- a preferred form of scraped film device is a wiped film evaporator.
- One such suitable wiped film evaporator is the 'Dryex system' based on a wiped film evaporator available from Ballestra S.p.A..
- Alternative equipment would be the Chemithon the Turbo Tube' dryer system wherein a high active surfactant paste is heated and metering to a multi tube, steam-jacketed drying vessel.
- 'Concentrated' or 'compact' powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes.
- Tablets may be prepared by compacting powders, especially 'concentrated' powders.
- SRI is a measure of how much of a stain on textile is removed during a washing process.
- the intensity of any stain can be measured by means of a reflectometer in terms of the difference between the stain and a clean cloth giving Z-E * for each stain. It is defined as
- a SRI of 100 means complete removal of a stain.
- ⁇ E after wash is the difference in L a b colour space between the clean (unwashed) fabric and the stain after wash. So a ⁇ E after wash of zero means a stain that is completely removed. Therefore, a SRI aw of 100 is a completely removed stain.
- the clean (or virgin) fabric is an "absolute standard" which is not washed. For each experiment, it refers to an identical piece of fabric to that which the stain is applied. Therefore, its point in L a b colour space stays constant.
- the potassium salt of octyl hydroxamate was prepared by the method disclosed by
- Example 2 Removal of red clay stains on knitted polyester (2:1) A wash liquor was formulated, containing as surfactants primary alkyl sulfate (PAS, anionic, ex Kao Emal PH10) and alcohol ethoxylate (nonionic Ci 2 -7EO, Neodol 25-7 ex Shell), as shown in table 1 at the indicated concentrations. Additionally the wash liquor contained NaCI at a concentration of 5 mM. Water hardness was 6°FH (soft water, about 24 milligram calcium per litre), and water temperature was 30 0 C. No builder or sequestrants were added to the composition, as these ingredients were not required due to the soft water used. Table 1 Concentrations of surfactants and hydroxamate in wash liquors.
- PAS primary alkyl sulfate
- Ci 2 -7EO alcohol ethoxylate
- the red clay used is a form of pottery clay.
- Example 3 Removal of Georgia clay stains from knitted polyester and grass stains from woven cotton
- the surfactants used were sodium alkyl benzene sulphonate (Na LAS, anionic), alcohol ethoxylate (nonionic Ci 2 -7EO, Neodol 25-7 ex Shell) and a neutralised saturated soap (coco fatty acid (Prifac 5908 ex Uniqema)) as shown in table 3 at the indicated concentrations. Also used were standard compounds of a laundry liquid detergent (builder (sodium citrate), hydrotrope (5% glycerol and 9% propylene glycol), buffer and sequestrant (Dequest 2066 phosphonate), enzyme
- This example shows the effect of varying the ration of anionic to nonionic surfactant for the removal of Georgia Clay stains from knitted polyester, as measured in the Tergotometer hard wash protocol described above.
- the formulations are given in table 1 1 and the comparative formulations without the hydroxamate are given in table 10.
- Example 7 Higher Anionic to Nonionic ratios (Georgia Clay removal from woven cotton)
- Anionic/Nonionic formulations were made where the anionic to nonionic surfactant ratio was at least 4:1.
- a set of comparative formulations without hydroxamate was first made up as per table 13. Then a set of corresponding formulations comprising 5 wt% of octyl hydroxamate was made up as per table 14.
- the soap used was Prifac 5908.
- the hydrotropes were glycerol and propylene glycol.
- Example 8 Alternative Anionic: Primary Alkyl sulphate
- Table 18 The following results in table 18 were obtained for the removal of Georgia Clay stains from knitted polyester, as measured using the hard water Tergotometer wash protocol using 2.6 g/L formulation in wash.
- the comparative formulations without hydroxamate are given in table 16 and the hydroxamate containing formulations are given in table 17.
- the hydrotrope system as usual, comprised 5 wt% glycerol and 9 wt% propylene glycol.
- Compositions N-OH and P-OH are comparative as the ratio of anionic to nonionic is outside of the claimed range. Table 18
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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ES09768105T ES2731593T3 (en) | 2008-12-17 | 2009-12-15 | Composition of laundry detergent |
EP09768105.0A EP2358852B1 (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
CA2745559A CA2745559A1 (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition comprising hydroxamic acid |
AU2009327141A AU2009327141B2 (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
PL09768105T PL2358852T3 (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
CN2009801510329A CN102257109B (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
BRPI0922587-0A BRPI0922587B1 (en) | 2008-12-17 | 2009-12-15 | Detergent Wash Composition |
ZA2011/03716A ZA201103716B (en) | 2008-12-17 | 2011-05-20 | Laundry detergent composition |
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EP08171904.9 | 2008-12-17 | ||
EP08171904 | 2008-12-17 |
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PCT/EP2009/067193 WO2010069957A1 (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
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EP (1) | EP2358852B1 (en) |
CN (1) | CN102257109B (en) |
AU (1) | AU2009327141B2 (en) |
BR (1) | BRPI0922587B1 (en) |
CA (1) | CA2745559A1 (en) |
ES (1) | ES2731593T3 (en) |
PL (1) | PL2358852T3 (en) |
TR (1) | TR201906017T4 (en) |
WO (1) | WO2010069957A1 (en) |
ZA (1) | ZA201103716B (en) |
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Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863636A (en) * | 1988-02-12 | 1989-09-05 | American Cyanamid Company | Substituted N-hydroxyphthalimides and their use as detergent additives |
EP0388389A2 (en) * | 1989-03-16 | 1990-09-19 | Monsanto Europe S.A./N.V. | Improved detergent compositions |
-
2009
- 2009-12-15 CA CA2745559A patent/CA2745559A1/en not_active Abandoned
- 2009-12-15 WO PCT/EP2009/067193 patent/WO2010069957A1/en active Application Filing
- 2009-12-15 CN CN2009801510329A patent/CN102257109B/en active Active
- 2009-12-15 BR BRPI0922587-0A patent/BRPI0922587B1/en active IP Right Grant
- 2009-12-15 ES ES09768105T patent/ES2731593T3/en active Active
- 2009-12-15 TR TR2019/06017T patent/TR201906017T4/en unknown
- 2009-12-15 AU AU2009327141A patent/AU2009327141B2/en active Active
- 2009-12-15 PL PL09768105T patent/PL2358852T3/en unknown
- 2009-12-15 EP EP09768105.0A patent/EP2358852B1/en active Active
-
2011
- 2011-05-20 ZA ZA2011/03716A patent/ZA201103716B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863636A (en) * | 1988-02-12 | 1989-09-05 | American Cyanamid Company | Substituted N-hydroxyphthalimides and their use as detergent additives |
EP0388389A2 (en) * | 1989-03-16 | 1990-09-19 | Monsanto Europe S.A./N.V. | Improved detergent compositions |
Cited By (103)
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CN102257109A (en) | 2011-11-23 |
CN102257109B (en) | 2013-11-20 |
PL2358852T3 (en) | 2019-09-30 |
BRPI0922587A2 (en) | 2016-07-26 |
BRPI0922587B1 (en) | 2019-04-09 |
AU2009327141A1 (en) | 2010-06-24 |
CA2745559A1 (en) | 2010-06-24 |
EP2358852A1 (en) | 2011-08-24 |
EP2358852B1 (en) | 2019-03-27 |
ZA201103716B (en) | 2012-07-25 |
ES2731593T3 (en) | 2019-11-18 |
AU2009327141B2 (en) | 2014-03-20 |
TR201906017T4 (en) | 2019-05-21 |
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