CA2254799C - Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof - Google Patents
Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof Download PDFInfo
- Publication number
- CA2254799C CA2254799C CA002254799A CA2254799A CA2254799C CA 2254799 C CA2254799 C CA 2254799C CA 002254799 A CA002254799 A CA 002254799A CA 2254799 A CA2254799 A CA 2254799A CA 2254799 C CA2254799 C CA 2254799C
- Authority
- CA
- Canada
- Prior art keywords
- stage
- process according
- compound
- bromine
- aminofunctional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000000034 method Methods 0.000 title claims abstract description 139
- 230000008569 process Effects 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 110
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 50
- 238000004061 bleaching Methods 0.000 title claims abstract description 36
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 31
- 239000000460 chlorine Substances 0.000 title claims abstract description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000004615 ingredient Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000007844 bleaching agent Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 50
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 50
- -1 bromine compound Chemical class 0.000 claims description 48
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 28
- 239000004094 surface-active agent Substances 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 15
- 125000001475 halogen functional group Chemical group 0.000 claims description 15
- 239000002304 perfume Substances 0.000 claims description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 230000006641 stabilisation Effects 0.000 claims description 9
- 238000011105 stabilization Methods 0.000 claims description 9
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000003082 abrasive agent Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 150000003842 bromide salts Chemical class 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 235000006708 antioxidants Nutrition 0.000 claims description 3
- 230000002070 germicidal effect Effects 0.000 claims description 3
- 239000003752 hydrotrope Substances 0.000 claims description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical class BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000000375 suspending agent Substances 0.000 claims description 3
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 125000004422 alkyl sulphonamide group Chemical group 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 150000003456 sulfonamides Chemical class 0.000 claims description 2
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 8
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000007792 addition Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 19
- 239000002253 acid Substances 0.000 description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 150000008051 alkyl sulfates Chemical class 0.000 description 8
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000019645 odor Nutrition 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- RMHAWGNPQWVACM-UHFFFAOYSA-M sodium sulfuric acid bromide Chemical compound [Na+].[Br-].OS(O)(=O)=O RMHAWGNPQWVACM-UHFFFAOYSA-M 0.000 description 6
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000645 desinfectant Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000010451 perlite Substances 0.000 description 3
- 235000019362 perlite Nutrition 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000467 phytic acid Substances 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229940067741 sodium octyl sulfate Drugs 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical compound CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101100037762 Caenorhabditis elegans rnh-2 gene Proteins 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- QWCKQJZIFLGMSD-UHFFFAOYSA-N alpha-aminobutyric acid Chemical class CCC(N)C(O)=O QWCKQJZIFLGMSD-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical class [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
An improved process for the manufacture of alkaline bleaching compositions, especially liquid and/or gel compositions of high solubility and low abrasiveness, useful to the consumer, especially as products for hard surface cleaning, bleaching or disinfectancy. The products are made by a three-stage process and comprise particular chlorine and bromine bleach sources and particular aminofunctional materials such as low-impurity sulfamate. The process has mixing sequences and starting ingredient selections which provide unexpectedly improved product.
Description
PROCESS FOR MANUFACTURING BLEACHING COMPOSITIONS
COMPRISING CHLORINE AND BROMINE SOURCES
AND PRODUCT THEREOF
FIELD OF THE INVENTION
The present invention relates to a process for the manufacture of alkaline bleaching compositions useful to the consumer, especially as products for hard surface cleaning, bleaching or disinfectancy. The products comprise both chlorine and bromine bleach sources. The process has mixing sequences and starting ingredient selections which provide unexpectedly improved product.
BACKGROUND OF THE INVENTION
Hard surface cleaners, bleaches and disinfectants are well-known formulated consumer products. They are useful for treating all manner of soiled kitchen, bathroom, sink, tub, shower, toilet bowl and counter top surfaces.
Such consumer products are known to include hypochlorite bleach.
Hypochlorite is desirable for its high effectiveness as a bleach and disinfectant.
However, it has several disadvantages, including that it can sometimes be too aggressive, tends to leave an unpleasant odor on the hands, and is not always stable on storage in a consumer product formulation.
Bromine containing compounds have been used in specialized circumstances for bleaching or disinfectancy. However they tend to be expensive and are often even more demanding in terms of storage stability than the chlorine analogs.
Sulfamic acid has been used as a cleaner, especially in acidic cleaners delivering high concentrations of the acid.
The chemistry of sulfamate-containing systems with halogens is extraordinarily complex and research in this area continues to this day.
Despite the partly known features of the art, there is an ongoing need for hard surface cleaners, bleaches and disinfectants suitable for consumer use which are improved in one or more of their characteristics including having superior effectiveness as a bleach and disinfectant, being less aggressive, tending to leave very low odor or even pleasant odor on the hands, and being highly stable on storage.
Accordingly, an improved process for making such compositions is provided herein, and the alkaline bleaching compositions secured thereby.
The process herein has several advantages, including that it is easy to operate and is safe and effective for its intended purpose. Surprisingly, it delivers a product which is actually superior to the product which is achieved when numerous other mixing sequences are employed.
BACKGROUND ART
Commonly assigned U.S. 3,583,922, Mc Clain and Meyer, June 8, 1971 and Canadian Patent Publ. CA 860279 A, published January 5, 1971 describe a solid composition for rapid removal of tannic acid stains having pH not less than 10.5 consisting of 0-95°~ abrasive, up to 10% surfactant, 0-60%
alkaline builder, a stable compound, preferably chlorinated trisodium orthophosphate, to provide 0.5°r6-5°~ available chlorine, sulfamic acid to produce preferably a ratio of CI to sulphamic acid of 500 to 1:1, preferably 3:1 to 6:1, optionally with additives. Such additives can include bromides, perfumes or borax. The compositions can be adjusted for sink cleaning or mechanical dishwashing.
COMPRISING CHLORINE AND BROMINE SOURCES
AND PRODUCT THEREOF
FIELD OF THE INVENTION
The present invention relates to a process for the manufacture of alkaline bleaching compositions useful to the consumer, especially as products for hard surface cleaning, bleaching or disinfectancy. The products comprise both chlorine and bromine bleach sources. The process has mixing sequences and starting ingredient selections which provide unexpectedly improved product.
BACKGROUND OF THE INVENTION
Hard surface cleaners, bleaches and disinfectants are well-known formulated consumer products. They are useful for treating all manner of soiled kitchen, bathroom, sink, tub, shower, toilet bowl and counter top surfaces.
Such consumer products are known to include hypochlorite bleach.
Hypochlorite is desirable for its high effectiveness as a bleach and disinfectant.
However, it has several disadvantages, including that it can sometimes be too aggressive, tends to leave an unpleasant odor on the hands, and is not always stable on storage in a consumer product formulation.
Bromine containing compounds have been used in specialized circumstances for bleaching or disinfectancy. However they tend to be expensive and are often even more demanding in terms of storage stability than the chlorine analogs.
Sulfamic acid has been used as a cleaner, especially in acidic cleaners delivering high concentrations of the acid.
The chemistry of sulfamate-containing systems with halogens is extraordinarily complex and research in this area continues to this day.
Despite the partly known features of the art, there is an ongoing need for hard surface cleaners, bleaches and disinfectants suitable for consumer use which are improved in one or more of their characteristics including having superior effectiveness as a bleach and disinfectant, being less aggressive, tending to leave very low odor or even pleasant odor on the hands, and being highly stable on storage.
Accordingly, an improved process for making such compositions is provided herein, and the alkaline bleaching compositions secured thereby.
The process herein has several advantages, including that it is easy to operate and is safe and effective for its intended purpose. Surprisingly, it delivers a product which is actually superior to the product which is achieved when numerous other mixing sequences are employed.
BACKGROUND ART
Commonly assigned U.S. 3,583,922, Mc Clain and Meyer, June 8, 1971 and Canadian Patent Publ. CA 860279 A, published January 5, 1971 describe a solid composition for rapid removal of tannic acid stains having pH not less than 10.5 consisting of 0-95°~ abrasive, up to 10% surfactant, 0-60%
alkaline builder, a stable compound, preferably chlorinated trisodium orthophosphate, to provide 0.5°r6-5°~ available chlorine, sulfamic acid to produce preferably a ratio of CI to sulphamic acid of 500 to 1:1, preferably 3:1 to 6:1, optionally with additives. Such additives can include bromides, perfumes or borax. The compositions can be adjusted for sink cleaning or mechanical dishwashing.
JP 63108099 A, Lion Corp., published May 12, 1988 describes a bleaching agent for controlling chlorine odor containing a specific ratio of hypochlorite and sulfamic acid and/or sulfamate and pH adjusting agents. The ratio is 2-8 wt% hypochlorite based on "the amount of the effective chlorine" (sic) and there is a 0.25 to 1.5 mol ratio of sulfamic acid, and/or a sulfamate, to hypochlorite.
JP 63161088 A, Lion Corp., published July 4, 1988 describes bleaching compositions for cloth comprising mainly hydrogen peroxide and sulfamic acid andlor water-soluble sulfamate and hypohalous acid and/or a water-soluble hypohalite salt such as NaClO, Ca(OCI)2, bleaching powder or NaBrO, the sulfamate being present in an amount of 0.5-5 mol per mol hypohalite.
U.S. 4,992,209, February 12, 1991, Smyk et al describes a bactericidal, fungicidal system having a nitrite-containing corrosion inhibitor, for example cooling systems, prepared by reacting NaBr with NaOCI or C12 and sodium sulfamate or sulfamic acid and the product is assertedly "reacted within 5 hours of preparation".
U.S. 5,431,839, Guillou, July 11,1995 describes sulfamic acid cleaning/stripping compositions comprising heteropoiysaccharide thickening agents. U.S. 5,047,164, September 10, 1991, Corby, describes compositions containing interhalogens and acid especially adapted for cleaning and disinfecting milk- and food-handling equipment. U.S. 4,279,764, Brubaker, July 21, 1981 describes encapsulated bleaches comprising storage stable chlorinated isocyanurates. U.S. 4,233,173, Mayer et al, November 11,1980 and U.S. 4,201,687, Crutchfield et a1 describe detergent compositions containing chloroimidodisuifate bleaching agent. U.S. 5,470,499, Choy et al, November 28, 1995 describes thickened aqueous abrasive cleansers with improved rinsability. Commonly assigned U.S. 4,051,056, September 27, 1977, Hartman describes abrasive scouring compositions with perlite and hypochlorite bleach. Commonly assigned U.S. 3,715,314, Morgenstern, February 6, 1973 describes scouring cleanser compositions. Commonly assigned U.S. 5,384,061, Wise, January 24, 1995 describes stable thickened aqueous bleaching compositions comprising chlorine bleach and phytic acid.
industrial uses of sulfamic acid are included in a literature review, see "Inorganic Sulfur Chemistry", G. Nickless, Ed., Elsevier, 1968, Chapter 18, "Amido- and Imido-sulphonic acids", 607-667 and references cited therein; see also Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed., Wifey-Interscience, Vol. 21, "Sulfamic Acid and Sulfamates", pp 949-960.
Chloramines, Bromamines and N-halamines more generally are reviewed in Kirk Othmer's Encyclopedia of Chemical Technology, Wiley-Interscience, 4th Ed., Vol. 5, pp 911-932; see also a corresponding article in the 3rd edition of the same Encyclopedia. Chlorine gas has previously been mixed with solutions containing sulfamic acid: see Korshak et al., Zh. Obsch. Khim., Vol. 18 (1948), pages 753-756, but the mixture decomposed.
SUMMARY OF THE INVENTION
The present invention encompasses a process for manufacturing an alkaline bleaching composition, preferably an aqueous liquid bleaching composition, said process comprising at least three stages. These stages include, in sequence (I) a pre-bromine stage, (II) a bromine compound addition stage, and (III) a product stabilization stage, and each of said stages has at least one mixing step.
In said process, said pre-bromine stage, (I), comprises a step, (a), of mixing in any order components comprising a hypochlorite source and an aminofunctional compound having a stable N-halo derivative; thereby forming a stage (I) mixture; provided that at the end of said pre-bromine stage, said stage (1) mixture has a pH not exceeding about 11, preferably lower; said bromine compound addition stage, {II), is initiated at said pH and comprises a step, {b), of mixing in any order with said stage (I) mixture, a bromine compound;
thereby forming a stage (II) mixture; and said product stabilization stage, (111), comprises at least one step, (c), of mixing in any order with said stage (II) mixture, an alkali in an amount suitable to arrive at a final pH for the product of said process of at least about 13.
