WO1997024429A9 - Compositions de blanchiment au peroxyde active par des derives piperidone - Google Patents
Compositions de blanchiment au peroxyde active par des derives piperidoneInfo
- Publication number
- WO1997024429A9 WO1997024429A9 PCT/US1996/020174 US9620174W WO9724429A9 WO 1997024429 A9 WO1997024429 A9 WO 1997024429A9 US 9620174 W US9620174 W US 9620174W WO 9724429 A9 WO9724429 A9 WO 9724429A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- agents
- piperidone
- bleaching
- peroxygen
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 28
- XUWHAWMETYGRKB-UHFFFAOYSA-N 2-Piperidinone Chemical class O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004061 bleaching Methods 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000011780 sodium chloride Substances 0.000 claims abstract description 20
- 102000004190 Enzymes Human genes 0.000 claims abstract description 14
- 108090000790 Enzymes Proteins 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract 3
- 239000003381 stabilizer Substances 0.000 claims abstract 3
- 239000004094 surface-active agent Substances 0.000 claims abstract 3
- 239000012190 activator Substances 0.000 claims description 28
- OKBMCNHOEMXPTM-UHFFFAOYSA-M Potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 11
- NZAXGZYPZGEVBD-UHFFFAOYSA-N 1-benzoylpiperidin-4-one Chemical group C=1C=CC=CC=1C(=O)N1CCC(=O)CC1 NZAXGZYPZGEVBD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012425 OXONE® Substances 0.000 claims description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- 125000004416 alkarylalkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Chemical group 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 230000002335 preservative Effects 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 2
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 claims description 2
- 239000004902 Softening Agent Substances 0.000 claims 2
- 239000002216 antistatic agent Substances 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 2
- 230000003213 activating Effects 0.000 claims 1
- 239000008365 aqueous carrier Substances 0.000 claims 1
- 238000010936 aqueous wash Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M buffer Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 5
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-Piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 239000002979 fabric softener Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 description 13
- -1 aliphatic peroxyacids Chemical class 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002689 soil Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229940088598 Enzyme Drugs 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- ASQQEOXYFGEFKQ-UHFFFAOYSA-N Dioxirane Chemical compound C1OO1 ASQQEOXYFGEFKQ-UHFFFAOYSA-N 0.000 description 5
- 229940110715 ENZYMES FOR TREATMENT OF WOUNDS AND ULCERS Drugs 0.000 description 5
- 238000004851 dishwashing Methods 0.000 description 5
- 229940020899 hematological Enzymes Drugs 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 108091005771 Peptidases Proteins 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052570 clay Inorganic materials 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000001187 sodium carbonate Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- 244000269722 Thea sinensis Species 0.000 description 3
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical group [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000996 additive Effects 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000003625 amylolytic Effects 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing Effects 0.000 description 3
- 238000004900 laundering Methods 0.000 description 3
- 230000002366 lipolytic Effects 0.000 description 3
- 150000004967 organic peroxy acids Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- 229920001888 polyacrylic acid Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 102000033147 ERVK-25 Human genes 0.000 description 2
- 230000035693 Fab Effects 0.000 description 2
- 102000035443 Peptidases Human genes 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229940024999 Proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000003997 cyclic ketones Chemical class 0.000 description 2
- 230000000994 depressed Effects 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002522 swelling Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000011778 trisodium citrate Substances 0.000 description 2
- RWHGRWSDPVNGMH-UHFFFAOYSA-N 1-acetylpiperidin-3-one Chemical compound CC(=O)N1CCCC(=O)C1 RWHGRWSDPVNGMH-UHFFFAOYSA-N 0.000 description 1
- NNFOVLFUGLWWCL-UHFFFAOYSA-N 1-acetylpiperidin-4-one Chemical compound CC(=O)N1CCC(=O)CC1 NNFOVLFUGLWWCL-UHFFFAOYSA-N 0.000 description 1
- SBQPFUPQROCYRR-UHFFFAOYSA-N 1-benzoylpiperidin-3-one Chemical compound C=1C=CC=CC=1C(=O)N1CCCC(=O)C1 SBQPFUPQROCYRR-UHFFFAOYSA-N 0.000 description 1
