EP0150613B1 - Reinigungsmittelzusammensetzungen - Google Patents
Reinigungsmittelzusammensetzungen Download PDFInfo
- Publication number
- EP0150613B1 EP0150613B1 EP84308962A EP84308962A EP0150613B1 EP 0150613 B1 EP0150613 B1 EP 0150613B1 EP 84308962 A EP84308962 A EP 84308962A EP 84308962 A EP84308962 A EP 84308962A EP 0150613 B1 EP0150613 B1 EP 0150613B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- granules
- weight
- base powder
- sodium
- aluminosilicate
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000003599 detergent Substances 0.000 title claims abstract description 57
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 71
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000008187 granular material Substances 0.000 claims abstract description 42
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- 239000007844 bleaching agent Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000011149 active material Substances 0.000 claims abstract description 13
- 159000000011 group IA salts Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 229910001868 water Inorganic materials 0.000 claims description 38
- 239000002585 base Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 36
- 239000004115 Sodium Silicate Substances 0.000 claims description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000344 soap Substances 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 18
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- 229960001922 sodium perborate Drugs 0.000 claims description 9
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 9
- 239000000271 synthetic detergent Substances 0.000 claims description 8
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 13
- 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 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- -1 alkali metal salts Chemical class 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 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 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 235000019488 nut oil Nutrition 0.000 description 2
- 239000010466 nut oil Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 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 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 150000004685 tetrahydrates Chemical class 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
- QRXQKFYWKYJUBM-UHFFFAOYSA-N 2,3-dimethylnonadecan-2-amine Chemical compound CCCCCCCCCCCCCCCCC(C)C(C)(C)N QRXQKFYWKYJUBM-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 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
- 229920002472 Starch Polymers 0.000 description 1
- 235000004240 Triticum spelta Nutrition 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
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003926 complexometric titration Methods 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
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 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
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- BNVZBQVIMPLFNA-UHFFFAOYSA-L disodium;2-(carboxymethoxy)butanedioate Chemical compound [Na+].[Na+].OC(=O)COC(C([O-])=O)CC([O-])=O BNVZBQVIMPLFNA-UHFFFAOYSA-L 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
- 229940088598 enzyme Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940012017 ethylenediamine Drugs 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 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
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000006174 pH buffer Substances 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
- 235000020030 perry Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-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
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/39—Organic or inorganic per-compounds
Definitions
- Granular detergent compositions invariably contain water. Most or all of this water is relatively loosely bound and is lost when the composition is heated to say 135°C. This loosely bound water is constituted by water of crystallization of the components in the composition, and further water which is more loosely bound to ingredients such as detergent active materials.
- moisture is the water which is lost from the composition when it is heated to 135°C.
- compositions containing amorphous aluminosilicate and also in compositions containing NTA (sodium nitrilotriacetate) some water is not lost at 135°C. This more tightly bound water however adds to the total water content of the composition.
- compositions containing amorphous aluminosilicate are dependent upon the moisture content of the composition rather than the total water content.
- composition comprises a spray-dried base powder containing at least a detergent active and an amorphous aluminosilicate builder material, to which have been post-dosed various further components such as bleaches, the critical factor in the ion-exchange properties of the composition of the moisture content of the base powder.
- a detergent composition comprising spray-dried base powder granules, together with one or more post-dosed ingredients which include a peroxygen bleach compound, the base powder granules containing at least a synthetic detergent active material, an amorphous aluminosilicate builder material, moisture, optionally soap, optionally crystalline aluminosilicate builder material, and optionally an alkaline salt selected from alkali metal silicates, alkali metal carbonates, alkali metal phosphates and mixtures thereof, characterised in that the moisture content of said granules is determined by the formula where M is the moisture content of said granules in parts by weight, as measured by the water loss from said granules at 135°C, A is the amount of the detergent active material including soap, if any, in said granules in parts by weight, S is the amount of the alkaline salt in said granules in parts by weight, X is the amount of a
- y preferably lies between 0.25 and 0.5. Otherwise, the preferred level for y is from 0.5 to 0.6.
