US2848420A - Nontarnishing detergent compositions - Google Patents
Nontarnishing detergent compositions Download PDFInfo
- Publication number
- US2848420A US2848420A US442895A US44289554A US2848420A US 2848420 A US2848420 A US 2848420A US 442895 A US442895 A US 442895A US 44289554 A US44289554 A US 44289554A US 2848420 A US2848420 A US 2848420A
- Authority
- US
- United States
- Prior art keywords
- tarnish
- detergent
- detergent composition
- group
- accordance
- 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 - Lifetime
Links
- 239000003599 detergent Substances 0.000 title claims description 56
- 239000000203 mixture Substances 0.000 title claims description 55
- 239000001205 polyphosphate Substances 0.000 claims description 28
- 235000011176 polyphosphates Nutrition 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005494 tarnishing Methods 0.000 claims description 4
- -1 cyclic radical Chemical class 0.000 description 34
- 229920000388 Polyphosphate Polymers 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 14
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000000271 synthetic detergent Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 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 8
- 239000002253 acid Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000010956 nickel silver Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 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 4
- 125000000913 palmityl 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])C([H])([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 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 3
- 229940123208 Biguanide Drugs 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005275 alkylenearyl group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000010685 fatty oil Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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 3
- 239000003784 tall oil Substances 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- MLCIKWISJBFZKS-UHFFFAOYSA-N 6-undecyl-1,3,5-triazine-2,4-diamine Chemical compound CCCCCCCCCCCC1=NC(N)=NC(N)=N1 MLCIKWISJBFZKS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001117 oleyl 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])/C([H])=C([H])\C([H])([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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 2
- ZIRURAJAJIQZFG-UHFFFAOYSA-N 1-aminopropane-1-sulfonic acid Chemical compound CCC(N)S(O)(=O)=O ZIRURAJAJIQZFG-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- VJYAJQFKKLYARJ-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 VJYAJQFKKLYARJ-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- YZVJFFKAKLWXOE-UHFFFAOYSA-N 6-heptadecyl-1,3,5-triazine-2,4-diamine Chemical group CCCCCCCCCCCCCCCCCC1=NC(N)=NC(N)=N1 YZVJFFKAKLWXOE-UHFFFAOYSA-N 0.000 description 1
- 241000969130 Atthis Species 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006945 Knorr synthesis reaction Methods 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([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 1
- 125000005070 decynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000002960 margaryl 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])C([H])([H])C([H])([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 1
- 239000000463 material Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- WSVDSBZMYJJMSB-UHFFFAOYSA-N octadecylbenzene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1 WSVDSBZMYJJMSB-UHFFFAOYSA-N 0.000 description 1
- VXNSQGRKHCZUSU-UHFFFAOYSA-N octylbenzene Chemical compound [CH2]CCCCCCCC1=CC=CC=C1 VXNSQGRKHCZUSU-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UDEJEOLNSNYQSX-UHFFFAOYSA-J tetrasodium;2,4,6,8-tetraoxido-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 UDEJEOLNSNYQSX-UHFFFAOYSA-J 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
Definitions
- German silver is frequently used for household articles commonly washed in polyphospirate-built detergent compositions, it is evident that this is a serious problem.
- polyphosphate and detergent compositions are provided containing a tarnish inhibitor which compositions will not tarnish copper, and nickel and copper alloys such as German silver.
- a tarnish inhibitor which compositions will not tarnish copper, and nickel and copper alloys such as German silver.
- stituted guanamine (2,4-diamino-s-triazine) which is.described by the following formula:
- R is a hydrocarbon or hetero'cyclic radical and can be selected from the group consistingof aliphatic, aryl, mixed alkylene aryl, mixed phenylene heterocyclic and mixed alkyl'eneheterocyclic hydrocarbon radicals, and the other R radicals can be hydrogen or any of the radicals selectedfrom the above-mentioned:
- R is an aliphatic hydrocarbon group" it can have-either a straight or branched chain, and can be saturated or unsaturated.
- the number of carbon atoms in the R" groups is'ir'n-- portant. Form'oguanamine' is not effective. Good tarnish-inhibiting properties appear when at' least one" of R R R3, R1; or R is a' radical having three carbon atoms and theremaining R groups are hydrogen, but relatively large amounts of such guanamines may be necessary for complete protection.