- YIGJYHWHNWKKOM-UHFFFAOYSA-N 1-octadecylpiperidin-3-one Chemical compound CCCCCCCCCCCCCCCCCCN1CCCC(=O)C1 YIGJYHWHNWKKOM-UHFFFAOYSA-N 0.000 description 1
- RBFKRPBJQZUGFK-UHFFFAOYSA-N 1-octadecylpiperidin-4-one Chemical compound CCCCCCCCCCCCCCCCCCN1CCC(=O)CC1 RBFKRPBJQZUGFK-UHFFFAOYSA-N 0.000 description 1
- QOLXLZRNPULJIL-UHFFFAOYSA-N 1-propanoylpiperidin-4-one Chemical compound CCC(=O)N1CCC(=O)CC1 QOLXLZRNPULJIL-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N 2-(2-Ethoxyethoxy)ethanol Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- BAYGWLFODTUOOA-UHFFFAOYSA-N 2-carbonoperoxoyl-5-chlorobenzoic acid Chemical compound OOC(=O)C1=CC=C(Cl)C=C1C(O)=O BAYGWLFODTUOOA-UHFFFAOYSA-N 0.000 description 1
- SORZZSBKOXQKCB-UHFFFAOYSA-N 3-oxopiperidine-1-carbaldehyde Chemical compound O=CN1CCCC(=O)C1 SORZZSBKOXQKCB-UHFFFAOYSA-N 0.000 description 1
- NMDUFFZOCLWSIP-UHFFFAOYSA-N 4-oxopiperidine-1-carbaldehyde Chemical compound O=CN1CCC(=O)CC1 NMDUFFZOCLWSIP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 108010004032 Bromelains Proteins 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- XAPRFLSJBSXESP-UHFFFAOYSA-N Oxycinchophen Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=C(O)C=1C1=CC=CC=C1 XAPRFLSJBSXESP-UHFFFAOYSA-N 0.000 description 1
- 229940113115 POLYETHYLENE GLYCOL 200 Drugs 0.000 description 1
- 229940055729 Papain Drugs 0.000 description 1
- 108090000526 Papain Proteins 0.000 description 1
- 108090000284 Pepsin A Proteins 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 229920001021 Polysulfide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N Propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N Propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- JBUKJLNBQDQXLI-UHFFFAOYSA-N Sodium perborate Chemical compound [Na+].[Na+].O[B-]1(O)OO[B-](O)(O)OO1 JBUKJLNBQDQXLI-UHFFFAOYSA-N 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
- 229920002472 Starch Polymers 0.000 description 1
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetone amine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 240000005148 Vaccinium uliginosum Species 0.000 description 1
- IGWHDMPTQKSDTL-JXOAFFINSA-N [(2R,3S,4R,5R)-3,4-dihydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl dihydrogen phosphate Chemical compound O=C1NC(=O)C(C)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(O)=O)O1 IGWHDMPTQKSDTL-JXOAFFINSA-N 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- MWOBKFYERIDQSZ-UHFFFAOYSA-N benzene;sodium Chemical compound [Na].C1=CC=CC=C1 MWOBKFYERIDQSZ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 230000000368 destabilizing Effects 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 150000004844 dioxiranes Chemical class 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000019674 grape juice Nutrition 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003165 hydrotropic Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229940071676 hydroxypropylcellulose Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002452 interceptive Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000003472 neutralizing Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000019834 papain Nutrition 0.000 description 1
- 239000002245 particle Substances 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
- 229940111202 pepsin Drugs 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L phosphate Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000002797 proteolythic Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 230000002829 reduced Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960001322 trypsin Drugs 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 230000002087 whitening Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Definitions
- This invention relates to bleach compositions containing a peroxygen bleaching compound More particularly it relates to bleaching compositions containing inorganic peroxygen compounds activated with derivatives of piperidone
- Bleaching compositions have been used in the home and in industrial applications for bleaching stains on hard surfaces and soiled fabrics Hypochlorite bleaches are effective in removing such stains, when used in relatively high concentrations, but hypochlorite, along with other active chlorine bleaches, cause severe damage to fabric colors as well as to the textile fibers Furthermore, hypochlorite liquid bleaches present handling and packaging problems Color and fabric damage can be minimized by using milder oxygen bleaches, such as, sodium perborate or potassium monopersulfate The stain removal characteristics of these peroxygen bleaches, however, are much less desirable than those of the harsher halogen bleaching agents As a result, commercial bleaching compositions that contain peroxygen bleaches commonly employ activators, i e., compounds that enhance the performance of the peroxygen bleaches.