The product provided by this process has unique advantages in terms of excellent bleaching effect at the same time as permitting a minimization of "bleach odor" on skin. The preferred product is a transparent yellow aqueous liquid, which may optionally be thickened andlor perfumed.
JP 63161088 A, Lion Corp., published July 4, 1988 describes bleaching compositions for cloth comprising mainly hydrogen peroxide and sulfamic acid andlor water-soluble sulfamate and hypohalous acid and/or a water-soluble hypohalite salt such as NaClO, Ca(OCI)2, bleaching powder or NaBrO, the sulfamate being present in an amount of 0.5-5 mol per mol hypohalite.
U.S. 4,992,209, February 12, 1991, Smyk et al describes a bactericidal, fungicidal system having a nitrite-containing corrosion inhibitor, for example cooling systems, prepared by reacting NaBr with NaOCI or C12 and sodium sulfamate or sulfamic acid and the product is assertedly "reacted within 5 hours of preparation".
U.S. 5,431,839, Guillou, July 11,1995 describes sulfamic acid cleaning/stripping compositions comprising heteropoiysaccharide thickening agents. U.S. 5,047,164, September 10, 1991, Corby, describes compositions containing interhalogens and acid especially adapted for cleaning and disinfecting milk- and food-handling equipment. U.S. 4,279,764, Brubaker, July 21, 1981 describes encapsulated bleaches comprising storage stable chlorinated isocyanurates. U.S. 4,233,173, Mayer et al, November 11,1980 and U.S. 4,201,687, Crutchfield et a1 describe detergent compositions containing chloroimidodisuifate bleaching agent. U.S. 5,470,499, Choy et al, November 28, 1995 describes thickened aqueous abrasive cleansers with improved rinsability. Commonly assigned U.S. 4,051,056, September 27, 1977, Hartman describes abrasive scouring compositions with perlite and hypochlorite bleach. Commonly assigned U.S. 3,715,314, Morgenstern, February 6, 1973 describes scouring cleanser compositions. Commonly assigned U.S. 5,384,061, Wise, January 24, 1995 describes stable thickened aqueous bleaching compositions comprising chlorine bleach and phytic acid.
industrial uses of sulfamic acid are included in a literature review, see "Inorganic Sulfur Chemistry", G. Nickless, Ed., Elsevier, 1968, Chapter 18, "Amido- and Imido-sulphonic acids", 607-667 and references cited therein; see also Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed., Wifey-Interscience, Vol. 21, "Sulfamic Acid and Sulfamates", pp 949-960.
Chloramines, Bromamines and N-halamines more generally are reviewed in Kirk Othmer's Encyclopedia of Chemical Technology, Wiley-Interscience, 4th Ed., Vol. 5, pp 911-932; see also a corresponding article in the 3rd edition of the same Encyclopedia. Chlorine gas has previously been mixed with solutions containing sulfamic acid: see Korshak et al., Zh. Obsch. Khim., Vol. 18 (1948), pages 753-756, but the mixture decomposed.
SUMMARY OF THE INVENTION
The present invention encompasses a process for manufacturing an alkaline bleaching composition, preferably an aqueous liquid bleaching composition, said process comprising at least three stages. These stages include, in sequence (I) a pre-bromine stage, (II) a bromine compound addition stage, and (III) a product stabilization stage, and each of said stages has at least one mixing step.
In said process, said pre-bromine stage, (I), comprises a step, (a), of mixing in any order components comprising a hypochlorite source and an aminofunctional compound having a stable N-halo derivative; thereby forming a stage (I) mixture; provided that at the end of said pre-bromine stage, said stage (1) mixture has a pH not exceeding about 11, preferably lower; said bromine compound addition stage, {II), is initiated at said pH and comprises a step, {b), of mixing in any order with said stage (I) mixture, a bromine compound;
thereby forming a stage (II) mixture; and said product stabilization stage, (111), comprises at least one step, (c), of mixing in any order with said stage (II) mixture, an alkali in an amount suitable to arrive at a final pH for the product of said process of at least about 13.
The product provided by this process has unique advantages in terms of excellent bleaching effect at the same time as permitting a minimization of "bleach odor" on skin. The preferred product is a transparent yellow aqueous liquid, which may optionally be thickened andlor perfumed.
All percentages, ratios. and proportions herein are on a weight basis unless otherwise indicated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents a schematic outline of the present process, showing the conversion of starting-materials (ingredients) to product via a series of stages, comprising, in sequence, Stage (I), Stage (II) and Stage (ill). Each stage, as indicated, includes one or more steps. Stage (I) includes an essential step, namely Step (a). Stage (II) includes an essential step, namely Step (b), and Stage (111) includes an essential Step, namely step (c). The present process in the most reduced form which c;an be constructed from Fig. 1 consists of the sequence of three steps (a) followed by (b) followed by (c). Each of the essential stages and steps, as well as suitable ingredients and characteristics of the product are described in detail hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
In acaxdan ce with the present invention, it has been discovered that in order to seaxe an alkaline bleaching composition having superior technical performance and dexirability for the consumer, it is necessary to provide two distinct types of halogen ingredient including at least one having, at the outset, the form of a bromine compound and at least one having, at the outset, the form of a hypohalite compound. It has also been found essential to particularly soled and include a certain aminofundional compound; and to provide a particular process, especially in tonne of mixing sequence, to secure the product benefits.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents a schematic outline of the present process, showing the conversion of starting-materials (ingredients) to product via a series of stages, comprising, in sequence, Stage (I), Stage (II) and Stage (ill). Each stage, as indicated, includes one or more steps. Stage (I) includes an essential step, namely Step (a). Stage (II) includes an essential step, namely Step (b), and Stage (111) includes an essential Step, namely step (c). The present process in the most reduced form which c;an be constructed from Fig. 1 consists of the sequence of three steps (a) followed by (b) followed by (c). Each of the essential stages and steps, as well as suitable ingredients and characteristics of the product are described in detail hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
In acaxdan ce with the present invention, it has been discovered that in order to seaxe an alkaline bleaching composition having superior technical performance and dexirability for the consumer, it is necessary to provide two distinct types of halogen ingredient including at least one having, at the outset, the form of a bromine compound and at least one having, at the outset, the form of a hypohalite compound. It has also been found essential to particularly soled and include a certain aminofundional compound; and to provide a particular process, especially in tonne of mixing sequence, to secure the product benefits.
Alkaline Bleaching Compositions Accordingly, the present invention relates to processes for making alkaline bleaching compositions and to the products thereof. "Alkaline bleaching compositions" as defined herein are strongly alkaline. The "alkaline bleaching compositions" herein have a pH as is of at least about 13, and are made from ingredients comprising a hypophalite source and a bromine compound along with at least one particularly selected aminofunctional compound. Alkaline beaching compositions herein are useful to the consumer as products for hard surface cleaning, bleaching or disinfectancy. They can, in general, have any suitable physical form, such as granular, tablet, paste, gel ar liquid form, and can be aqueous or non-aqueous. However, the process herein is especially well adapted for making aqueous, alkaline, liquid-form or gel-form bleaching compositions: technical problems of processing are greatest for such compositions. Unless otherwise noted, embodiments hereinafter which illustrate the processes and product of the invention therefore relate to the aqueous liquid forms.
Process Stases Processes herein generally comprise at least three stages:
(I) a pre-bromine stage;
(II) a bromine compound addition stage, and (III) a product stabilization stage.
The stages are carried out in the order (I) then (II) then (III). The stages are identified in Fig. 1. Each stage includes one or more steps. In a minimum configuration, the process includes, in Stage (I), step (a); in Stage (II), step (b), and in Stage (III), step (c). Additional steps, for example of adding and/or mixing other ingredients such as perfumes, surfactants and the like, may be inserted before or after any of the essential steps, provided that they do not affect the indicated sequence of essential steps and further, that they are perfomed compatibly with respecting the pH criticaiities described herein.
In more detail, Stage (I), the pre-bromine addition stage, is a stage used to bring together a hypochlorite source and a particular aminofunctional compound; Stage (II), the bromine compound addition stage, is a stage used to introduce a bromine compound; and stage (III), the product stabilization stage, is a stage used to stabilize the product by increasing pH.
Thus the invention encompasses a process for manufacturing an alkaline bleaching composition, said process comprising at least three stages including, in sequence, (I) a pre-bromine stage, (II) a bromine compound addition stage, and (III) a product stabilization stage, each of said stages having at least one mixing step; wherein in said process, said pre-bromine stage comprises a step, (a), of mixing in any order components comprising a hypochlorite source and an aminofunctional compound having a stable N-halo derivative; thereby forming a stage (I) mixture; provided that at the end of said pre-bromine stage, said stage (I) mixture has a pH not exceeding about 11; said bromine compound addition stage is initiated at said pH and comprises a step, (b), of mixing in any order with said stage (I) mixture, a bromine compound; thereby forming a stage (II) mixture; and said product stabilization stage comprises at least one step, (c), of mixing in any order with said stage (11) mixture, an alkali in an amount suitable to arrive at a final pH for the product of said process of at least about 13.
Particularly preferred processes herein are restrictive in terms of when the bromine compound may be added. In preferred processes, no stage other than (II) and no step other than (b) comprises adding a bromine compound.
Surprisingly, it has been found that adding bromine compound elsewhere in the sequence has a negative impact on product performance.
Optional Process Steps The present process can include various optional steps. An optional step useful herein is illustrated by a dilution step, included in the process after completion of stage (III). Such a step as a dilution step can in fact be carried out either by the manufacturer, or by the user of the product of stages (I), (II) and (III). Dilution steps can in general be included in stage (I), stage (II) or stage (III) of the present process, though prefereably, dilution is avoided in those stages. Typically for best storage stability, a dilution step is not carried out in the plant, but rather, by the consumer who uses the composition.
Dilution can result in pH variation, typically including pH decrease.
Process Stases Processes herein generally comprise at least three stages:
(I) a pre-bromine stage;
(II) a bromine compound addition stage, and (III) a product stabilization stage.
The stages are carried out in the order (I) then (II) then (III). The stages are identified in Fig. 1. Each stage includes one or more steps. In a minimum configuration, the process includes, in Stage (I), step (a); in Stage (II), step (b), and in Stage (III), step (c). Additional steps, for example of adding and/or mixing other ingredients such as perfumes, surfactants and the like, may be inserted before or after any of the essential steps, provided that they do not affect the indicated sequence of essential steps and further, that they are perfomed compatibly with respecting the pH criticaiities described herein.
In more detail, Stage (I), the pre-bromine addition stage, is a stage used to bring together a hypochlorite source and a particular aminofunctional compound; Stage (II), the bromine compound addition stage, is a stage used to introduce a bromine compound; and stage (III), the product stabilization stage, is a stage used to stabilize the product by increasing pH.
Thus the invention encompasses a process for manufacturing an alkaline bleaching composition, said process comprising at least three stages including, in sequence, (I) a pre-bromine stage, (II) a bromine compound addition stage, and (III) a product stabilization stage, each of said stages having at least one mixing step; wherein in said process, said pre-bromine stage comprises a step, (a), of mixing in any order components comprising a hypochlorite source and an aminofunctional compound having a stable N-halo derivative; thereby forming a stage (I) mixture; provided that at the end of said pre-bromine stage, said stage (I) mixture has a pH not exceeding about 11; said bromine compound addition stage is initiated at said pH and comprises a step, (b), of mixing in any order with said stage (I) mixture, a bromine compound; thereby forming a stage (II) mixture; and said product stabilization stage comprises at least one step, (c), of mixing in any order with said stage (11) mixture, an alkali in an amount suitable to arrive at a final pH for the product of said process of at least about 13.
Particularly preferred processes herein are restrictive in terms of when the bromine compound may be added. In preferred processes, no stage other than (II) and no step other than (b) comprises adding a bromine compound.
Surprisingly, it has been found that adding bromine compound elsewhere in the sequence has a negative impact on product performance.