- Tarnish-inhibiting ability materially improves as the' R groups increase further in molecular weight; and lesser amounts of guanamine can be used;
- Optimum tarnish-inhibiting properties are displayed by compounds; in which the sumof the R groups-is from seven to seventeen carbon atoms, especially compounds in which at least one'R has from seven to seventeencarbon atoms, and. invsuch compounds the number of carboniatoms in the remaining R groups is .not critical, .although the lower alkyl groups,
- the tarnish inhibitor of the invention is a sub-- '2 i. e., those having from one to about five carbon atoms, and hydrogen are preferred.
- R radicals are straight and branched chain methyl, ethyl, propyl, heptyl, octyl, nonyl, butyl, hexyl, decyl, undecyl, dodecyl, tri'decyl, tetradecyl, pentade'cyl, decenyl, heptylenyl, hexadecyl, heptadecyl, decynyl, dodecenyl, octa'de'cenyl, oct'adecadienyl, dodecynyl, the mixed alkyl radicals derived from fatty' oils such as palm oil, rapeseed oil, tall oil, linseed oil, etc., phenyl, benzyl, phenyl guanamyl, decylene guanamyl and octylene guanamyl
- the mixture of the nitrile, acid or ester and biguanide is heated at an elevated temperature, say 180 C., for several hours. Temperatures from 120 to 250 C. have been found satisfactory.
- the crude mixture which is obtained as a result of this reaction can be used without further purification and consists mainly of the substituted guanamide and, in the case of acid or ester reactants, of the amide of the acid or ester starting material in approximately equal amounts.
- the guanamine has been isolated and shown to be the principal antitarnishing constituent of the mixture.
- guanamines in accordance with the invention are nontoxic, sparingly water-soluble substances, but sufficiently water-soluble to permit their incorporation in polyphosphate and synthetic detergent solutions in the amounts required to impart tarnish inhibition thereto.
- guanamine An amount of the guanamine would be added to the polyphosphate and/or synthetic detergent composition suflicient to give tarnish inhibition when the composition is used in its normal way. Usually about 0.1% of the guanamine gives adequate tarnish inhibition, but larger amounts can be used if desired. From 0.1 to 5% is efiective under nearly all conditions and therefore is preferred. The maximum amount of guanamine is not critical but more than is necessary to give the desired effect usually would not be used, and of course an amount in excess of that soluble in the solution would not be used.
- the amount required will depend in part upon the tarnish-inhibiting properties of the particular guanamine in question, upon the tendency of the polyphosphate and/or synthetic detergent with which it is used to tarnish copper and nickel alloys and copper alloys, and upon the amounts of polyphosphate and synthetic detergent present.
- the guanamines of the invention are effective as tarnish inhibitors in both hard and soft water.
- tarnish inhibitors of the invention are effective with water-soluble polyphosphates as a class at pH values where such polyphosphates tend to tarnish German silver (usually pH 6 or above) and particularly those polyphosphates identified by the following general formula from which it is seen that both the acids and their various salts are contemplated:
- M M and M are hydrogen or an alkali metal, such as sodium, potassium and ammonium, and can be the same or different, and M is M and/ or M and/or M a is an integer of l or more, usually 1 to 4,
- I b is an integer of 1 or more, usually 1 or 2,
- x' is an integer of 1 or more, usually 1 to 6.
- polyphosphoric acids and their alkali metal salts coming within the invention are the polymetaphosphoric acids (HPO (a is 1, b is 1, x is more than 1), pyrophosphoric acid H P O (a is 2, b is 1, x is 1), triphosphoric acid H P O (a is 3, b is 2, x is 1), and tetraphosphoric acid H P O (a is 4, b is 3, x is 1).
- the guanamine tarnish inhibitors can be incorporated in compositions containing polyphosphates, and in compositions containing synthetic detergents, and are efiective to reduce tarnish due to polyphosphate or detergent in each of these types of compositions. They are particularly useful in synthetic detergent compositions which contain one or more polyphosphates as builders and one or more synthetic detergents, i. e., anionic detergents, cationic detergents, nonionic detergents, and mixtures thereof. In many instances they display an enhanced fifteen carbon atoms. whose preparation and properties are set forth in U. S.
- the polyphosphate-built detergent compositions should contain conventional proportions of active detergent, usually within the range between '5 to 40%, polyphosphate in any amount, usually between 5 to-50%, based on the total composition, and the residue builders and inert materials.
- guanamines are useful with a wide variety of anionic, cationic and nonionic synthetic detergents, with and without polyphosphates.
- alkyl aryl sulfonates are a class of detergents well known in the art under this name.