- compositions of the invention necessarily contain a synthetic detergent active material otherwise known as a detergent surfactant, preferably present at an overall level of between 2% and 60% by weight, especially between 5% and 40% of the composition.
- a synthetic detergent active material otherwise known as a detergent surfactant
- Suitable detergent surfactants are well known and readily available, as described for example in "Surface Active Agents and Detergents", Volumes I and II by Schwartz, Perry and Berch.
- Synthetic anionic detergent compunds which can be used 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 the higher (C 8 -C la ) alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl (C 9 -C 2o ) 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 acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 ⁇ C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of
- Nonionic detergent active compounds may alternatively or additionally be used.
- nonionic detergent active compounds include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5 to 25 EO; ie 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C 8 -C, 8 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine.
- Other so-called nonionic detergent active compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
- compositions for example mixed anionic or mixed anionic and nonionic compounds, may be used in the detergent compositions, particularly to impart thereto controlled low sudsing properties. This is beneficial for compositions intended for use in suds-intolerant automatic washing machines.
- amphoteric or zwitterionic detergent active 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 active compounds are used, especially sulphobetaines such as hexadecyl dimethyl ammoniopropane sulphonate, it is generally in small amounts in compositions based on the much more commonly used anionic and/or nonionic detergent active compositions.
- Some soap can also be present in the compositions, especially in low sudsing compositions together with mixed synthetic and nonionic detergent compounds.
- Such soaps are the sodium, or less desirably potassium, salts of C 12 ⁇ C 22 fatty acids, especially natural fatty acids derived from nut oils, such as coconut oil or palm kernel oil, or preferably tallow class fats, such as beef and mutton tallows, palm oil, lard, some vegetable butters and castor oil, or mixtures thereof.
- tallow class soaps which are soaps of predominantly C l4 -C 20 (mainly C 18 ) fatty acids of which normally at least 40% are saturated fatty acids
- soaps from nut oils which are soaps of predominantly C 10 ⁇ C 14 (mainly C 12 ) fatty acids, of which normally at least 75% are saturated fatty acids.
- the amount of soap can be varied widely from 0.5% to 20% by weight of the composition, but is normally from 1% to about 5% if present for lather control purposes. Higher amounts of soap can be used as a supplementary detergent active compound.
- compositions of the invention necessarily contain an amorphous aluminosilicate builder material, preferably present at a level of from 10% to 60% by weight, especially 12.5% to 50% by weight of the composition..
- Amorphous aluminosilicate builder materials are described in detail in GB-A-1 473 202 (HENKEL).
- amorphous aluminosilicates described therein have one significant defect, namely that they react with sodium silicate, which is an important constituent of most detergent compositions.
- the mechanism of the reaction between amorphous aluminosilicate and sodium silicate is not fully understood, but its effect is to lessen the effectiveness of the aluminosilicate as a detergent builder in that it slows down the removal of hardness ions and may also reduce the capacity of the aluminosilicate for such ions.
- an amorphous aluminosilicate which can be used in the preparation of detergent compositions, using orthodox spray-drying equipment and not requiring special techniques to prevent the interaction between the sodium silicate and amorphous sodium aluminosilicate.
- This amorphous aluminosilicate can be produced in a particle size which is such that it can be used in detergent compositions without further size reduction and, also, in a sufficiently high solids content that excessive quantities of water do not have to be removed from the aluminosilicate and, hence, from a detergent slurry composition containing the aluminosilicate, making it commercially less attractive.
- a stable slurry of the aluminosilicate can be prepared in the presence of suitable dispersing agents and size reduced aluminosilicate by grinding or milling a slurry of aluminosilicate and dispersing agent.