Optional Process Steps The present process can include various optional steps. An optional step useful herein is illustrated by a dilution step, included in the process after completion of stage (III). Such a step as a dilution step can in fact be carried out either by the manufacturer, or by the user of the product of stages (I), (II) and (III). Dilution steps can in general be included in stage (I), stage (II) or stage (III) of the present process, though prefereably, dilution is avoided in those stages. Typically for best storage stability, a dilution step is not carried out in the plant, but rather, by the consumer who uses the composition.
Dilution can result in pH variation, typically including pH decrease.
Other optional steps useful herein include surfactant addition steps, or steps of adding or mixing any suitable optional ingredient, such as those identified under "optional ingredients" hereinafter.
Process Means Any suitable means may be employed for accomplishing the present process.
Reactors are desirably chemically inert to halogen bleach and strongly alkaline conditions, plastics andlor borosilicate glass lined apparatus is desirably used both for durability and to minimize contamination of the product by metals.
Reactors need not be designed for operation under pressure provided that suitable venting is provided. Mixing of ingredients can be accomplished using any suitable mixer, such as a motor-driven paddle. Alternately, a centrifugal pump can be used to provide a recirculating jet of product solution, driving agitation of the mixture. Other useful process means herein include means for removing vapors from the work environment. Such means include conventional scrubbers, etc.
Process Conditions Temperature In general the present process can be carried out at widely ranging temperatures. Preferably, each of said steps (b) and (c) is performed at a temperature in the range from about 5 °C to about 80 °C, preferably from about °C to about 45 °C, most preferably at or about ambient temperature, e.g., about 20°C. Highly preferred process herein accomplish all steps in stages (I), (II) and (III) at such temperatures. At higher temperatures, there may be an increased decomposition tendency and at lower temperatures, freezing can be a problem.
pH's The present process requires particular limits on pH variation. There is a general requirement that at the end of the pre-bromine stage and at the beginning of the bromine stage, the pH of the stage (I) mixture is not in excess of about 11. In preferred embodiments, this pH is not in excess of about 8, more preferably, it lies in the range from about 1 to about 6.9.
Process Means Any suitable means may be employed for accomplishing the present process.
Reactors are desirably chemically inert to halogen bleach and strongly alkaline conditions, plastics andlor borosilicate glass lined apparatus is desirably used both for durability and to minimize contamination of the product by metals.
Reactors need not be designed for operation under pressure provided that suitable venting is provided. Mixing of ingredients can be accomplished using any suitable mixer, such as a motor-driven paddle. Alternately, a centrifugal pump can be used to provide a recirculating jet of product solution, driving agitation of the mixture. Other useful process means herein include means for removing vapors from the work environment. Such means include conventional scrubbers, etc.
Process Conditions Temperature In general the present process can be carried out at widely ranging temperatures. Preferably, each of said steps (b) and (c) is performed at a temperature in the range from about 5 °C to about 80 °C, preferably from about °C to about 45 °C, most preferably at or about ambient temperature, e.g., about 20°C. Highly preferred process herein accomplish all steps in stages (I), (II) and (III) at such temperatures. At higher temperatures, there may be an increased decomposition tendency and at lower temperatures, freezing can be a problem.
pH's The present process requires particular limits on pH variation. There is a general requirement that at the end of the pre-bromine stage and at the beginning of the bromine stage, the pH of the stage (I) mixture is not in excess of about 11. In preferred embodiments, this pH is not in excess of about 8, more preferably, it lies in the range from about 1 to about 6.9.
In preferred embodiments, from the end of stage I, the entire process is conducted at a rising pH. Such rising pH desirably corresponds with a value of dpH/dt of at least about + 0.1 pH units/min, preferably about + 0.5 pH
unitslmin, or higher.
In such embodiments, it will be appreciated that the instant process contains a pH minimum. The position in the overall sequence of the present process of this minimum is found at the end of stage (I).
Pressure The present process can be conducted at any convenient pressure. For example, chlorine gas and alkali can be reacted under pressure, for example up to about 5 atm., in stage (I) prior to adding the aminofunctional compound;
and the following stages of the process can be conducted at atmospheric pressure, or even at reduced pressure if scrubbers or condensers are provided for collecting lost halogen. Preferred processes are conducted at atmospheric pressure.
Time The present process can be conducted in batch or continuous mode. Unless otherwise indicated, illustrations of the process hereinafter are batch-mode.
Times for completion of a batch may in general vary widely. Typically, times of about 5 min to about 1.5 hours are typical for each of stages (I) , (II) and (III).
In preferred embodiments, Stage (II) will allow at least sufficient time to permit the bromine compound to substantially dissolve before proceeding with stage (III). Also preferably, stage (II) is continued until development of a yellow color in the stage {II) mixture. In general, the longer process times are associated with larger-scale processes. It is preferred herein to minimize the overall reaction time, and in particular, while allowing sufficient time for stage (II), to proceed without delay from that stage to the end of stage (III). Moreover, it is highly preferred to minimize any time period between the end of step (a) and the beginning of step (b), and between the end of step (b) and the beginning of step (c).
Concentration and Concentration Ratios The present process can be conducted over a wide range of concentrations of the ingredients in water. In preferred embodiments, the process is characterized by a dilution factor for the sure of stages subsequent to stage (I) which is not in excess of about twofold. In general, concentrations of the ingredients are adjusted such that the product of stage (/I1), comprises from about 0.01 °~ to about 10 % Available Chlorine. Also, in terms of relative proportions of the ingredients, the present process preferably relies on an interhalogen ratio [8r] : [0C/-] of from about 10 : 1 to about 1 : 10, preferably 1:2 to 1:5, wherein (Br] represents total moles Br added into said process from said bromine compound and [0C/- ] represents total moles hypochlorite added into said process from said hypochlorite source. Moreover, the preferred processes herein employ an amino-halo ratio [A] : (X] of from about 10 : 1 to about 1 : 10, wherein [A) represents the total of moles of amino moieties of said aminofunctional compound used to form said composition and wherein [X]
represents total moles of bleaching halogen, measurable as Available Chlorine, added into said composition.
Very preferably, said amino-halo ratio is from about 1.0 : 1.0 to about 1.5 :
1Ø
To illustrate, with repect to the above quantities, sulfamic acid, which contains one mole of amino moieties per mole of the compound, is easily computed in the above relation: [A] is simply the number of moles of sulfamate; but to give another illustration, when melamine is used, [A] is the number of moles of melamine used multiplied by the number of moles (which is 3) of amino moieties contained in any one mole of melamine.
In4redients HYpochlorite Source In general, any convenient hypochiorite source can be used in the instant process. Preferred hypochlorite sources are selected from chlorine, hypochlorous acid, alkali metal hypochlorites, alkaline earth metal hypochiorites, the product of mixing a hypochlorite-liberating compound with aqueous alkali, and mixtures thereof. Suitable hypochlorite-liberating compounds, in the sense immediately above, are illustrated by dichloroisocyanuric acid and its sodium salts and hydrates, which hydrolyze rather readily to release hypochlorite. Highly preferred hypochlorite sources herein are selected from alkali metal hypochlorites and the product of mixing said hypochlorite-liberating compound and aqueous alkali.
Aminofunctional compound From the thousands of available aminofunctional compounds, the present invention selects a limited few which are found operative. In processes of the invention, suitable aminofunctional compounds are those having stable N-halo derivatives. The term "having a stable N-halo derivative" herein is defined as "capable of forming an N-halo derivative and it is stable", rather than as necessarily "possessing a stable N-halo moiety at the inception of the present process". Suitable aminofunctional compounds meeting the needs of the present invention are selected from (i) primary aminofunctional compounds selected from sulfamic acid, alkali-metal sulfamates, alkaline earth sulfamates, tetra-alkylammonium sulfamates, and mixtures thereof; (ii) secondary aminofunctionai compounds selected from secondary amine derivatives having formula RR'NH or (R")2NH wherein R, R' and R" are organic moieties and wherein carbon atoms of said organic moieties are bonded covalently to NH;
(iii) sulfonamides selected from sulfamide, p-toluenesulfonamide, imidodisulfonamide, benZenesulfonamide, alkyl sulfonamides, and mixtures thereof; (iv) melamine, cyanamide; and (v) mixtures thereof.
Suitable secondary aminofunctional compounds (ii) include those not specifically identified in (i), (iii), (iv) and (v), wherein R, R' and R" are independently selected from C1-C12 linear saturated and C3-C12 branched saturated moieties which can be alkyl, aryl or heterocyclic, optionally substituted by carboxylic acid or carboxylate: an example of the latter carboxylic-substituted derivatives is the alpha-aminobutyrates. Preferred secondary aminofunctional compounds are known for use as disinfectants, especially those which are water-soluble and those having N-halo derivatives which are relatively insensitive to shock.
In alternate terms, the present process is believed to be applicable wherever the aminofunctional compound has a hydrolysis constant, K, as defined by K=[HOCI][RNH2] I [RNHCI]
or K=[HOCI][RR'NH] I [RR'NCI]
or K=[HOCI][(R")2NH] I [(R")2NC1]
in the range of from about 10 ~ to about 10 -9, provided that no isocyanurate or chlorinated isocyanurate is included as the essential aminofunctional compound.
O
Hydrolysis constants such as the above are well known in the art and are defined conventionally. See, for example, Kirk Othmer's Encyclopedia of Chemical Tectanology, 3rd Ed., Vol. 5, article entitled "Chloramines and Bromamines", see especially page 567, and Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 3, see especially pages 940-941.
Subject to the abave-identified requirements, preferred secondary aminofunctional compounds can be selected from those identified in Kirk Othmer, Encyclopedia of Chemical Technology, 4th. Ed., 1993, pages 918-925 and include compounds. identified under the headings "Organic Chloramines and Bromamines", "~4liphatic Compounds", "Aromatic Compounds" and "Heterocyclic Compounds'".
Sulfamic acid or sodium sulfamate are highly preferred aminofunctional compounds herein.
Alkali Suitable alkali in the present process is selected from alkali-metal-, alkaline-earth-, and tetraalkylamrnonium- oxides, hydroxides, carbonates, bicarbonates, silicates, phosphates, borates, and mixtures thereof.
Bromine compound Suitable bromine compounds in the present process are selected from the group consisting of bromine, water-soluble bromide salts, water-soluble hypobromits salts, hypobromous acid, and mixtures thereof.
Overall Preferred Combinations of Ingredients In an overall preferred process herein, said hypochlorite source is selected from alkali metal hypachlorites and the product of mixing a hypochlorite-liberating compound and aqueous alkali; said aminofunctional compound is selected from sulfamic acid, alkali-metal suifamates, alkaline earth sulfamates, tetra-aikylammonium sulfamates, and mixtures thereof; and said bromine compound is selected from the group consisting of water-soluble bromide salts.
Highly preferred herein is a process wherein said hypochiorite source is sodium hypochlorite, said aminafunctional compound is sulfamic aud; and said bromine compound is selected from sodium bromide, potassium bromide and mixtures thereof.
Ingredients or Impurities Desirably Excluded The present process and product thereof preferably limits certain compounds which have been found to adversely affect product stability and effectiveness.
Especially undesirable compounds herein are those aminofunctional compounds which do not form stable N-halo derivatives. Such compounds include simple ammonium (NH4+) salts, such as ammonium sulfate; urea;
amino acids such as aspartic acid; and mixtures thereof, any of which may, for example, produce unpleasant odors of undesirable chloramines. Preferred herein are processes wherein throughout, and at least in the essential aminofunctional compound, no ingredient comprises more than about 1 % of aminofunctional impurity compounds having unstable N-halo derivatives.
Translating this requirement in practical terms, sulfamic acid is commercially available in a range of grades, certain of which may include urea as an impurity.
The crystal grade of sulfamic acid, which minimizes urea impurity, is found to be preferred. fn other process embodiments, the present process is conducted using starting materials which are all water-soluble that is to say, excluding insoluble materials such as abrasives, thereby avoiding any tendency for surface-catalyzed bleach decomposition.
Acids and Bases for pH Adiustment Any convenient alkali or base can be used herein as a pH-adjusting agent for increasing pH, and any convenient acid can be used herein as a pH-adjusting agent for decreasing pH; always provided that such alkali or acid is non-reactive with hypohalite. Preferred alkalis for pH adjustment include water-soluble alkalis such as sodium hydroxide, potassium hydroxide or mixtures thereof, and preferred acids include the common mineral acids such as sulfuric, hydrochloric or nitric, though sulfuric is preferred in this group.