- One example thereof are the sulfonated phenylpolypropylene alkanes, charac- -terized by thebranched chain structure of polypropylene and a tertiary alkyl carbon at the benzene ring, and having the following general structure:
- R and R are alkyls, of the type formula C H and at least one R is a polypropylene group, the whole alkyl group containing preferably twelve to These are known compounds,
- Patent No. 2,477,383 to Lewis issued July 26, 1949; they are available in'commerce' under the trade names Oronite, Ultrawet and Neolene.
- amidoalkane sulfonates which are characterized: bythe following structure:
- A is hydrogen oran alkali metal, i. e., ammonium, I
- n is a small whole number from one to about five, preferably two or three
- R is hydrogen, or an alkyl, aryl, or cycloaliphatic group, such as methyl
- R is an alkyl'or alkylene radical, such as myristyl, palmityl, oleyl and stearyl.
- These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an or- V ganic aliphatic aminosulfonic acid, such as taur'ine and the various N substituted taurines, such as N-methyl taurine, or aminopropane sulfonic acid;-NI-I (CH SOH.
- the invention is also applicable to 'other-water-soluble alkyl aromatic sulfonic acids, such as those prepared by alkylating benzene or naphthalene with a kerosene frac- G and. thioether-andester.detergentshaving the following general formula:
- R-A-tcrn Hte-it-.cH-l- Hz n where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an, aralkyl group having a straight or branched saturatedor unsaturated hydrocarbon group of' from eight to eighteen carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selectedfrom the group consisting ofethereal oxygen and-sulfur,jca'rboxylic esterand thiocarboxylicester groups and x is a. number'from eight to twenty.
- R can for examplebe a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group, or an alkyl aryl group such as octylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc.
- R is alkyl
- the detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid ofhighmolecular weight, by condensa'tion with ethylene oxide.
- Typical of this type of alkyl ether are the condensation-products of oleyl or 'dodecyl alcohol orrn'ercaptan .with from eight to seventeen 'zmoles of ethylene oxide, such -'as Emulfor ON, Nonic 218 and .SteroxI SE andSK.
- Typical alkyl 'esters are 61226 and R'enex (polyoxyethyleneester of tall oil acids), Sterox CD and Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).
- R is aralkyl
- the detergent can be derived from an alkyl phenol or thiophenol.
- the ethoxynated alkyl phenols and thiophenols have the following general formula:
- R is a straight or branched saturated or unsaturated hydrocarbon group having at least eight carbon atoms up to. approximately eighteen carbon atoms, A is oxygen or sulfur and x is a number from eight to twenty.
- R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names NIW, Antarox A-400, Igepal CA and CO, Triton X-100, Neutronyx 600 and Tergitol NFX.
- the detergent composition can contain supplemental builders including alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates, metaphosphates, and orthophosphates, such as sodium silicate, magnesium sulfate, sodium tetraborate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, disodium orthophosphate, sodium metaphosphate, calcium sulfate, calcium chloride, sodium chloride, sodium borate and potassium metaphosphate.
- the builder should but need not be water-soluble.
- organic materials such as starch, polyethylene glycols, polyvinyl alcohols and salts of carboxymethylcellulose can be used as builders. It has been found that between about 0.1 and 1% of an al- -kali--metal carboxymethylcellulose increases detergency "and" sudsing.
- the builder mixture is so chosen among alkaline, neutral and acidic salts that the composition obtained in an aqueous 0.14% washing solution has a pH of 7 or above. Preferably, its pH lies within the range from 7 8 for one-ha1f hour.
- the efiectiveness of the inhibitor is rated as follows:
- the detergent composition is prepared by conventional lowing f latio methods, as by blending the ingredients thereof in an percent aq u solution or slurry and then drymg the result- Sodium Oronite (active) (sodium phenylpolypromg mixture in a spray or drum dryer at elevated tempylene lf t p Tetrasodiurn pyrophosphate 30.0
- the tarnish inhibitor may be added to the polyphoss i tripolyphosphate 15 phate or detergent composition at any stage of its manu- Sodium carboxymethylcellulose 0.5 facture, to the finished polyphosphate or detergent coms di i1i 6,0 position, or to the polyphosphate or detergen solution.
- guanamines employed in the following examples s di ulfat and i 20,5 were prepared by heating mixtures of biguanide and the Water 7.0 corresponding nitrile at ISO-200 C. for about two to four hours. 1:1 molar ratios were taken of biguanide 10() and the nitrile. The crude product was used unless other- Wi in i Guanamine 1 0.02 to 5 2 33 212; g f i g f s P actlon of the composl' 1 0.044 to 11.1% based on the weight of the polyphosphates.