- activators i e., compounds that enhance the performance of the peroxygen bleaches.
- Bleaching compositions containing different types of bleach activators are known in the art including such compounds as esters, carboxylic acid anhydrides, quaternary ammonium salts and carboxylic acid salts
- U S 5,437,686 discloses an inorganic peroxygen compound and a bicyclic or tricyclic diketone as an activator for the peroxygen compound
- U.S. 3,822,1 14 discloses a process for the activation of peroxygen bleaching agents which comprises conjointly dissolving in aqueous solution certain peroxygen bleaching agents, certain aldehyde or ketone bleach activators and buffering agents Concentrated dry bleach compositions containing these compounds are also disclosed Among a host of other ketones there is also taught the use of certain piperidone compounds. Despite the effectiveness of prior bleach activators for use in the cleaning of fabrics and hard surfaces, there is still a need for more efficient activators which are fabric safe and environmentally friendly.
- Another object is to provide activators for enhancing the efficiency of peroxygen bleaches.
- R is hydrogen, an aryl monovalent group having 6 to about 10 carbon atoms, an alkyl having 1 to about 18 carbon atoms, alkaryl or aralkyl group having about 7 to about 20 carbon atoms, or a nitrogen substituted hydrocarbyl group, and the piperidone ring carbon atoms can be mono- or disubstituted by one or more groups defined by R.
- the peroxygen bleaching compositions of this invention can be used directly or in aqueous solution to bleach a fabric or in the alternative the bleaching compositions can be incorporated as an additive to a cleaning composition, such as, a powdered laundry detergent, a non-aqueous laundry detergent, a scouring powder, a hard surface cleaning composition, a powdered automatic dish washing composition, a non-aqueous automatic dish washing composition, a hair bleaching composition, a wound cleansing composition, a dental cleansing composition, a paper bleaching composition, a prespotter and the like.
- a cleaning composition such as, a powdered laundry detergent, a non-aqueous laundry detergent, a scouring powder, a hard surface cleaning composition, a powdered automatic dish washing composition, a non-aqueous automatic dish washing composition, a hair bleaching composition, a wound cleansing composition, a dental cleansing composition, a paper bleaching composition, a prespotter and the like.
- the present invention is directed to peroxygen bleaching compositions, and bleaching and/or stain removal processes carried out in an aqueous solution.
- These peroxygen bleaching compositions exhibit many practical utilities both domestic and industrial.
- the bleaching compound-activator compositions can be used alone or in combination with other conventional ingredients to effect (1) direct bleaching of stains on fabrics. (2) removal by bleaching of stains found on hard surfaces,and (3) inhibition of the transfer to fabrics of solution or suspended dyes found in fabric laundering solutions.
- the bleach compositions of the instant invention comprise a mixture of a peroxygen bleaching compound, preferably a monoperoxysulfate and more preferably potassium monoperoxysulfate and a piperidone derivative peroxygen bleaching compound activator, in a weight ratio of peroxygen bleaching compound to peroxygen bleaching compound activator of about 1 :1 to about 100: 1, preferably about 1 : 1 to about 50:1, and most preferably of about 1 : 1 to about 10: 1.