Alternately relatively weak acids can be used; these include acetic acid.
Examples of bases which knowledgeable practitioners will avoid entirely in the present process include ammonia because it is chemically reactive with other essential ingredients herein for purposes other than pH change, forming, for example, an undesirable type of chloramine when it reacts with hypochlorite.
In general, any simple mineral acid or base additions in the present process will be carried out in a manner consistent with preserving the chemical integrity of the aminofunctional compound. For example, when using sulfamic acid as the aminofunctional compound, mineral acid additions are conducted under sufficient dilution to avoid decomposition of the sulfamic acid. Concentrated nitric acid, for example, is known to decompose sulfamic acid at HN03 concentrations of 73%, especially at elevated temperatures, with formation of nitrous oxide, and such combination of concentrated mineral acid and elevated temperature is avoided in the instant process.
Water Water used for making liquid compositions according to the present process is suitably city water. In general, hard, soft, softened or deionized water may be used. Distilled or reverse-osmosis treated water are especially desirable.
When using water of uncertain quality, for example ferruginous water or high-manganese water from boreholes, it is desirable to reduce the dissolved metal content by conventional water treatment approaches, for example, cv ~7enation, ~Itra . and settling. Moreover a chelant or sequestrant can be us to treat process water. It is prudent to monitor or periodically check, and if needed, minimize transition metal ion content of the water by conventional techniques since transition metal ions are well-known to affect bleach product stabiliy.
Suitable analysis is by atomic absorption spectroscopy or inductively coupled plasma spectroscopy (1CP).
pH Measurement pH herein is measured using a glass electrode or combination electrode such as Corning General Purpose Combination electrode Cat. No. 476530, and a commercial pH meter such as the ~ 40 pH meter available from Beckman.
~H Rampiny It is desirable, and indeed characteristic of the present process as best currently known, for there to be present a downward pH ramp (a "ramp" herein being a relatively linear increase or decrease in pH with time) followed by an upward pH ramp, there being a strong minimum in the pH as indicated in the process definition. In the latter part of the process, as noted hereinabove, the upward ramp of pH, measurable by dpH/dt, is specifically in a defined range believed to be linked to stability and performance.
Bleach in4redient measurement: Available Chlorine The term "Available Chlorine" sometimes abbreviated "AvCl2" as used herein is described in Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4, 4th Ed. (1992) pages 274-275 published by Wiley-Interscience.
Reactions which produce an oxidant from chlorine include the following:
C12(gas) ~ C12 (aqueous) C12(aqueous) + H20 ~-- ~ HOC/ + H+ + CI-HOCI ~ H+ + OCI-RR'NCI + H2p ~- ~ HOC/ + RR'NH
The total concentration or amount of any given chlorine-based oxidant is often expressed on an equivalent basis, as though all the oxidant were chlorine.
Available Chlorine is thus the equivalent concentration or amount of chlorine needed to produce an oxidant, for example according to the above reactions, and can be measured by conventional measures, such as iodometric methods referenced in Kirk-Othmer (op. city.
Available Chlorine can be calculated from the following relation:
Available Chlorine (%) _ 70.9 x moles of oxidant x (number of active CI atoms / molecule) x 100 In the above relation, the term "active CI atoms" needs definition: Because only accepts two electrons, as does HOCI and monochloroamines, it has only one "active" CI atom according to the present definition.
When determining the Available Chlorine expected for product of the instant process, "moles of oxidant" in the above relation is replaced by "total moles of bleaching halogen added in forming the composition".
Note that "Available Chlorine" can be determined for bleaches that do not actually form hypochlorite in solution, such as bromine-containing bleaches, and other nonchlorine bleaches, by substituting the number of electrons accepted divided by two for the number of active chlorine atoms in the above relation. This can also be measured by iodometric titration.
Note also that the Available Chlorine unit is a dimensioniess percentage, not a percentage by weight. It should be apparent from the definition that it is in fact possible in general terms to obtain Available Chlorine values which exceed 100%; this can happen in the case of a chlorine bleach which is more mass efficient than C12, recalling that only one chlorine atom in C12 is a bleaching chlorine atom; however, such levels are not encountered in the present process.
Amounts and Ratios of ingredients In general, amounts and aqueous concentrations of ingredients herein may vary quite widely; nonetheless there is a strong preference for particular interhalogen ratios as defined elsewhere herein and it is commercially attractive to use ingredients such as sodium hypochlorite at the most economic concentrations provided by their manufacturers.
Advantages As noted, the present invention has significant advantages, for example improved bleaching. By "improved bleaching" it is meant herein that a composition obtainable with the process of the present invention delivers better bleaching performance on bleachable stains like tea stains, as compared to the bleaching performance delivered by the same composition made by another process, for example one involving numerous alternate orders of addition or mixing of the ingredients. Importantly, concurrent with improved bleaching, the formulations provided by the process leave low residual odor on skin and are w milder than those otherwise manufactured with different ingredient selections and/or orders of addition. In short the combination of overall performance and desirable skin safetylaesthetics offered by the present process are believed to be measurably superior to those attainable by any art-recognized process.
Product Characteristics The product of the present process is not in general limited as to form, though it is highly preferred for the compositions produced to be aqueous liquids or aqueous gels. Another product form potentially preferred herein is a "high-solubility solid concentrate" or "high solubility tablet" form. Such product forms are free from abrasives. The product of the process is preferably transparent, and, as described elsewhere herein, may be both colored and perfumed.
Processing of Optional Ingredients The present process and the product thereof allow for the presence of at least one additional mixing step other than the essential minimum (a), (b), (c);
wherein there is added an ingredient selected from the group consisting of surfactants, buffers, builders, cheiants, perfumes, colorants, dyes, bleach stabilizers, pigments, suds supressors, anti-tarnish andlor anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removallanti-redeposition agents, thickeners, solvents, and mixtures thereof. For other optional ingredients, see U.S. 3,583,922 or other references cited in the background, recognizing that '922 relates to solid compositions as distinct from the liquids herein.
Other ramifications The present process can accomodate perfumes and colorants, most particularly known bleach-stable colorants such as various yellows; and perfumes offering citrus or pine character. Perfumes for use herein are desirably hydrophobic, having relatively high octanol/water partition coefficients such as 6 or above. In process terms, it has been found desirable to incorporate perfume in a step which follows (III) (a). Without being limited by theory, this is believed to be due to a reduced tendency for reaction of sulfamate derivatives with perfume aldehydes when they are incorporated late in the process. Also desirably, bleach-stable thickeners such as those referenced in background and/or Laponite ~, a special clay available from Laporte, and/or fatty amine oxides may be combined using the present process to deliver product having a wide range of useful properties.
Optional Ingredients in More Detail Optional ingredients are now nonlimitingly illustrated in more detail. Such ingredients as noted include surfactants, bleach stabilizers, colorants, suds boosters, suds supressors, anti-tarnish and/or anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removal/anti-redeposition agents, polymeric dispersing agents, and the like; and mixtures thereof.
The processes herein may make use of, based on the composition of the product, from about 0.1 °~ to about 95% of a surtactant or mixtures thereof selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surface active agents. For liquid systems, surtactant is preferably present to the extent of from about 0.1 % to 20%,. though higher levels, e.g., 30°~ are possible, for example in viscous gels, aqueous pastes or semi-solids.
Anionic surtactants herein can include water-soluble salts, particularly the alkali metal salts, of Cg-C22 organic sulfuric reaction products and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
Sodium or potassium alkyl sulfates, especially those obtained by sulfating Cg-C1g alcohols are useful, as are linear or branched alkyl benzene sulfonates especially the Cg-C15 alkyl-substituted sodium- or potassium- salt forms; also useful are the sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids derived from coconut oil sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
Additionally, conventional primary alkyl sulfates, such as those having the general formula ROS03 M+ wherein R is typically a linear Cg-C22 hydrocarbon group and M is a water solublizing ration are useful herein, as are the secondary alkyl sulfates and/or branched chain primary alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20 carbon atoms, see EP
439,316 A Smith et al. Secondary alkyl sulfate surfactants include those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH3(CH2)n{CHOS03-M+)(CH2)mCH3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 17, and M is a water-solublizing ration.
In addition, the selected secondary (2,3) alkyl sulfate surfactants used herein may comprise structures of formulas I and II
CH3{CH2)x(CHOSOg'M+)CH3 I
CH3(CH2)y(CHOS03-M+)CH2CH3 II
for the 2-sulfate and 3-sulfate, respectively. Mixtures of the 2- and 3-sulfate can be used herein. In formulas I and II, x and (y+1 ) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about to about 16. M is a ration, such as an alkali metal, ammonium, alkanolammonium, triethanol-ammonium, potassium, ammonium, and the like, can also be used.
The aforementioned secondary alkyl sulfates are those prepared by the addition of H2S04 to olefins. A typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued February 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. The synthesis conducted in solvents which afford the secondary (2,3) alkyl sulfates on cooling, yields products which, when purified to remove the unreacted materials, randomly sulfated materials, unsulfated by-products such as C10 and higher alcohols, secondary olefin sulfonates, and the like, are typically + % pure mixtures of 2- and 3- sulfated materials (some sodium sulfate may be present) and are white, non tacky, apparently crystalline, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5 % of the mixture of secondary (2,3) alkyl mono-sulfates. Such materials are available as under the name "DAN", e.g., "DAN 200" from Shell Oil Company.
Especially preferred surfactants for use in the present process are those having the highest possible bleach stability, including Cg-C22 fatty amine oxides such as hexadecyldimethylamine N- oxide or saturated fatty alkyl alkoxylates.
Particularly objectionable surfactants are those having a high degree of unsaturation, and any surfactants comprising hypohalite-reactive nitrogen moieties. Somewhat less problematic, but still a potential source of difficulty, are the use of any alcohols. Thus, when using alkyl ethoxylates, etc., the so-called "capped" forms in which terminal -OH is replaced by -OCH3 or similarly unreactive groups, is particularly preferred.
The most bleach-stable and hydrolytically-stable surfactants can be added at various stages of the present process, but for convenience, their addition will generally be done in such manner as to minimize foaming which may undesirably slow down the process. Silicone anti-foams are desirable for limiting foam; such anti-foams are commercially available from Dow Corning Corp.
When processing a surfactant having susceptibility to acid hydrolysis, such as an alkyl sulfate, it is incorporated into the product in the present process at any point at which the pH of the mixture of ingredients has exceeded about 7, preferably, when said pH has exceeded about 8.
Although preferred processes and compositions herein are free from insoluble materials and are non-abrasive, products of the present process can be formulated in a solid or viscous semi-solid form further comprising an abrasive material, such as expanded perlite abrasive in combination with the surfactants, filler material, or other optional scouring material ingredients listed herein.
When desired, abrasive materials can be those contained in U.S. Pat. No.
4,051,056, Hartman, issued September 27, 1977.
Other optional ingredients to be used herein include buffers, for purposes which include to adjust the cleaning surface pH to optimize the hard surface cleaner composition effectiveness relative to a particular type of soil or stain.
Buffers may also be included to stabilize the adjunct ingredients with respect to extended shelf life or for the purpose of maintaining compatibility between various aesthetic ingredients. The hard surface cleaner of the present invention optionally contains buffers to help adjust and maintain the pH at about 13 or in a range above about 13. Non-limiting examples of such suitable buffers are potassium carbonate, sodium carbonate, and trisodium phosphate, however, the formulator is not restricted to these examples or combinations thereof.
The cleaning compositions obtainable according to the process of the present invention may also desirably be prepared with inclusion of a heavy metal ion control system, especially one comprising one or more agents for the control of bleach destabilization caused by soluble, insoluble or colloidal iron and/or manganese andlor copper. A simple but effective agent is sodium tripolyphosphate, optionally supported by at least partially polymeric hydrous sodium silicate. Examples of other chelating or heavy-metal control agents are phytic acid and ethane-1-hydroxy-1,1-diphosphonic acid (EHDP), though other materials, such as a number of commercial phosphonate types, may be used.