- guanamin'ewithout an-R' substituent is a guanamin'ewithout an-R' substituent,.is.-noteifective as a tarnishinhibitor.
- R is a higher alkyl group.
- compositions also were "evaluated for-their sud sing properties. This wasdoneusing the Terg-O-Tometer em-- ploy-ing thefollowingprocedurezl2.64 g. of thedetergent composition Without the tarnish inhibitor was weighed into:a 100 ml. beakerand 'the appropriateamount'of the tarnish inhibitor tobe testedwas added. "'Fifty mL of SO p.;p.-m. Waterwas'then added and the solids brought 'into solution with the aid of heat; The solution was-diluted to 1,000 ml. with 50 p. p..-m. water, brought to 120 F. and placed in the cup of a standard Terg-O-Tometer.
- Compositions containingv tarnish inhibitors of the-invention do not tarnish copper, nickel-copper-Zi'n-c alloys such as German silver, coinage nickel or brass, whichnorma'lly tarnish whenexposed to aqueous' solutions containing-polyphosphates and/ or synthetic detergents. It isnot possible atthis tim'e to explain whythe-compounds-of theinventhe weight of the-tarnish producin'g substance, i: e.',polyphosphate and/or detergent, unless otherwisestated.
- the-compounds-of theinventhe weight of the-tarnish producin'g substance i: e.',polyphosphate and/or detergent, unless otherwisestated.
- the weightsofguanamine are given as based'on the dry weightof the total composition.
- a detergent composition consisting essentially of a water-soluble substance selected from the group consisting of polyphosphates and synthetic organic nonsoap anionic and nonionic detergents which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the substance and having the general formula:
- N /NR4R5 where at least one R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remain ing R radicals are selected from the group consisting of hydrogen, hydrocarbon, and guanamine radicals.
- R is the mixed alkyl radicals derived from a naturally-occurring fatty oil.
- a detergent composition consisting essentially of a water-soluble polyphosphate which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the polyphosphate and having the general formula:
- R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remaining R radicals are selected from the group consisting of hydrogen, hydrocarbon, and guanamine radicals.
- a detergent composition consisting essentially of a water-soluble synthetic organic nonsoap detergent selected from the group consisting of anionic and nonionic detergents which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the detergent and having the general formula:
- R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remaining R radicals are selected from the group consisting of hydrogen, hydrocarbon and guanamine radicals.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE539762D BE539762A (enrdf_load_stackoverflow) | 1954-07-12 | ||
| US442895A US2848420A (en) | 1954-07-12 | 1954-07-12 | Nontarnishing detergent compositions |
| FR1127340D FR1127340A (fr) | 1954-07-12 | 1955-07-11 | Perfectionnements aux compositions détergentes |
| DEU3428A DE969642C (de) | 1954-07-12 | 1955-07-13 | Reinigungsmittel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US442895A US2848420A (en) | 1954-07-12 | 1954-07-12 | Nontarnishing detergent compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2848420A true US2848420A (en) | 1958-08-19 |
Family
ID=23758578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US442895A Expired - Lifetime US2848420A (en) | 1954-07-12 | 1954-07-12 | Nontarnishing detergent compositions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2848420A (enrdf_load_stackoverflow) |
| BE (1) | BE539762A (enrdf_load_stackoverflow) |
| DE (1) | DE969642C (enrdf_load_stackoverflow) |
| FR (1) | FR1127340A (enrdf_load_stackoverflow) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110049052A1 (en) * | 2009-09-02 | 2011-03-03 | Hirsch Keith A | Method for inhibiting the deposition of silica and/or silicate compounds in aqueous systems |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2618603A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
| US2618605A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE508905A (enrdf_load_stackoverflow) * | 1951-02-03 |
-
0
- BE BE539762D patent/BE539762A/xx unknown
-
1954
- 1954-07-12 US US442895A patent/US2848420A/en not_active Expired - Lifetime
-
1955
- 1955-07-11 FR FR1127340D patent/FR1127340A/fr not_active Expired
- 1955-07-13 DE DEU3428A patent/DE969642C/de not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2618603A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
| US2618605A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110049052A1 (en) * | 2009-09-02 | 2011-03-03 | Hirsch Keith A | Method for inhibiting the deposition of silica and/or silicate compounds in aqueous systems |
Also Published As
| Publication number | Publication date |
|---|---|
| DE969642C (de) | 1958-06-26 |
| FR1127340A (fr) | 1956-12-13 |
| BE539762A (enrdf_load_stackoverflow) |
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