EP0009953B1 - Reinigungsmittelzusammensetzungen - Google Patents
Reinigungsmittelzusammensetzungen Download PDFInfo
- Publication number
- EP0009953B1 EP0009953B1 EP79302058A EP79302058A EP0009953B1 EP 0009953 B1 EP0009953 B1 EP 0009953B1 EP 79302058 A EP79302058 A EP 79302058A EP 79302058 A EP79302058 A EP 79302058A EP 0009953 B1 EP0009953 B1 EP 0009953B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- phosphate
- weight
- orthophosphate
- detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 239000003599 detergent Substances 0.000 title claims abstract description 77
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 79
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 72
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 67
- 239000010452 phosphate Substances 0.000 claims abstract description 59
- -1 alkali metal orthophosphate Chemical class 0.000 claims abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 28
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 14
- 235000011180 diphosphates Nutrition 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 3
- 159000000000 sodium salts Chemical group 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 abstract description 64
- 239000000843 powder Substances 0.000 abstract description 22
- 239000004744 fabric Substances 0.000 abstract description 20
- 239000002585 base Substances 0.000 abstract description 18
- 238000005406 washing Methods 0.000 abstract description 15
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 13
- 238000001694 spray drying Methods 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 20
- 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 19
- 239000000047 product Substances 0.000 description 16
- 239000000344 soap Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 229960001922 sodium perborate Drugs 0.000 description 8
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 159000000011 group IA salts Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- JQUQNGYUEFSZBS-UHFFFAOYSA-N [Na].CC Chemical compound [Na].CC JQUQNGYUEFSZBS-UHFFFAOYSA-N 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- JSZVAKSQKFZKNG-UHFFFAOYSA-K P(=O)(O)(O)C(C(C(=O)[O-])(C(=O)[O-])C(=O)[O-])CC.[Na+].[Na+].[Na+] Chemical compound P(=O)(O)(O)C(C(C(=O)[O-])(C(=O)[O-])C(=O)[O-])CC.[Na+].[Na+].[Na+] JSZVAKSQKFZKNG-UHFFFAOYSA-K 0.000 description 1
- BVBIQASDHXEFKW-UHFFFAOYSA-N P1(OCCCCO1)=O.C(CN)N.[Na] Chemical compound P1(OCCCCO1)=O.C(CN)N.[Na] BVBIQASDHXEFKW-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical class ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000019488 nut oil Nutrition 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 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
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 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
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D3/06—Phosphates, including polyphosphates
Definitions
- the present invention relates to powdered detergent compositions which are adapted for fabric washing, and which contain synthetic detergent active compounds together with mixed phosphate detergency builders.
- the invention concerns in particular the production of detergent compositions which contain levels of the mixed phosphate detergency builders which can be lower than conventional phosphate builder levels, but which still retain good detergency properties.
- a particulate detergent composition based on mixed phosphate detergency builders comprises a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof, an alkali metal orthophosphate, and discrete particles of alkali metal or ammonium polymer phosphate.
- the invention includes a process for the preparation of the detergent composition, which comprises forming a detergent base powder containing some or all of the detergent active compound or compounds and optionally some of the alkali metal orthophosphate, and admixing an alkali metal or ammonium polymer phosphate in discrete particulate form with the base powder.
- the base powder is prepared by spray drying in the normal way using conventional equipment and process conditions.
- other conventional techniques may be used for preparing the base powder containing some or all of the detergent active compound or compounds and of the alkali metal orthophosphate.
- Other heat-sensitive ingredients may be admixed with the base powder together with or separately from the alkali metal or ammonium polymer phosphate, for example oxygen bleach compounds such as sodium perborate.
- the alkali metal polymer phosphate used in the compositions of the invention is preferably sodium polymer phosphate, but if desired the potassium or ammonium salts can be used.
- alkali metal polymer phosphate is used below and in the claims to include the sodium, potassium and ammonium salts.
- the alkali metal polymer phosphates are generally represented as having the formula M20(MPO,)n, where M is sodium, potassium or ammonium and n is an integer which is at least 4 and up to 100 or more, preferably from 6 to 50.
- these figures correspond to a P 2 0 5 content of at least 60.4% by weight up to a theoretical maximum of 69.6%, preferably 63% to 69% P 2 0 5 by weight of the polymer phosphates.