Preferred chelating agents herein, are free from alcohol sites, halogen-reactive nitrogen donor sites, and hydrolytically sensitive sites. In process terms, a preferred addition of at least some chelating agent or heavy-metal ion control agent takes place at or near the beginning of the process, for example immediately before, or concurrent with, step I(a). However, when adding a silicate for the purpose at least in part of helping control heavy metal ions, it is added at a point in the process which is remote from both the pH minimum and the pH maximum of the process.
Perfumes when used are typically at levels of from 0% to 5%. See U.S. Pat.
No. 4,246,129, Kacher, issued January 20, 1981.
The compositions obtainable according to the process of the present invention typically have a yellow color. However, it is possible to provide a preferred solution which has some other color, for example, by the addition of a bleach-stable dye; moreover, preferred solutions may readily be diluted, in which case yellow color is difficult to detect. In process terms, dyes are preferably added at the end of the process, in which case product-making can be more conveniently monitored on a colorant-free product.
The liquid compositions obtainable according to the process of the present invention may be formulated with different viscosities. In one embodiment of the present invention the compositions obtainable with the process herein have a viscosity of from about 1 to about 150cps. Said compositions are convenient for spray bottle application. Likewise, said liquid compositions obtainable according to the present invention can be further thickened, e.g., by the addition of additional bleach-stable thickener, such as the commercially available DOWFAX. A suitable gel formulation has a viscosity of from about 100 cps to about 2000 cps, preferably from 300 cps to 1000 cps as measured, for example, by techniques and methods described in "Physico-Chemical Methods", Reilly, J. and Rae, W. N.; Vol. 1 (5th ed.), pages 667-692; D. Van Nostran pub. Thickeners, when added in the instant process, are desirably used toward the end of the process, for example, adding them immediately after, or concurrent with, stage (III).
(I) Pre-Bromine Sta4e All operations are conducted at ambient temperature, about 20 °C.
30 grams distilled water is placed in a chemically inert, plastic-lined reaction vessel. The vessel is set for operation at atmospheric pressure and as a precaution is connected to a scrubber for removing any minor quantity of chlorine vapors which might be emitted. The vessel is equipped with an inert-plastic-coated paddle stirrer. While stirring at 300 rpm, 13.05 grams of aqueous sodium hypochlorite, assayed as comprising 10.73% Available Chlorine, is added.
Immediately thereafter, sulfamic acid (2.2 grams, Aldrich, 99.3%, crystalline) is added with continued stirring until the added solid has dissolved. At this point, the pH of the stage (l) mixture is about 1Ø
(II) Bromine Compound Addition Sta4e To the stirred stage (I) mixture is added Sodium Bromide (0.5 grams, EM
Science). The mixture is stirred until the added solid has dissolved (about 5 minutes) and a yellow color has appeared. The mixture at this point is identified as a Stage (II) mixture.
L11) Product Stabilization Sta4e To the stirred stage (II) mixture is added Sodium Hydroxide (about 3.0 grams, 50% in water) until the pH of the mixture is about 13.2.
Water is added until the total weight of the stage (III) mixture is about 100 grams.
EXAMPLE II
The process of Example 1 is repeated with the following differences: The scale of operations is increased 1000-fold. In a pre-processing step, chlorine gas is passed into sodium hydroxide solution, forming sodium hypochlorite solution.
The sodium hypochlorite solution is passed into the above-identified reactor in batches, where it is treated with sulfamic acid, forming a stage (1) mixture.
Steps subsequent to stage (I) are conducted in the manner of Example I.
EXAMPLE III
The process of Example II is repeated with the following difference: Sodium Sulfamate is substituted for sulfamic acid.
In the examples below, a heavy line indicates the boundary separating Stages (I), (II) and (III) of the process.
EXAMPLE IV
WO 97!43392 PCT/US96/07089 The process of Example III is repeated with the following difference: prior to completion of Stage I, aqueous hydrochloric acid is added to reduce the pH to about 7Ø
EXAMPLE V
Ingredient Addition Seauence %
wt Hydrous Sodium Silicate(2) 0.20 (Britesil H20, PQ Corp.) Sodium Tripolyphosphate(3) 0.20 First portion Sodium Hypochlorite (4) 0.90 Sulfamic Acid (5) 1.30 Potassium Bromide (6) 1.10 Sodium Tripolyphosphate (7) 7.60 Second Portion Sodium Hydroxide (8) 0.80 Cocodimethylamine N- Oxide(9) 0.25 ~Ye ( 10) 0.15 Perfume ( 11 ) 0.60 Water (1 ) and (12) bal.
("bal."means "balance to 100%"
EXAMPLE VI
Inctredient Addition Sectuence % wt Sodium Hypochlorite (2) 1.4 Sulfamic Acid (3) 1.9 Sodium Silicate (4) 0.04 Sodium Bromide (5) 1,g Sodium Hydroxide (6) 1.6 Surfactant (7) 3.5 Dyes / perfume (8) 0.28 Water (1 ) and (9) bal.
Note:
""Surfactant" refers to C8 Alkyl Sulfate, C12-C14 Dimethylamine N- Oxide or a mixture thereof.
EXAMPLE VII
Ingredient Addition Sequence % wt Sodium Hypochlorite (1 ) 1.4 Sodium Sulfamate / (2) 2.2*"' Sulfuric acid Sodium Bromide (3) 1.5 Potassium Bromide (4) 1.1 _ Sodium Silicate (5) 0.05 Perfume (6) 0.1 Sodium Hydroxide (7) 1.g Sodium Octyl Sulfate (8) 5.5 Yeliow Dye (9) 0.28 Water (10) bal.
("bal."means "balance to 100%") '"' weight equivalent to sulfamic acid content, dry basis EXAMPLE VIII
Ingredient Addition Seguence wt Cocodimethylamine N- oxide (1 ) 3.0 Sodium Sulfamate (Sulfuric(2) 0.5'*
acid Calcium Hypochlorite (3) 0.5 Sodium Dichlorocyanurate (4) 0.50 Potassium Bromide (5) 1.5 Sodium Hydroxide (6) 0.8 Sodium Tripolyphosphate (7) 1.6 Sodium Acetate (8) 0.3 Potassium Hydroxide (9) 0.85 Sodium Octyl Sulfate (10) 3.00 Dyes I perfume ( 11 ) 0.28 Water (12) bal.
"" weight equivalent to sulfamic acid content, dry basis EXAMPLE IX
Ingredient Addition Sequence wt Surfactant (2) 6.1 Sodium Dichlorocyanurate(3) 1.2 Melamine (4) 0.23 Potassium Bromide (5) 1.0 Tetrapotassium Pyrophosphate.(6) 13.0 Tripotassium Phosphate (7) 12.0 Sodium Silicate (8) 0.5 Calcium Carbonate (9) 39.0 Calcium Oxide {10) 2.8 Perlite Abrasive (11 ) 22.5 Sodium Hydroxide (12) 1.1 Water (1 ) and (13); bal.
split 1:1 by weight Note 1:
"'Surfactant" refers to C8 Alkyl Sulfate, C12-C14 Dimethylamine N- Oxide or a mixture thereof.
unitslmin, or higher.
In such embodiments, it will be appreciated that the instant process contains a pH minimum. The position in the overall sequence of the present process of this minimum is found at the end of stage (I).
Pressure The present process can be conducted at any convenient pressure. For example, chlorine gas and alkali can be reacted under pressure, for example up to about 5 atm., in stage (I) prior to adding the aminofunctional compound;
and the following stages of the process can be conducted at atmospheric pressure, or even at reduced pressure if scrubbers or condensers are provided for collecting lost halogen. Preferred processes are conducted at atmospheric pressure.
Time The present process can be conducted in batch or continuous mode. Unless otherwise indicated, illustrations of the process hereinafter are batch-mode.
Times for completion of a batch may in general vary widely. Typically, times of about 5 min to about 1.5 hours are typical for each of stages (I) , (II) and (III).
In preferred embodiments, Stage (II) will allow at least sufficient time to permit the bromine compound to substantially dissolve before proceeding with stage (III). Also preferably, stage (II) is continued until development of a yellow color in the stage {II) mixture. In general, the longer process times are associated with larger-scale processes. It is preferred herein to minimize the overall reaction time, and in particular, while allowing sufficient time for stage (II), to proceed without delay from that stage to the end of stage (III). Moreover, it is highly preferred to minimize any time period between the end of step (a) and the beginning of step (b), and between the end of step (b) and the beginning of step (c).
Concentration and Concentration Ratios The present process can be conducted over a wide range of concentrations of the ingredients in water. In preferred embodiments, the process is characterized by a dilution factor for the sure of stages subsequent to stage (I) which is not in excess of about twofold. In general, concentrations of the ingredients are adjusted such that the product of stage (/I1), comprises from about 0.01 °~ to about 10 % Available Chlorine. Also, in terms of relative proportions of the ingredients, the present process preferably relies on an interhalogen ratio [8r] : [0C/-] of from about 10 : 1 to about 1 : 10, preferably 1:2 to 1:5, wherein (Br] represents total moles Br added into said process from said bromine compound and [0C/- ] represents total moles hypochlorite added into said process from said hypochlorite source. Moreover, the preferred processes herein employ an amino-halo ratio [A] : (X] of from about 10 : 1 to about 1 : 10, wherein [A) represents the total of moles of amino moieties of said aminofunctional compound used to form said composition and wherein [X]
represents total moles of bleaching halogen, measurable as Available Chlorine, added into said composition.
Very preferably, said amino-halo ratio is from about 1.0 : 1.0 to about 1.5 :
1Ø
To illustrate, with repect to the above quantities, sulfamic acid, which contains one mole of amino moieties per mole of the compound, is easily computed in the above relation: [A] is simply the number of moles of sulfamate; but to give another illustration, when melamine is used, [A] is the number of moles of melamine used multiplied by the number of moles (which is 3) of amino moieties contained in any one mole of melamine.
In4redients HYpochlorite Source In general, any convenient hypochiorite source can be used in the instant process. Preferred hypochlorite sources are selected from chlorine, hypochlorous acid, alkali metal hypochlorites, alkaline earth metal hypochiorites, the product of mixing a hypochlorite-liberating compound with aqueous alkali, and mixtures thereof. Suitable hypochlorite-liberating compounds, in the sense immediately above, are illustrated by dichloroisocyanuric acid and its sodium salts and hydrates, which hydrolyze rather readily to release hypochlorite. Highly preferred hypochlorite sources herein are selected from alkali metal hypochlorites and the product of mixing said hypochlorite-liberating compound and aqueous alkali.
Aminofunctional compound From the thousands of available aminofunctional compounds, the present invention selects a limited few which are found operative. In processes of the invention, suitable aminofunctional compounds are those having stable N-halo derivatives. The term "having a stable N-halo derivative" herein is defined as "capable of forming an N-halo derivative and it is stable", rather than as necessarily "possessing a stable N-halo moiety at the inception of the present process". Suitable aminofunctional compounds meeting the needs of the present invention are selected from (i) primary aminofunctional compounds selected from sulfamic acid, alkali-metal sulfamates, alkaline earth sulfamates, tetra-alkylammonium sulfamates, and mixtures thereof; (ii) secondary aminofunctionai compounds selected from secondary amine derivatives having formula RR'NH or (R")2NH wherein R, R' and R" are organic moieties and wherein carbon atoms of said organic moieties are bonded covalently to NH;
(iii) sulfonamides selected from sulfamide, p-toluenesulfonamide, imidodisulfonamide, benZenesulfonamide, alkyl sulfonamides, and mixtures thereof; (iv) melamine, cyanamide; and (v) mixtures thereof.
Suitable secondary aminofunctional compounds (ii) include those not specifically identified in (i), (iii), (iv) and (v), wherein R, R' and R" are independently selected from C1-C12 linear saturated and C3-C12 branched saturated moieties which can be alkyl, aryl or heterocyclic, optionally substituted by carboxylic acid or carboxylate: an example of the latter carboxylic-substituted derivatives is the alpha-aminobutyrates. Preferred secondary aminofunctional compounds are known for use as disinfectants, especially those which are water-soluble and those having N-halo derivatives which are relatively insensitive to shock.