- the piperidone derivatives used herein are N-acyl 3- or 4-piperidones having the formula shown above.
- the bleaching compounds used in the instant invention are inorganic peroxygen salts, organic peroxygen acids and their water soluble salts.
- inorganic peroxygen salts include the water-soluble monopersulfates and water-soluble monoperoxyphosphates. Specific examples of such salts include sodium monopersulfate, potassium monopersulfate, disodium monoperphosphate, and dipotassium monoperphosphate.
- Highly preferred peroxygen salts, namely, those which are most highly activated by the piperidone derivative activators used in the instant invention are the sodium and potassium monopersulfates having the generic formulae NaHS05 and KHS05 respectively. Potassium monopersulfate is available commercially from E. I. duPont de Nemours and Company, Inc. under the trade name "Oxone". Oxone contains approximately 41.5% by weight KHS05 with the balance being KHS04 and K2S04 in about equal proportions.
- Peroxyacids which are suitable in the instant invention have the general formula:
- R is an alkylene group containing from 1 to about 16 carbon atoms or an arylene group containing from 6 to about 8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
- Y includes the following structures:
- organic peroxyacids or salts thereof suitable for use in this invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
- the organic peroxyacid is aliphatic
- the unsubstituted acid has the general formula:
- Y' can be :
- Preferred aliphatic peroxyacids include diperazelaic acid and diperadipic acid.
- organic peroxyacid is aromatic, the unsubstituted acid has the general formula:
- aromatic peroxy acids or salts thereof include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chloroperoxyphthalic acid and the monosodium salt of diperoxyterephthalic acid.
- a preferred aromatic peroxyacid is diperoxyisophthalic acid.
- the concentration of the peroxygen bleaching compound in the compositions of this invention is about 1 to about 75% by weight, preferably about 5 to about 60% by weight and most preferably about 5 to about 50% by weight.
- the concentration of the peroxygen bleaching compound is at a sufficient level in the bleaching composition to provide about 1 ppm to about 1000 ppm, when the composition is contacted with and dissolved in water at room temperature or higher.
- the bleaching system acts through a mechanism first involving the reaction of an acylpiperidone with a peroxygen bleaching compound, such as, a monoperoxysulfate upon contact with water to form a dioxirane intermediate.
- a peroxygen bleaching compound such as, a monoperoxysulfate
- the intermediate then reverts back to the original acylpiperidone liberating nascent oxygen at the same time functioning in the bleaching operation. Because of the reversion, the acylpiperidone may be considered as a catalyst since it is not consumed in the process.
- acylpiperidones of this invention are stable solids having a melting point of at least 25oC that can be conveniently post blended with the conventional powder detergents of bleach additives, unlike liquid peroxy bleach activators Additionally, these peroxygen bleach of the instant invention have the advantage that they are fully activated in the presence of water over a broad range of temperatures from below room temperature to higher temperatures, are stable solids resistant to hydrolysis and are biodegradable leaving no nitrogen residues and thus are environmentally safe and acceptable
- the concentration of the dioxirane formed from these acylpiperidones in use in the water is about 1 to about 10,000 parts per million (ppm), more preferably about 1 to about 5,000 ppm and most preferably about 1 to about 1,000 ppm
- the peroxygen bleaching composition can be utilized as an additive to a fully formulated composition at a concentration level of about 1 to about 75% by weight preferably about 6 to about 60 weight % and most preferably about 5 to about 50 weight % depending upon the kind of cleaning composition
- either the peroxygen bleaching compound, the monopersulfate for example, or the piperidone bleach activator can be encapsulated using any of the known encapsulating techniques and agents which are water soluble at a preselected temperature
- a typical powder form automatic dishwashing composition (by weight) containing the claimed peroxygen bleach composition comprises
- a typical nonaqueous liquid automatic dishwashing composition (by weight) comprises
- a typical powder form detergent composition (by weight) comprises
- An exemplary nonaqueous laundry detergent comprises (by weight)
- a typical scouring powder composition suitable for removing stains from hard surfaces comprises by weight: (1) 90.85% of White Silex
- a typical nonconcentrated powdered bleach composition comprises by weight: (1) 1-75% of Potassium Monopersulfate (2) 1-75% of the claimed acylpiperidone
- a buffering agent is defined as any non-interfering compound which can alter and/or maintain a specified pH
- Useful buffers include phosphates, carbonates, or bicarbonates designed to buffer in the range of 7-12 Specific examples include sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate, and disodiu hydrogen phosphate.