- the polymer phosphates must of course be water-soluble. It should be appreciated that the chemical structures of the polymer phosphates are not precisely defined, and some degree of ring formation or branching may be present in the otherwise normally linear polymer structure, especially with the shorter polymer chain lengths.
- the polymer phosphates are sometimes also known as glassy phosphates or Graham's salt.
- alkali metal polymer phosphate should be admixed with the detergent base powder, ie postdosed, to obtain the most benefit of lower alkali metal pyrophosphate content in the product.
- some alkali metal polymer phosphate can be included in the base powder if desired, and this can help to improve the powder properties, particularly when relatively low alkali metal orthophosphate levels are used.
- the alkali metal polymer phosphate which is postdosed should, of course, have a suitable particulate form for post-dosing, that is to say it should have an appropriate particle size range and powder density for uniform mixing with the base powder, so as to avoid undue segregation in the finished product.
- the alkali metal orthophosphate used is either potassium or preferably sodium orthophosphate, as the latter is cheaper and more readily available. Normally the tri-alkali metal salts are used, but orthophosphoric acid or the di- or mono-alkali metal salts, eg disodium hydrogen orthophosphate or monosodium dihydrogen orthophosphate could be used if desired in the production of the compositions. In the latter event other more alkaline salts should also be present to maintain a high pH in the end product, ie with full neutralisation to the trialkali metal orthophosphate salts.
- a mixture of the monosodium dihydrogen and disodium hydrogen orthophosphates in the ratio of 1:3 to 2:3, especially about 1:2, is particularly advantageous, as such a mixture (known as kiln-feed) is made in the production of sodium tripolyphosphate and is readily available. It is preferred to have all the alkali metal orthophosphate present in the detergent base powder, eg by inclusion in an aqueous detergent slurry and then spray dried, but part of the orthophosphate can be postdosed if desired, either separately or together with the alkali metal polymer phosphate.
- the alkali metal orthophosphate can be used in the form of the anhydrous or hydrated salts, but in the former case it is preferred to promote hydration during processing, eg by adding the anhydrous orthophosphate to a detergent slurry and spray drying to form the base powder.
- the alkali metal polymer phosphates do not form hydrated salts as such, and are normally used in anhydrous form, but they are hygroscopic and tend to absorb atmospheric moisture. The amounts of the salts used are expressed in anhydrous form.
- the total amounts of the essential alkali metal polymer phosphate and alkali metal orthophosphate, and any other phosphates which may be present in the detergent compositions are chosen according to the overall detergency builder level which is desired in the detergent compositions or according to the maximum permitted phosphorus content.
- the total phosphate builder level which is preferably derived solely from alkali metal polymer phosphate and alkali metal orthophosphate, is between 10% and 40%, by weight of the composition, preferably with an amount of at least 5% and at least 2% up to 20% each of the alkali metal polymer phosphate and orthophosphate, respectively.
- the amounts of the alkali polymer phosphate and alkali metal orthophosphate are each from 5% to 15%, especially 5% to 10%, by weight of the composition.
- the total amount of alkali metal polymer phosphate and alkali metal orthophosphate is preferably from 10% to 25%, especially 15% to 20%, by weight of the composition.
- alkali metal polymer phosphate and the alkali metal orthophosphate generally within the ratio of from 3:1 to 1:3, especially 2:1 to 1:2, parts by weight, respectively.
- ratios of polymer phosphate to orthophosphate are particularly suitable for detergent compositions used at relatively high product concentrations, ie 0.3% to 0.8% by weight, as is common practice in Europe, especially in front-loading automatic washing machines, and where moderate levels of phosphates are allowed in the products, ie equivalent to about 3% to 7% P.
- the only phosphate detergency builders used to make the compositions of the invention should be the alkali metal polymer phosphate and alkali metal orthophosphate.
- some alkali metal tripolyphosphate may be present if desired either in the base powder or postdosed thereto, for example because of its beneficial effect on the base powder properties or because of its relative cheapness. But for optimum detergency in relation to total phosphate content, it is preferred to have not more than 10% by weight of other alkali metal phosphate builders, and especially not more than 5% of tripolyphosphate present in the detergent composition.