In alternate terms, the present process is believed to be applicable wherever the aminofunctional compound has a hydrolysis constant, K, as defined by K=[HOCI][RNH2] I [RNHCI]
or K=[HOCI][RR'NH] I [RR'NCI]
or K=[HOCI][(R")2NH] I [(R")2NC1]
in the range of from about 10 ~ to about 10 -9, provided that no isocyanurate or chlorinated isocyanurate is included as the essential aminofunctional compound.
O
Hydrolysis constants such as the above are well known in the art and are defined conventionally. See, for example, Kirk Othmer's Encyclopedia of Chemical Tectanology, 3rd Ed., Vol. 5, article entitled "Chloramines and Bromamines", see especially page 567, and Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 3, see especially pages 940-941.
Subject to the abave-identified requirements, preferred secondary aminofunctional compounds can be selected from those identified in Kirk Othmer, Encyclopedia of Chemical Technology, 4th. Ed., 1993, pages 918-925 and include compounds. identified under the headings "Organic Chloramines and Bromamines", "~4liphatic Compounds", "Aromatic Compounds" and "Heterocyclic Compounds'".
Sulfamic acid or sodium sulfamate are highly preferred aminofunctional compounds herein.
Alkali Suitable alkali in the present process is selected from alkali-metal-, alkaline-earth-, and tetraalkylamrnonium- oxides, hydroxides, carbonates, bicarbonates, silicates, phosphates, borates, and mixtures thereof.
Bromine compound Suitable bromine compounds in the present process are selected from the group consisting of bromine, water-soluble bromide salts, water-soluble hypobromits salts, hypobromous acid, and mixtures thereof.
Overall Preferred Combinations of Ingredients In an overall preferred process herein, said hypochlorite source is selected from alkali metal hypachlorites and the product of mixing a hypochlorite-liberating compound and aqueous alkali; said aminofunctional compound is selected from sulfamic acid, alkali-metal suifamates, alkaline earth sulfamates, tetra-aikylammonium sulfamates, and mixtures thereof; and said bromine compound is selected from the group consisting of water-soluble bromide salts.
Highly preferred herein is a process wherein said hypochiorite source is sodium hypochlorite, said aminafunctional compound is sulfamic aud; and said bromine compound is selected from sodium bromide, potassium bromide and mixtures thereof.
Ingredients or Impurities Desirably Excluded The present process and product thereof preferably limits certain compounds which have been found to adversely affect product stability and effectiveness.
Especially undesirable compounds herein are those aminofunctional compounds which do not form stable N-halo derivatives. Such compounds include simple ammonium (NH4+) salts, such as ammonium sulfate; urea;
amino acids such as aspartic acid; and mixtures thereof, any of which may, for example, produce unpleasant odors of undesirable chloramines. Preferred herein are processes wherein throughout, and at least in the essential aminofunctional compound, no ingredient comprises more than about 1 % of aminofunctional impurity compounds having unstable N-halo derivatives.
Translating this requirement in practical terms, sulfamic acid is commercially available in a range of grades, certain of which may include urea as an impurity.
The crystal grade of sulfamic acid, which minimizes urea impurity, is found to be preferred. fn other process embodiments, the present process is conducted using starting materials which are all water-soluble that is to say, excluding insoluble materials such as abrasives, thereby avoiding any tendency for surface-catalyzed bleach decomposition.
Acids and Bases for pH Adiustment Any convenient alkali or base can be used herein as a pH-adjusting agent for increasing pH, and any convenient acid can be used herein as a pH-adjusting agent for decreasing pH; always provided that such alkali or acid is non-reactive with hypohalite. Preferred alkalis for pH adjustment include water-soluble alkalis such as sodium hydroxide, potassium hydroxide or mixtures thereof, and preferred acids include the common mineral acids such as sulfuric, hydrochloric or nitric, though sulfuric is preferred in this group.
Alternately relatively weak acids can be used; these include acetic acid.
Examples of bases which knowledgeable practitioners will avoid entirely in the present process include ammonia because it is chemically reactive with other essential ingredients herein for purposes other than pH change, forming, for example, an undesirable type of chloramine when it reacts with hypochlorite.
In general, any simple mineral acid or base additions in the present process will be carried out in a manner consistent with preserving the chemical integrity of the aminofunctional compound. For example, when using sulfamic acid as the aminofunctional compound, mineral acid additions are conducted under sufficient dilution to avoid decomposition of the sulfamic acid. Concentrated nitric acid, for example, is known to decompose sulfamic acid at HN03 concentrations of 73%, especially at elevated temperatures, with formation of nitrous oxide, and such combination of concentrated mineral acid and elevated temperature is avoided in the instant process.
Water Water used for making liquid compositions according to the present process is suitably city water. In general, hard, soft, softened or deionized water may be used. Distilled or reverse-osmosis treated water are especially desirable.
When using water of uncertain quality, for example ferruginous water or high-manganese water from boreholes, it is desirable to reduce the dissolved metal content by conventional water treatment approaches, for example, cv ~7enation, ~Itra . and settling. Moreover a chelant or sequestrant can be us to treat process water. It is prudent to monitor or periodically check, and if needed, minimize transition metal ion content of the water by conventional techniques since transition metal ions are well-known to affect bleach product stabiliy.
Suitable analysis is by atomic absorption spectroscopy or inductively coupled plasma spectroscopy (1CP).
pH Measurement pH herein is measured using a glass electrode or combination electrode such as Corning General Purpose Combination electrode Cat. No. 476530, and a commercial pH meter such as the ~ 40 pH meter available from Beckman.
~H Rampiny It is desirable, and indeed characteristic of the present process as best currently known, for there to be present a downward pH ramp (a "ramp" herein being a relatively linear increase or decrease in pH with time) followed by an upward pH ramp, there being a strong minimum in the pH as indicated in the process definition. In the latter part of the process, as noted hereinabove, the upward ramp of pH, measurable by dpH/dt, is specifically in a defined range believed to be linked to stability and performance.
Bleach in4redient measurement: Available Chlorine The term "Available Chlorine" sometimes abbreviated "AvCl2" as used herein is described in Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4, 4th Ed. (1992) pages 274-275 published by Wiley-Interscience.
Reactions which produce an oxidant from chlorine include the following:
C12(gas) ~ C12 (aqueous) C12(aqueous) + H20 ~-- ~ HOC/ + H+ + CI-HOCI ~ H+ + OCI-RR'NCI + H2p ~- ~ HOC/ + RR'NH
The total concentration or amount of any given chlorine-based oxidant is often expressed on an equivalent basis, as though all the oxidant were chlorine.
Available Chlorine is thus the equivalent concentration or amount of chlorine needed to produce an oxidant, for example according to the above reactions, and can be measured by conventional measures, such as iodometric methods referenced in Kirk-Othmer (op. city.
Available Chlorine can be calculated from the following relation:
Available Chlorine (%) _ 70.9 x moles of oxidant x (number of active CI atoms / molecule) x 100 In the above relation, the term "active CI atoms" needs definition: Because only accepts two electrons, as does HOCI and monochloroamines, it has only one "active" CI atom according to the present definition.
When determining the Available Chlorine expected for product of the instant process, "moles of oxidant" in the above relation is replaced by "total moles of bleaching halogen added in forming the composition".
Note that "Available Chlorine" can be determined for bleaches that do not actually form hypochlorite in solution, such as bromine-containing bleaches, and other nonchlorine bleaches, by substituting the number of electrons accepted divided by two for the number of active chlorine atoms in the above relation. This can also be measured by iodometric titration.
Note also that the Available Chlorine unit is a dimensioniess percentage, not a percentage by weight. It should be apparent from the definition that it is in fact possible in general terms to obtain Available Chlorine values which exceed 100%; this can happen in the case of a chlorine bleach which is more mass efficient than C12, recalling that only one chlorine atom in C12 is a bleaching chlorine atom; however, such levels are not encountered in the present process.
Amounts and Ratios of ingredients In general, amounts and aqueous concentrations of ingredients herein may vary quite widely; nonetheless there is a strong preference for particular interhalogen ratios as defined elsewhere herein and it is commercially attractive to use ingredients such as sodium hypochlorite at the most economic concentrations provided by their manufacturers.
Advantages As noted, the present invention has significant advantages, for example improved bleaching. By "improved bleaching" it is meant herein that a composition obtainable with the process of the present invention delivers better bleaching performance on bleachable stains like tea stains, as compared to the bleaching performance delivered by the same composition made by another process, for example one involving numerous alternate orders of addition or mixing of the ingredients. Importantly, concurrent with improved bleaching, the formulations provided by the process leave low residual odor on skin and are w milder than those otherwise manufactured with different ingredient selections and/or orders of addition. In short the combination of overall performance and desirable skin safetylaesthetics offered by the present process are believed to be measurably superior to those attainable by any art-recognized process.
Product Characteristics The product of the present process is not in general limited as to form, though it is highly preferred for the compositions produced to be aqueous liquids or aqueous gels. Another product form potentially preferred herein is a "high-solubility solid concentrate" or "high solubility tablet" form. Such product forms are free from abrasives. The product of the process is preferably transparent, and, as described elsewhere herein, may be both colored and perfumed.
Processing of Optional Ingredients The present process and the product thereof allow for the presence of at least one additional mixing step other than the essential minimum (a), (b), (c);
wherein there is added an ingredient selected from the group consisting of surfactants, buffers, builders, cheiants, perfumes, colorants, dyes, bleach stabilizers, pigments, suds supressors, anti-tarnish andlor anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removallanti-redeposition agents, thickeners, solvents, and mixtures thereof. For other optional ingredients, see U.S. 3,583,922 or other references cited in the background, recognizing that '922 relates to solid compositions as distinct from the liquids herein.
Other ramifications The present process can accomodate perfumes and colorants, most particularly known bleach-stable colorants such as various yellows; and perfumes offering citrus or pine character. Perfumes for use herein are desirably hydrophobic, having relatively high octanol/water partition coefficients such as 6 or above. In process terms, it has been found desirable to incorporate perfume in a step which follows (III) (a). Without being limited by theory, this is believed to be due to a reduced tendency for reaction of sulfamate derivatives with perfume aldehydes when they are incorporated late in the process. Also desirably, bleach-stable thickeners such as those referenced in background and/or Laponite ~, a special clay available from Laporte, and/or fatty amine oxides may be combined using the present process to deliver product having a wide range of useful properties.
Optional Ingredients in More Detail Optional ingredients are now nonlimitingly illustrated in more detail. Such ingredients as noted include surfactants, bleach stabilizers, colorants, suds boosters, suds supressors, anti-tarnish and/or anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removal/anti-redeposition agents, polymeric dispersing agents, and the like; and mixtures thereof.
The processes herein may make use of, based on the composition of the product, from about 0.1 °~ to about 95% of a surtactant or mixtures thereof selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surface active agents. For liquid systems, surtactant is preferably present to the extent of from about 0.1 % to 20%,. though higher levels, e.g., 30°~ are possible, for example in viscous gels, aqueous pastes or semi-solids.
Anionic surtactants herein can include water-soluble salts, particularly the alkali metal salts, of Cg-C22 organic sulfuric reaction products and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
Sodium or potassium alkyl sulfates, especially those obtained by sulfating Cg-C1g alcohols are useful, as are linear or branched alkyl benzene sulfonates especially the Cg-C15 alkyl-substituted sodium- or potassium- salt forms; also useful are the sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids derived from coconut oil sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
Additionally, conventional primary alkyl sulfates, such as those having the general formula ROS03 M+ wherein R is typically a linear Cg-C22 hydrocarbon group and M is a water solublizing ration are useful herein, as are the secondary alkyl sulfates and/or branched chain primary alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20 carbon atoms, see EP
439,316 A Smith et al. Secondary alkyl sulfate surfactants include those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH3(CH2)n{CHOS03-M+)(CH2)mCH3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 17, and M is a water-solublizing ration.
In addition, the selected secondary (2,3) alkyl sulfate surfactants used herein may comprise structures of formulas I and II
CH3{CH2)x(CHOSOg'M+)CH3 I
CH3(CH2)y(CHOS03-M+)CH2CH3 II
for the 2-sulfate and 3-sulfate, respectively. Mixtures of the 2- and 3-sulfate can be used herein. In formulas I and II, x and (y+1 ) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about to about 16. M is a ration, such as an alkali metal, ammonium, alkanolammonium, triethanol-ammonium, potassium, ammonium, and the like, can also be used.