- Buffering agents generally comprise about 1% to about 85% of the instant concentrated bleaching compositions.
- Nonionic surfactants suitable for use herein include ethoxylated and propoxylated fatty alcohols, capped or uncapped. Typical nonionic surfactants are disclosed in U S Patent Nos. 4,316,812 incorporated herein by reference.
- Foam inhibition is important to increase dishwasher and laundry machine efficiency and minimize the destabilizing effects what may occur due to the presence of excess foam within the washer during laundering.
- the degree of foam is partly dependent on the hardness of the wash water where addition of builder salts, such as, NaTTP (sodium tripolyphosphate) which has a water softening effect may aid in providing a degree of foam inhibition
- builder salts such as, NaTTP (sodium tripolyphosphate) which has a water softening effect
- Particularly effective are silicones from Dow Chemical and the alkyl phosphoric acid esters derived from C12-C20 alkanols or ethoxylated alcohols. Commercially available examples of the latter are SAP from Hooker and LPKN from Knapsack
- alkali metal detergent builder salts include the polyphosphates, e.g , alkali metal pyrophosphates, alkali metal tripolyphosphates, alkali metaphosphates and the like
- Low molecular weight polyacrylates in the range of about 1,000 about 100,000 can be used in conjunction with the builder salts.
- a preferred polyacrylate is Norasol LMW45ND sold by Norsohaas as is Acusol TM 640D from Rohm & Haas These are employed in a range of about 0- 15% or 0 1 - 10%
- Other useful low molecular weight noncrosslinked polymers are Acusol 640D sold by
- compositions can also contain a nonphosphate builder system comprised of a mixture of phosphate-free particles formed from a builder salt and a low molecular weight polyacrylaate
- a preferred solid builder salt is an alkali metal carbonate, such as, sodium carbonate or sodium citrate or a mixture thereof When a mixture is used, a weight ratio of sodium carbonate to sodium citrate of about 9 1 to about 1 9 and preferably about 3 1 to about 1 3 is used
- the alkali metal silicates serve as anti-corrosion agents functioning to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts
- Sodium silicates of Na2/Si02 ratios of from 1 1 to 1 3 4 especially about 1 2 to 1 3 are preferred. Potassium silicates of the same ratios can also be used
- the preferred silicates are sodium disilicate (hydrated or anhydrous) and sodium metasilicate
- Thickening agents that can be used to ensure the physical stability of the suspension and to enhance its viscosity are those that will swell and develop thixotropic properties in a nonaqueous environment. These include organic polymers and inorganic and organic modified clays. Essentially, any clay can be used as long as it will swell in a nonaqueous environment and exhibits thixotropic properties.
- a preferred clay is bentonite
- a swelling agent is used with the bentonite clay
- a preferred swelling agent is a combination of propylene carbonate and tripropylene glycol methyl ether
- any other substance that will cause bentonite to swell in a nonaqueous environment and to develop thixotropic properties can be used
- the nonaqueous liquid canier materials that can be used for formulating nonaqueous liquid compositions include the higher glycols, polyglycols, polyoxides and glycol ethers Examples are propylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether acetate, and the like.
- a prefened nonaqueous carrier is polyethylene glycol 200 (PEG 200) or polyethylene glycol 300 (PEG 300).