- tripolyphosphate and pyrophosphate are also generally found as impurities at low levels in other commercial alkali metal phosphates, and some tripolyphosphate and pyrophosphate may be formed by hydrolysis of any polymer phosphate during processing, especially if some of it is present in the slurry rather than being all postdosed. Hence, total absence of alkali metal tripolyphosphate and pyrophosphate is generally unattainable in the detergent compositions. It is particularly preferred to have not more than 2.5% of alkali metal pyrophosphate present in the compositions, as at higher levels the amounts of inorganic deposits on the washing machine parts become significantly more noticeable.
- the detergent compositions of the invention necessarily include from 2.5% to 50%, preferably 5% to 30%, and especially 10% to 25%, by weight of a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof.
- a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry & Berch.
- the preferred detergent compounds which can be used are synthetic anionic and nonionic compounds.
- the former are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
- suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 ⁇ C 18 ) alcohols produced for example from tallow or coconut oil; sodium and potassium alkyl (C - C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 ⁇ C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 9 ⁇ C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isothionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurate
- Suitable nonionic detergent compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
- nonionic detergent compounds are alkyl (C 6 -C 22 ) phenol- ethylene oxide condensates, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C 8 ⁇ C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, or with both ethylene and propylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
- Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain terttary-phosphine oxides and dialkyl sulphoxides.
- detergent compounds for example mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions, particularly in the latter case to provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds-intolerant automatic washing machines.
- some nonionic detergent compounds in the compositions decreases the tendency of insoluble phosphate salts to deposit on the washed fabrics, especially when used in admixture with some soaps as described below.
- Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds. For example, mixtures of amine oxides and ethoxylated nonionic detergent compounds can be used.
- Soaps may also be present in the detergent compositions of the invention, but not as the sole detergent compounds.
- the soaps are particularly useful at low levels in binary and ternary mixtures, together with nonionic or mixed synthetic anionic and nonionic detergent compounds, which have low sudsing properties.
- the soaps which are used are the sodium, or less desirably potassium, salts of C 1o -C 24 fatty acids. It is particularly preferred that the soaps should be based mainly on the longer chain fatty acids within this range, that is with at least half of the soaps having a carbon chain length of 16 or over.
- soaps from natural sources such as tallow, palm oil or rapeseed oil, which can be hardened if desired, with lesser amounts of other shorter chain soaps, prepared from nut oils such as coconut oil or palm kernel oil.
- the amount of such soaps can be varied between 0.5% and 25% by weight, with lower amounts of 0.5% to 5% being generally sufficient for lather control.
- Amounts of soap between 2% and 20%, especially between 5% and 15%, can advantageously be used to give a beneficial effect on detergency.
- the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric washing detergent compositions.
- these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates, waxes and silicones, antiredeposition agents such as sodium carboxymethylcellulose and polyvinyl pyrrolidone optionally copolymerised with vinyl acetate, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, per acid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softening agents, inorganic salts such as sodium sulphate, sodium carbonate and magnesium silicate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and
- an amount of sodium perborate preferably between 10% and 4.0%, for example 15% to 30%, by weight. It has been found that the bleaching action of sodium perborate is boosted under the highly alkaline conditions which also give optimum detergency building action for the alkali metal orthophosphate. Thus, it becomes possible to achieve improved bleaching properties by using the same levels of sodium perborate as normal; or decreased levels of sodium perborate can be used to give equal bleaching properties to those of conventional products with higher levels of perborate and sodium tripolyphosphate as the sole detergency builder. The latter option can also be used to further decrease the raw materials costs of the compositions, if a cheap filler is used in place of part of the sodium perborate.
- the effective antideposition agents are materials which stabilise insoluble calcium orthophosphate particles and thereby inhibit their deposition onto the fabrics.
- the most effective antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates.
- the amount of any such antideposition agent can be from 0.01 % to 10% of the compositions, but is normally from 0.1% to 5% by weight, preferably from 0.2% to 2% by weight of the compositions.
- Specific preferred antideposition agents are the alkali metal or ammonium, preferably the sodium, salts of homo- and co-polymers of acrylic acid or substituted acrylic acids, such as sodium polyacrylate, the sodium salt of copolymethacrylamide/acrylic acid and sodium polyalpha-hydroxyacrylate, salts of copolymers of maleic anhydride with ethylene, acrylic acid, vinylmethylether or styrene, especially 1:1 copolymers, and optionally with partial esterification of the carboxyl groups.
- Such copolymers preferably have relatively low molecular weights, eg in the range of about 1,000 to 50,000.