The aforementioned secondary alkyl sulfates are those prepared by the addition of H2S04 to olefins. A typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued February 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. The synthesis conducted in solvents which afford the secondary (2,3) alkyl sulfates on cooling, yields products which, when purified to remove the unreacted materials, randomly sulfated materials, unsulfated by-products such as C10 and higher alcohols, secondary olefin sulfonates, and the like, are typically + % pure mixtures of 2- and 3- sulfated materials (some sodium sulfate may be present) and are white, non tacky, apparently crystalline, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5 % of the mixture of secondary (2,3) alkyl mono-sulfates. Such materials are available as under the name "DAN", e.g., "DAN 200" from Shell Oil Company.
Especially preferred surfactants for use in the present process are those having the highest possible bleach stability, including Cg-C22 fatty amine oxides such as hexadecyldimethylamine N- oxide or saturated fatty alkyl alkoxylates.
Particularly objectionable surfactants are those having a high degree of unsaturation, and any surfactants comprising hypohalite-reactive nitrogen moieties. Somewhat less problematic, but still a potential source of difficulty, are the use of any alcohols. Thus, when using alkyl ethoxylates, etc., the so-called "capped" forms in which terminal -OH is replaced by -OCH3 or similarly unreactive groups, is particularly preferred.
The most bleach-stable and hydrolytically-stable surfactants can be added at various stages of the present process, but for convenience, their addition will generally be done in such manner as to minimize foaming which may undesirably slow down the process. Silicone anti-foams are desirable for limiting foam; such anti-foams are commercially available from Dow Corning Corp.
When processing a surfactant having susceptibility to acid hydrolysis, such as an alkyl sulfate, it is incorporated into the product in the present process at any point at which the pH of the mixture of ingredients has exceeded about 7, preferably, when said pH has exceeded about 8.
Although preferred processes and compositions herein are free from insoluble materials and are non-abrasive, products of the present process can be formulated in a solid or viscous semi-solid form further comprising an abrasive material, such as expanded perlite abrasive in combination with the surfactants, filler material, or other optional scouring material ingredients listed herein.
When desired, abrasive materials can be those contained in U.S. Pat. No.
4,051,056, Hartman, issued September 27, 1977.
Other optional ingredients to be used herein include buffers, for purposes which include to adjust the cleaning surface pH to optimize the hard surface cleaner composition effectiveness relative to a particular type of soil or stain.
Buffers may also be included to stabilize the adjunct ingredients with respect to extended shelf life or for the purpose of maintaining compatibility between various aesthetic ingredients. The hard surface cleaner of the present invention optionally contains buffers to help adjust and maintain the pH at about 13 or in a range above about 13. Non-limiting examples of such suitable buffers are potassium carbonate, sodium carbonate, and trisodium phosphate, however, the formulator is not restricted to these examples or combinations thereof.
The cleaning compositions obtainable according to the process of the present invention may also desirably be prepared with inclusion of a heavy metal ion control system, especially one comprising one or more agents for the control of bleach destabilization caused by soluble, insoluble or colloidal iron and/or manganese andlor copper. A simple but effective agent is sodium tripolyphosphate, optionally supported by at least partially polymeric hydrous sodium silicate. Examples of other chelating or heavy-metal control agents are phytic acid and ethane-1-hydroxy-1,1-diphosphonic acid (EHDP), though other materials, such as a number of commercial phosphonate types, may be used.
Preferred chelating agents herein, are free from alcohol sites, halogen-reactive nitrogen donor sites, and hydrolytically sensitive sites. In process terms, a preferred addition of at least some chelating agent or heavy-metal ion control agent takes place at or near the beginning of the process, for example immediately before, or concurrent with, step I(a). However, when adding a silicate for the purpose at least in part of helping control heavy metal ions, it is added at a point in the process which is remote from both the pH minimum and the pH maximum of the process.
Perfumes when used are typically at levels of from 0% to 5%. See U.S. Pat.
No. 4,246,129, Kacher, issued January 20, 1981.
The compositions obtainable according to the process of the present invention typically have a yellow color. However, it is possible to provide a preferred solution which has some other color, for example, by the addition of a bleach-stable dye; moreover, preferred solutions may readily be diluted, in which case yellow color is difficult to detect. In process terms, dyes are preferably added at the end of the process, in which case product-making can be more conveniently monitored on a colorant-free product.
The liquid compositions obtainable according to the process of the present invention may be formulated with different viscosities. In one embodiment of the present invention the compositions obtainable with the process herein have a viscosity of from about 1 to about 150cps. Said compositions are convenient for spray bottle application. Likewise, said liquid compositions obtainable according to the present invention can be further thickened, e.g., by the addition of additional bleach-stable thickener, such as the commercially available DOWFAX. A suitable gel formulation has a viscosity of from about 100 cps to about 2000 cps, preferably from 300 cps to 1000 cps as measured, for example, by techniques and methods described in "Physico-Chemical Methods", Reilly, J. and Rae, W. N.; Vol. 1 (5th ed.), pages 667-692; D. Van Nostran pub. Thickeners, when added in the instant process, are desirably used toward the end of the process, for example, adding them immediately after, or concurrent with, stage (III).
(I) Pre-Bromine Sta4e All operations are conducted at ambient temperature, about 20 °C.
30 grams distilled water is placed in a chemically inert, plastic-lined reaction vessel. The vessel is set for operation at atmospheric pressure and as a precaution is connected to a scrubber for removing any minor quantity of chlorine vapors which might be emitted. The vessel is equipped with an inert-plastic-coated paddle stirrer. While stirring at 300 rpm, 13.05 grams of aqueous sodium hypochlorite, assayed as comprising 10.73% Available Chlorine, is added.
Immediately thereafter, sulfamic acid (2.2 grams, Aldrich, 99.3%, crystalline) is added with continued stirring until the added solid has dissolved. At this point, the pH of the stage (l) mixture is about 1Ø
(II) Bromine Compound Addition Sta4e To the stirred stage (I) mixture is added Sodium Bromide (0.5 grams, EM
Science). The mixture is stirred until the added solid has dissolved (about 5 minutes) and a yellow color has appeared. The mixture at this point is identified as a Stage (II) mixture.
L11) Product Stabilization Sta4e To the stirred stage (II) mixture is added Sodium Hydroxide (about 3.0 grams, 50% in water) until the pH of the mixture is about 13.2.
Water is added until the total weight of the stage (III) mixture is about 100 grams.
EXAMPLE II
The process of Example 1 is repeated with the following differences: The scale of operations is increased 1000-fold. In a pre-processing step, chlorine gas is passed into sodium hydroxide solution, forming sodium hypochlorite solution.
The sodium hypochlorite solution is passed into the above-identified reactor in batches, where it is treated with sulfamic acid, forming a stage (1) mixture.
Steps subsequent to stage (I) are conducted in the manner of Example I.
EXAMPLE III
The process of Example II is repeated with the following difference: Sodium Sulfamate is substituted for sulfamic acid.
In the examples below, a heavy line indicates the boundary separating Stages (I), (II) and (III) of the process.
EXAMPLE IV
WO 97!43392 PCT/US96/07089 The process of Example III is repeated with the following difference: prior to completion of Stage I, aqueous hydrochloric acid is added to reduce the pH to about 7Ø
EXAMPLE V
Ingredient Addition Seauence %
wt Hydrous Sodium Silicate(2) 0.20 (Britesil H20, PQ Corp.) Sodium Tripolyphosphate(3) 0.20 First portion Sodium Hypochlorite (4) 0.90 Sulfamic Acid (5) 1.30 Potassium Bromide (6) 1.10 Sodium Tripolyphosphate (7) 7.60 Second Portion Sodium Hydroxide (8) 0.80 Cocodimethylamine N- Oxide(9) 0.25 ~Ye ( 10) 0.15 Perfume ( 11 ) 0.60 Water (1 ) and (12) bal.
("bal."means "balance to 100%"
EXAMPLE VI
Inctredient Addition Sectuence % wt Sodium Hypochlorite (2) 1.4 Sulfamic Acid (3) 1.9 Sodium Silicate (4) 0.04 Sodium Bromide (5) 1,g Sodium Hydroxide (6) 1.6 Surfactant (7) 3.5 Dyes / perfume (8) 0.28 Water (1 ) and (9) bal.
Note:
""Surfactant" refers to C8 Alkyl Sulfate, C12-C14 Dimethylamine N- Oxide or a mixture thereof.
EXAMPLE VII
Ingredient Addition Sequence % wt Sodium Hypochlorite (1 ) 1.4 Sodium Sulfamate / (2) 2.2*"' Sulfuric acid Sodium Bromide (3) 1.5 Potassium Bromide (4) 1.1 _ Sodium Silicate (5) 0.05 Perfume (6) 0.1 Sodium Hydroxide (7) 1.g Sodium Octyl Sulfate (8) 5.5 Yeliow Dye (9) 0.28 Water (10) bal.
("bal."means "balance to 100%") '"' weight equivalent to sulfamic acid content, dry basis EXAMPLE VIII
Ingredient Addition Seguence wt Cocodimethylamine N- oxide (1 ) 3.0 Sodium Sulfamate (Sulfuric(2) 0.5'*
acid Calcium Hypochlorite (3) 0.5 Sodium Dichlorocyanurate (4) 0.50 Potassium Bromide (5) 1.5 Sodium Hydroxide (6) 0.8 Sodium Tripolyphosphate (7) 1.6 Sodium Acetate (8) 0.3 Potassium Hydroxide (9) 0.85 Sodium Octyl Sulfate (10) 3.00 Dyes I perfume ( 11 ) 0.28 Water (12) bal.
"" weight equivalent to sulfamic acid content, dry basis EXAMPLE IX
Ingredient Addition Sequence wt Surfactant (2) 6.1 Sodium Dichlorocyanurate(3) 1.2 Melamine (4) 0.23 Potassium Bromide (5) 1.0 Tetrapotassium Pyrophosphate.(6) 13.0 Tripotassium Phosphate (7) 12.0 Sodium Silicate (8) 0.5 Calcium Carbonate (9) 39.0 Calcium Oxide {10) 2.8 Perlite Abrasive (11 ) 22.5 Sodium Hydroxide (12) 1.1 Water (1 ) and (13); bal.
split 1:1 by weight Note 1:
"'Surfactant" refers to C8 Alkyl Sulfate, C12-C14 Dimethylamine N- Oxide or a mixture thereof.
Claims (21)
1. A process for manufacturing an alkaline bleaching composition, said process comprising at least three stages including, in sequence, (I) a pre-bromine stage, (II) a bromine compound addition stage, and (III) a product stabilization stage, each of said stages having at least one mixing step;
wherein in said process, said pre-bromine stage, (I), comprises a step (a) of mixing in any order components comprising a hypochlorite source and an aminofunctional compound capable of forming a stable N-halo derivative;
thereby forming a stage (I) mixture; provided that at the end of said pre-bromine stage, said stage (I) mixture has a pH not exceeding about 11; said bromine compound addition stage, (II), is initiated at said pH and comprises a step, (b) of mixing in any order with said stage (I) mixture, a bromine compound; thereby forming a stage (II) mixture; and said product stabilization stage, (III), comprises at least one step, (c) of mixing in any order with said stage (II) mixture, an alkali in an amount suitable to arrive at a final pH for the product of said process of at least about 13.
wherein in said process, said pre-bromine stage, (I), comprises a step (a) of mixing in any order components comprising a hypochlorite source and an aminofunctional compound capable of forming a stable N-halo derivative;
thereby forming a stage (I) mixture; provided that at the end of said pre-bromine stage, said stage (I) mixture has a pH not exceeding about 11; said bromine compound addition stage, (II), is initiated at said pH and comprises a step, (b) of mixing in any order with said stage (I) mixture, a bromine compound; thereby forming a stage (II) mixture; and said product stabilization stage, (III), comprises at least one step, (c) of mixing in any order with said stage (II) mixture, an alkali in an amount suitable to arrive at a final pH for the product of said process of at least about 13.
2. A process according to Claim 1 wherein no stage other than (II) and no step other than (b) comprises adding a bromine compound.
3. A process according to Claim 2 wherein each of said steps (b) and (c) is performed at a temperature in the range from about 5°C to about 80°C.
4. A process according to Claim 3 wherein said pH at the end of stage (I) and at the beginning of stage (II) is in the range from about 1 to about 6.9.