- the system that can be used in the instant compositions to ensure phase stability can comprise a finely divided silica, such as, Cab-O-Sil M5, Cab-O-Sil EH5 or Aerosil 200 used at a level of about 0 to about 4 0 weight % and preferably about 0 5 to about 3 0 weight %.
- a finely divided silica such as, Cab-O-Sil M5, Cab-O-Sil EH5 or Aerosil 200 used at a level of about 0 to about 4 0 weight % and preferably about 0 5 to about 3 0 weight %.
- the detergent formulation can also contain a mixture of a proteolytic enzyme and an amylolytic enzyme and optionally, a lipolytic enzyme that serves to attack and remove the organic residues on glasses, plates, pots, pans, and other eating utensils
- proteolytic enzymes attack protein residues, lipolytic enzymes fat residues and amylolytic enzymes starches
- Proteolytic enzymes include the protease enzymes subtilism, bromelin, papain, trypsin end pepsin.
- Amylolytic enzymes include amylase enzymes
- Lipolytic enzymes include the iipase enzymes.
- the preferred amylase enzyme is available under the name Maxamyl, derived from Bacillus lichenformis, from Gist-Brocades of the Netherlands in the form of a nonaqueous slurry (18% of enzyme) having an activity of about 40,000 TAU/g Maxatase is a preferred protease enzyme.
- Other conventional ingredients which may be included in these compositions in minor amounts, i.e., less than about 3 weight % include perfumes, hydrotropic agents, such as, sodium benzene, toluene, and cu ene sulphonates, preservatives, dyestuffs, pigments and the like.
- Especially prefened for coloring are the chlorinated phthalocyanines and polysulfides of aluminosilicate which provide, respectively, green and blue tints. Titanium dioxide may be used for whitening or neutralizing off-shades.
- EXAMPLE 1 In order to test the efficacy of the claimed compositions, the following compositions were prepared and the described procedures performed. A solution of 350 mg of potassium monopersulfate (Oxone) and 1000 ppm of NP Fab Ultra detergent in one liter of water was prepared to which was added 30 ppm of N-benzoyl-4- piperidone
- Dioxiranes were generated in situ by the addition of Oxone (0 35 g) and the N-acyl- piperidone (BPIP) to the terg-o-tometer which contained the Fab Ultra detergent After ten seconds of agitation of the above solution, stained swatches were added to the solution and agitation was continued for 15 minutes. The stains were then rinsed in tap water, dried and their reflectance measured on a reflectometer to determine the average soil removal (% ASR)
- the % Average Soil Removal (% ASR) value is calculated by averaging the individual % Soil Removal (%SR) values of the four stains evaluated.
- the % Soil Removal (%SR) of a stained swatch was determined by manipulating its reflectance values which are measured from a swatch both before and after washing A reflectance value is the amount of light that a surface (such as a swatch) will reflect The following procedure will illustrate this protocol
- Coffee/Tea (Cotton Percal) stained swatches were bleached in the Dioxirane system DMOP-Oxone) using the procedure above.
- Table A provides the measured reflectance values of the swatches without stain (No Soil), with the stain (Soiled), and after washing (Washed) For each stain there are two swatches evaluated in order that there be an average value calculated.
- the % SR value for the coffee/tea stained swatch at 70° F is 83.69.
- the individual % SR values of all four stains were added up and the sum is divided by four as shown in Table B below where the % ASR value for the BPIP/Oxone (30/350 ppm) system is shown to be 59 59.
- Tables 1 and 2 contain the % Soil Removal Values obtained at 70° F and 100° F respectively for Oxone alone at a concentration of 350 ppm (Control), Oxone (350 ppm) plus 30 ppm of N-benzoyl-4-piperidone (BPIP), a dioxirane of this invention, Oxone (350 ppm) plus 100 ppm of cyciohexanone and Oxone (350 ppm) plus 100 ppm of cyclohexanone These data show that the BPIP/Oxone system is superior to that of cyclohexanone/Oxone system at both 70° F and 100° F.