- antideposition agents include the sodium salts of polymaleic acid, polyitaconic acid and polyaspartic acid, phosphate esters of ethoxylated aliphatic alcohols, polyethylene glycol phosphate esters, and certain organic phosphonic acids or salts thereof such as sodium ethane - 1 - hydroxy - 1,1 - diphosphonate, sodium ethylenediamine tetramethylene phosphonate and sodium - 2 - phosphonobutane tricarboxylate. Mixtures of organic acids or substituted acrylic acids or their salts with protective colloids such as gelatin may also be used.
- the most preferred antideposition agents are sodium polyacrylates having a MW of 10,000 to 50,000, for example 20,000 to 30,000.
- non-phosphate detergency builders which may be either so-called precipitant builders, ion-exchange or sequestrant builders.
- precipitant builders ion-exchange or sequestrant builders.
- detergency builders examples include amine carboxylates such as sodium nitrilotriacetate, sodium carbonate, sodium aluminosilicate ion-exchange materials such as zeolites A and X, sodium citrate and soap, which can function as a detergency builder, as discussed above.
- amine carboxylates such as sodium nitrilotriacetate, sodium carbonate, sodium aluminosilicate ion-exchange materials such as zeolites A and X, sodium citrate and soap, which can function as a detergency builder, as discussed above.
- such other builder materials are not essential and it is a particular benefit of using the mixed alkali metal polymer phosphate and orthophosphate that satisfactory detergency properties can be achieved at lower total phosphate levels than hitherto considered necessary without other detergency builders.
- an amount of an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
- alkali metal silicates at levels of at least 1%, and preferably from 5% to 15%, by weight of the compositions, is advantageous in decreasing the corrosion of metal parts in washing machines, besides giving processing benefits and generally improved powder properties.
- the more highly alkaline ortho- and meta- silicates would normally only be used at lower amounts within this range, in admixture with the neutral or alkaline silicates.
- compositions of the invention are required to be alkaline, but not too strongly alkaline as this could result in fabric damage and also be hazardous for domestic usage.
- the compositions should give a pH of from 9 to 11 in use in aqueous wash solution. It is preferred in particular for domestic products to have a minimum pH of at least 9.25 and especially a pH of 9.5 or over, as lower pHs tend to be less effective for optimum detergency building, and a maximum pH of 10.5, as more highly alkaline products can be hazardous if misused.
- the pH is measured at the lowest normal usage concentration of 0.1% w/v of the product in water of 12°H (Ca), (French permanent hardness, calcium only) at 50°C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrations.
- the pH of the detergent compositions in use is controlled by the amount of alkali metal orthophosphate and any other alkaline salts such as alkali metal silicate, sodium perborate and sodium carbonate present.
- alkali metal silicates especially the alkali metal silicates
- the presence of such other alkaline salts, especially the alkali metal silicates, is particularly beneficial, because the alkalinity of the alkali metal orthophosphate is diminished in hard water due to precipitation of the calcium salt.
- the alkali metal polymer phosphate is more stable and resistant to hydrolysis under highly alkaline conditions.
- the other ingredients in the alkaline detergent compositions of the invention should of course be chosen for alkaline stability, especially the pH sensitive materials such as enzymes.
- the detergent compositions of the invention are in particulate form after admixture of the spray dried base powder and the alkali metal polymer phosphate. However, if desired the detergent compositions may be compressed or compacted into tablets or blocks, or otherwise treated for example by granulation, prior to packaging and sale. Because of the hygroscopic nature of the alkali metal polymer phosphates, it may be desirable to use moisture impermeable packaging for the detergent compositions, for example in plastic or fabric sachets containing pre-measured doses for washing machine usage.
- a series of detergent powders were prepared by firstly spray drying a detergent base powder to the following formulation: Amounts of additives as specified in the Table below were then added to this base powder to make the formulations as follows:
- detergent compositions were evaluated for washing performance, including especially inorganic deposition on fabrics.
- the tests were accomplished in laundrometer machines using a product concentration of 8 g/I in water of 40° French hardness at 95°C.
- the levels of deposition on the fabrics were determined after 10 repeat wash cycles using standard fabrics as indicated.