5. A process according to Claim 3 wherein, from the end of stage I, the entire process is conducted at a rising pH.
6. A process according to Claim 5 wherein said rising pH corresponds with a value of dpH/dt of at least about + 0.1 pH units/min.
7. A process according to Claim 6 characterized by a dilution factor for the sum of stages subsequent to stage (I) which is not in excess of about twofold.
8. A process according to Claim 7 wherein said hypochlorite source is selected from chlorine, hypochlorous acid, alkali metal hypochlorites, alkaline earth metal hypochlorites, the product of mixing a hypochloriteliberating compound with aqueous alkali, and mixtures thereof.
9. A process according to Claim 8 wherein said aminofunctional compound is selected from (i) primary aminofunctional compounds selected from sulfamic acid, alkali-metal sulfamates, alkaline earth sulfamates, tetra-alkylammonium sulfamates, and mixtures thereof;
(ii) secondary aminofunctional compounds selected from secondary amine derivatives having formula RR'NH or (R")2NH wherein R, R' and R" are organic moieties and wherein carbon atoms of said organic moieties are bonded covalently to NH;
(iii) sulfonamides selected from sulfamide, p-toluenesulfonamide, imidodisulfonamide, benzenesulfonamide, alkyl sulfonamides, and mixtures thereof;
(iv) melamine, cyanamide; and (v) mixtures thereof.
(ii) secondary aminofunctional compounds selected from secondary amine derivatives having formula RR'NH or (R")2NH wherein R, R' and R" are organic moieties and wherein carbon atoms of said organic moieties are bonded covalently to NH;
(iii) sulfonamides selected from sulfamide, p-toluenesulfonamide, imidodisulfonamide, benzenesulfonamide, alkyl sulfonamides, and mixtures thereof;
(iv) melamine, cyanamide; and (v) mixtures thereof.
10. A process according to Claim 9 wherein said bromine compound is selected from the group consisting of bromine, water-soluble bromide salts, water-soluble hypobromite salts, hypobromous acid, and mixtures thereof.
11. A process according to Claim 10 wherein said hypochlorite source is selected from alkali metal hypochlorites and the product of mixing a hypochlorite-liberating compound and aqueous alkali; said aminofunctional compound is selected from sulfamic acid, alkali-metal sulfamates, alkaline earth sulfamates, tetra-alkylammonium sulfamates, and mixtures thereof; and said bromine compound is selected from the group consisting of water-soluble bromide salts.
12. A process according to Claim 11 wherein said hypochlorite source is sodium hypochlorite, said aminofunctional compound is sulfamic acid; and said bromine compound is selected from sodium bromide, potassium bromide and mixtures thereof.
13. A process according to Claim 12 wherein any of said aminofunctional compounds comprises no more than about 1% of aminofunctional impurity compounds having unstable N-halo derivatives.
14. A process according to Claim 13 wherein said alkali is selected from alkali metal-, alkaline earth-, and tetraalkylammonium- oxides, hydroxides, carbonates, bicarbonates, silicates, phosphates, borates, and mixtures thereof.
15. A process according to Claim 14 further comprising at least one additional mixing step wherein there is added an ingredient selected from the group consisting of surfactants, buffers, builders, chelants, abrasives, perfumes, colorants, dyes, bleach stabilizers, pigments, color speckles, suds supressors, anti-tarnish and/or anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removal/anti-redeposition agents, thickeners, solvents, and mixtures thereof.
16. An alkaline bleaching composition obtained by a process according to Claim 1.
17. An alkaline bleaching composition according to Claim 16 comprising from about 0.01 % to about 10 % available chlorine.
18. An alkaline bleaching composition according to Claim 17 having an interhalogen ratio [Br]:[OC1-] of from about 10:1 to about 1:10 wherein [Br] represents total moles Br added into said process from said bromine compound and [OC1-]
represents total moles hypochlorite added into said process from said hypochlorite source.
represents total moles hypochlorite added into said process from said hypochlorite source.
19. An alkaline bleaching composition according to Claim 18 having an amino-halo ratio [A]:[X] of from about 10:1 to about 1:10 wherein [A] represents total moles of amino moieties of said aminofunctional compound used to form said composition and wherein [X] represents total moles of bleaching halogen measurable as available chlorine present in said composition.
20. An alkaline bleaching composition according to Claim 19 wherein said amino-halo ratio is from about 1.0:1.0 to about 1.5:1.0
21. A process according to Claim 1 conducted in the absence of insoluble solid materials.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US1996/007089 WO1997043392A1 (en) | 1996-05-15 | 1996-05-15 | Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof |
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CA2254799A1 CA2254799A1 (en) | 1997-11-20 |
CA2254799C true CA2254799C (en) | 2003-02-11 |
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CA002254799A Expired - Fee Related CA2254799C (en) | 1996-05-15 | 1996-05-15 | Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof |
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EP (1) | EP0912695A1 (en) |
JP (1) | JPH11511779A (en) |
AU (1) | AU6145196A (en) |
CA (1) | CA2254799C (en) |
CZ (1) | CZ368598A3 (en) |
HU (1) | HUP9903494A3 (en) |
WO (1) | WO1997043392A1 (en) |
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US6007726A (en) * | 1998-04-29 | 1999-12-28 | Nalco Chemical Company | Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control |
US6511682B1 (en) | 1998-06-01 | 2003-01-28 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
US6068861A (en) | 1998-06-01 | 2000-05-30 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
US6299909B1 (en) | 1998-06-01 | 2001-10-09 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
US6348219B1 (en) | 1998-06-01 | 2002-02-19 | Albemarle Corporation | Processes for preparing concentrated aqueous liquid biocidal compositions |
US6352725B1 (en) | 1998-06-01 | 2002-03-05 | Albemarle Corporation | Continuous processes for preparing concentrated aqueous liquid biocidal composition |
US6652889B2 (en) | 1998-06-01 | 2003-11-25 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation and use |
US8293795B1 (en) * | 1998-06-01 | 2012-10-23 | Albemarle Corporation | Preparation of concentrated aqueous bromine solutions and biocidal applications thereof |
US8414932B2 (en) | 1998-06-01 | 2013-04-09 | Albemarie Corporation | Active bromine containing biocidal compositions and their preparation |
US6123870A (en) * | 1998-06-29 | 2000-09-26 | Nalco Chemical Company | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
US6287473B1 (en) | 1998-06-29 | 2001-09-11 | Nalco Chemical Company | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
US6156229A (en) * | 1998-06-29 | 2000-12-05 | Nalco Chemical Company | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
WO2000034429A1 (en) * | 1998-12-09 | 2000-06-15 | The Procter & Gamble Company | Aqueous liquid automatic dishwashing detergent composition having bromine and chlorine bleach |
US6270722B1 (en) | 1999-03-31 | 2001-08-07 | Nalco Chemical Company | Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control |
US6669904B1 (en) | 1999-03-31 | 2003-12-30 | Ondeo Nalco Company | Stabilized bromine solutions, method of making and uses thereof for biofouling control |
US6911422B1 (en) | 1999-07-01 | 2005-06-28 | The Procter & Gamble Company | Transparent or translucent, liquid or gel type automatic dishwashing detergent product |
WO2001002531A1 (en) * | 1999-07-01 | 2001-01-11 | The Procter & Gamble Company | Transparent or translucent, liquid or gel type automatic dishwashing detergent product |
US6506418B1 (en) | 1999-09-24 | 2003-01-14 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
KR100339129B1 (en) * | 1999-12-13 | 2002-05-31 | 심상희 | A method of controlling microorganism using hypobromite of alkali metal or alkali earth metals and a control system therefor |
US6565868B1 (en) | 2000-01-18 | 2003-05-20 | Albemarle Corporation | Methods for microbiological control in aqueous systems |
US6809205B1 (en) | 2000-01-18 | 2004-10-26 | Albemarle Corporation | Process for producing N-halogenated organic compounds |
US6680070B1 (en) | 2000-01-18 | 2004-01-20 | Albemarle Corporation | Particulate blends and compacted products formed therefrom, and the preparation thereof |
US6495698B1 (en) | 2000-01-18 | 2002-12-17 | Albemarle Corporation | Binder-free compacted forms of 1,3-dihalo-5,5-dimethylhydantoins |
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US6448410B1 (en) | 2000-01-18 | 2002-09-10 | Albemarle Corporation | Production of compacted biocidal agent from particulate biocidal agent without using a binder |
US7999118B2 (en) | 2000-01-18 | 2011-08-16 | Albemarle Corporation | Process for producing N-halogenated hydantoins |
US6375991B1 (en) | 2000-09-08 | 2002-04-23 | Albemarle Corporation | Production of concentrated biocidal solutions |
DE10248313A1 (en) * | 2002-10-16 | 2004-05-06 | Henkel Kgaa | Transparent abrasive cleaning agent, especially hand dishwashing liquid |
US20050176614A1 (en) | 2002-10-16 | 2005-08-11 | Heinz-Dieter Soldanski | Transparent abrasive cleaning product, especially manual dishwashing liquid |
CA2544330A1 (en) * | 2003-11-19 | 2005-06-02 | Unilever Plc | Hypochlorite bleach composition |
CN100577013C (en) | 2004-09-07 | 2010-01-06 | 雅宝公司 | Concentrated aqueous bromine solutions and preparation thereof |
CN101494985B (en) | 2005-06-10 | 2013-03-20 | 雅宝公司 | High concentrated, biocidally active compositions and aqueous mixtures and methods of making the same |
US8921295B2 (en) | 2010-07-23 | 2014-12-30 | American Sterilizer Company | Biodegradable concentrated neutral detergent composition |
JP6401491B2 (en) | 2013-08-28 | 2018-10-10 | オルガノ株式会社 | Method for inhibiting slime of separation membrane, slime inhibitor composition for reverse osmosis membrane or nanofiltration membrane, and method for producing slime inhibitor composition for separation membrane |
KR101990262B1 (en) | 2014-05-08 | 2019-06-17 | 오르가노 코포레이션 | Filtration treatment system and filtration treatment method |
JP6401573B2 (en) * | 2014-10-23 | 2018-10-10 | オルガノ株式会社 | Cleaning composition |
US10897905B2 (en) | 2016-01-26 | 2021-01-26 | Metrex Research, LLC | Hypochlorite based hard surface disinfectants |
US10986841B2 (en) | 2018-11-06 | 2021-04-27 | The Clorox Company | Bleach compositions |
US11845916B2 (en) | 2020-06-24 | 2023-12-19 | The Clorox Company | Burstable sporicidal cleaning wipe system containing stabilized hypochlorite |
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DK133825A (en) * | 1967-10-02 | |||
US3749672A (en) * | 1971-04-19 | 1973-07-31 | Du Pont | Stabilized solutions of n-halo compounds |
DE3308850C2 (en) * | 1983-03-12 | 1985-03-07 | B. Braun Melsungen Ag, 3508 Melsungen | Hypohalite-based bleaching, cleaning and disinfecting agents with improved storage stability |
JPS63108099A (en) * | 1986-10-24 | 1988-05-12 | ライオン株式会社 | Liquid bleaching composition |
JPH01164701A (en) * | 1987-12-18 | 1989-06-28 | Chiyoda Kagaku Kenkyusho:Kk | Method for stabilizing aqueous sodium hypochlorite solution |
-
1996
- 1996-05-15 HU HU9903494A patent/HUP9903494A3/en unknown
- 1996-05-15 CA CA002254799A patent/CA2254799C/en not_active Expired - Fee Related
- 1996-05-15 EP EP96918994A patent/EP0912695A1/en not_active Withdrawn
- 1996-05-15 CZ CZ983685A patent/CZ368598A3/en unknown
- 1996-05-15 AU AU61451/96A patent/AU6145196A/en not_active Abandoned
- 1996-05-15 JP JP9540825A patent/JPH11511779A/en active Pending
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WO1997043392A1 (en) | 1997-11-20 |
CZ368598A3 (en) | 1999-05-12 |
HUP9903494A2 (en) | 2000-03-28 |
HUP9903494A3 (en) | 2001-10-29 |
EP0912695A1 (en) | 1999-05-06 |
AU6145196A (en) | 1997-12-05 |
JPH11511779A (en) | 1999-10-12 |
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