- BPIP N-benzoyl-4-piperidone
- N-acyl 3- or 4-piperididones of this invention are N-benzoyl-3- piperidone or N-benzoyi-4-piperidone, the invention is not limited to these specific piperidones
- Other piperidones which evince peroxygen bleaching compound activation include but are not limited to N-formyl-3 -piperidone, N-formyl-4-piperidone, N-acetyl-3- piperidone, N-acetyl-4-piperidone, N-propionyI-3 -piperidone, N-propionyl-4-piperidone, N- stearyl-3 -piperidone, N-stearyl-4-piperidone as well as N-acyl 3- or 4-piperidones where R in the generic formula on page 3 are benzyl, xylyl, phenylethyl, amino, substituted amino and like groups
- compositions of this invention inhibit dye transfer from taking place from aqueous media in which soiled fabrics are being cleaned by the bleaching of the fabrics
Abstract
La présente invention concerne des compositions de blanchiment à base d'un composé de blanchiment et d'un N-acyl-3 ou 4-pipéridone, présents l'un et l'autre à raison d'environ 1 % à environ 75 % de la masse. Ces compositions peuvent également comporter des additifs tels que, notamment, des agents tensio-actifs, des agents anti-mousse, des adoucissants textiles, des stabilisants, des adjuvants minéraux de détergence, des tampons, des enzymes. En outre, ces compositions peuvent être formulées notamment en mélanges concentrés secs encapsulés ou en poudre en vrac, en solutions aqueuses, en solutions aqueuses contenant des solvants non-aqueux. Efficaces comme agents de blanchiment à des températures comprises entre une température inférieure à la température ambiante et des températures bien plus élevées, ces compositions sont biodégradables et ne présentent aucun risque de nature écologique.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU14257/97A AU1425797A (en) | 1995-12-28 | 1996-12-18 | Peroxygen bleach composition activated by piperidone derivatives |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US942695P | 1995-12-28 | 1995-12-28 | |
US60/009,426 | 1995-12-28 | ||
US1148696P | 1996-02-12 | 1996-02-12 | |
US60/011,486 | 1996-02-12 |
Publications (2)
Publication Number | Publication Date |
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WO1997024429A1 WO1997024429A1 (fr) | 1997-07-10 |
WO1997024429A9 true WO1997024429A9 (fr) | 1997-09-04 |
Family
ID=26679455
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/020174 WO1997024429A1 (fr) | 1995-12-28 | 1996-12-18 | Compositions de blanchiment au peroxyde active par des derives piperidone |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU1425797A (fr) |
CO (1) | CO4770895A1 (fr) |
WO (1) | WO1997024429A1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0915150A1 (fr) * | 1997-10-31 | 1999-05-12 | The Procter & Gamble Company | Procédés de trempage de tissus avec un composition liquide aqueuse contenant un sel de persulfate |
EP0913462A1 (fr) * | 1997-10-31 | 1999-05-06 | The Procter & Gamble Company | Compositions de blanchiment liquides aqueuses emballées dans un conteneur résistant aux UV |
DE10054693A1 (de) * | 2000-11-03 | 2002-05-08 | Clariant Gmbh | Reinigungsmittel für Zahnprothesen |
EP1288283A1 (fr) * | 2001-09-04 | 2003-03-05 | Unilever Plc | Compositions antimicrobiennes |
DE102006017837A1 (de) * | 2006-04-13 | 2007-10-18 | Henkel Kgaa | Aufhellmittel mit Piperidonen |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1368400A (en) * | 1971-08-05 | 1974-09-25 | Procter & Gamble | Bleaching process and compositions therefor |
ES2133710T3 (es) * | 1993-11-25 | 1999-09-16 | Warwick Int Group | Composiciones blanqueantes. |
-
1996
- 1996-12-18 AU AU14257/97A patent/AU1425797A/en not_active Abandoned
- 1996-12-18 WO PCT/US1996/020174 patent/WO1997024429A1/fr active Application Filing
- 1996-12-26 CO CO96067871A patent/CO4770895A1/es unknown
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