- a detergent composition was prepared to the following formulation by dry mixing the ingredients to which the particulate sodium polymer phosphate was added:
- the composition was tested for detergency and inorganic deposition on washed fabrics (ash). Considering the low phosphate builder level the detergency properties were good, and the ash levels were particularly low, being 0.5% on cotton poplin fabric and 1.5% on Krefeld cotton after 10 wash cycles. The tests were conducted at a product concentration of 8 g/I in an Atlas launderometer at 95°C in 23° GH water. By way of comparison, the ash levels for a similar sodium tripolyphosphate-sodium orthophosphate built formulation were 2.0% and 5.7% respectively, under the same conditions.
- compositions were evaluated for detergency and inorganic fabric deposition, and found to be good in both respect.
- the average figures for the latter on different cotton types after 10 wash cycles were only 0.3%, 0.65%, 0.75% and 1.3%, respectively, under the same conditions as for
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Claims (10)
Priority Applications (1)
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AT79302058T ATE3056T1 (de) | 1978-10-03 | 1979-10-01 | Reinigungsmittelzusammensetzungen. |
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GB3907378 | 1978-10-03 | ||
GB7839073 | 1978-10-03 |
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EP0009953A1 EP0009953A1 (de) | 1980-04-16 |
EP0009953B1 true EP0009953B1 (de) | 1983-04-13 |
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EP79302058A Expired EP0009953B1 (de) | 1978-10-03 | 1979-10-01 | Reinigungsmittelzusammensetzungen |
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EP (1) | EP0009953B1 (de) |
JP (1) | JPS5550096A (de) |
AT (1) | ATE3056T1 (de) |
AU (1) | AU533317B2 (de) |
BR (1) | BR7906347A (de) |
CA (1) | CA1128401A (de) |
DE (1) | DE2965209D1 (de) |
ES (1) | ES484666A1 (de) |
ZA (1) | ZA795231B (de) |
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DE3035805A1 (de) * | 1980-09-23 | 1982-05-06 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von granulaten kondensierter phosphate |
FR2552446B1 (fr) * | 1983-09-27 | 1985-12-20 | Camp Sa | Detergents granulaires a faible teneur en phosphates, et leur procede de fabrication |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1792434B2 (de) * | 1967-09-04 | 1977-09-15 | Unilever N V, Rotterdam (Niederlande) | Verfahren zur herstellung eines wasch- und reinigungsmittels |
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US4115307A (en) * | 1974-12-13 | 1978-09-19 | Erco Industries Limited | Phosphate composition |
US4116852A (en) * | 1975-02-14 | 1978-09-26 | The Procter & Gamble Company | Builders and built detergent compositions |
GB1530799A (en) * | 1975-08-28 | 1978-11-01 | Unilever Ltd | Detergent compositions |
DE2816770C2 (de) * | 1977-04-22 | 1984-10-18 | The Procter & Gamble Co., Cincinnati, Ohio | Gerüststoffhaltiges Textilwaschmittel |
-
1979
- 1979-10-01 AT AT79302058T patent/ATE3056T1/de not_active IP Right Cessation
- 1979-10-01 EP EP79302058A patent/EP0009953B1/de not_active Expired
- 1979-10-01 DE DE7979302058T patent/DE2965209D1/de not_active Expired
- 1979-10-02 AU AU51361/79A patent/AU533317B2/en not_active Ceased
- 1979-10-02 BR BR7906347A patent/BR7906347A/pt unknown
- 1979-10-02 ES ES484666A patent/ES484666A1/es not_active Expired
- 1979-10-02 ZA ZA00795231A patent/ZA795231B/xx unknown
- 1979-10-02 CA CA336,796A patent/CA1128401A/en not_active Expired
- 1979-10-03 JP JP12783679A patent/JPS5550096A/ja active Granted
Patent Citations (1)
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DE1792434B2 (de) * | 1967-09-04 | 1977-09-15 | Unilever N V, Rotterdam (Niederlande) | Verfahren zur herstellung eines wasch- und reinigungsmittels |
Also Published As
Publication number | Publication date |
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ZA795231B (en) | 1981-05-27 |
BR7906347A (pt) | 1980-05-27 |
JPS5550096A (en) | 1980-04-11 |
EP0009953A1 (de) | 1980-04-16 |
CA1128401A (en) | 1982-07-27 |
AU533317B2 (en) | 1983-11-17 |
ES484666A1 (es) | 1980-09-01 |
JPS6131751B2 (de) | 1986-07-22 |
DE2965209D1 (en) | 1983-05-19 |
AU5136179A (en) | 1980-04-17 |
ATE3056T1 (de) | 1983-04-15 |
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