- the preferred amorphous hydrated sodium aluminosilicate is characterised by a chemical composition calculated on an anhydrous basis: and has, calculated on a dry basis, a calcium ion-exchange capacity greater than 100 mg CaO/g, a magnesium capacity greater than 50 mg MgO/g, an average particle size in the range 2 to 20 ⁇ m, and the ability to form a filter cake having a solids content in the range 35-50%, in a filter press with a closing pressure of 5.5 x 10- 5 Pa, which filter cake can be converted into a pumpable slurry in said solids range, and has a silicate resistance (as hereinafter defined) such that the second order rate constant k s for the calcium exchange process is greater than 0.2°H -1 min -1 and a residual water hardness after 10 minutes of less than 1.5°H and which after drying at 50°C to 80% solids has a rate constant k d (as hereinafter defined) greater than 0.42°H -1 min -1 and a residual
- the amorphous hydrated sodium aluminosilicate has a chemical composition of:
- an inert soluble salt such as sodium sulphate.
- the calcium and magnesium ion-exchange capacities are determined as follows.
- Sodium aluminosilicate (equivalent to 1.00 g anhydrous solids determined as the residue after heating to constant weight at 700°C) is added to 1 litre of 5.0 x 10- 3 M CaC1 2 solution and stirred for 15 minutes at 20°C.
- the aluminosilicate is then removed by Millipore® membrane filitration and the residual calcium concentration (Z x 10- 3 M) of the filtrate is determined by complexometric titration or atomic absorption spectrophotometry.
- the calcium exchange capacity is calculated as 56(5.0-Z) mg CaO/g aluminosilicate.
- Magnesium ion-exchange capacity is measured in a similar fashion using a 5 x 10- 3 M MgC1 2 stock solution and a pH in the range 9.5 ⁇ 10.5.
- the test is designed to simulate some of the conditions which prevail when sodium aluminosilicate is used in a detergent system.
- the response of a Radiometer calcium ion specific electrode is determined by the addition of aliquots (0-20 mls) of calcium chloride (3 x 10 -2 M) to a solution of 5 mls M NaCI in 175 mls of water at 50°C. The resulting solution is 0.025 M in Na + and 3 x 10 -3 M in Ca ++ . To this is added sufficient aluminosilicate to give 2.5 g/litre (anhydrous basis) and stirring is maintained throughout the water softening measurement. The electrode response is measured over the next 10 minutes and, using the calibration data, is calculated as Ca ++ concentration (°H) versus time. Water softening may be conveniently summarised by the hardness remaining after 1 and 10 minutes.
- the electrode test is applied to filter cake, dried powders and to the slurries produced by the silicate resistance test.
- the test may still be performed provided allowance is made when weighing samples for the ion-exchange measurement.
- the water softening kinetics involved in the determination of the rate constant k involve the use of data obtained using the calcium specific electrode as described above.
- the equilibrium hardness is determined from:
- the most effective sodium aluminosilicates for use according to this invention have a rate constant k s greater than 2 and an equilibrium calcium concentration (Ca eq ) less than 1°H after silicate treatment.
- Amorphous aluminosilicates which will yield, economically, a filter cake of relatively high solids content containing an aluminosilicate at a particle size suitable for inclusion in detergent compositions according to the invention and having the benefits of silicate resistance previously spelt out, may be prepared by a process in which aqueous sodium silicate, having a composition Na 2 0 2-4 SiO 2 and a concentration in the range 1-4 moles/litre Si0 2 ; an aqueous aluminate having a composition 1-2 Na 2 O A1 2 0 3 and a concentration in the range 0.5 to 2.0 moles/litres A1 2 0 3 , are intimately mixed together at a temperature of up to 45°C in a mixing device to produce a sodium aluminosilicate composition which is immediately subjected to high shear in a disintegrator to produce a particle size of aluminosilicate less than 20 pm and subsequently aged.
- aqueous sodium silicate having a composition Na 2 0
- aluminate and silicate solutions can conveniently be achieved using a mixer such as that described in Handbook of Chemical Engineering by Perry & Chilton, 5th Edition, Chapter 21, ref 21-4, under the heading "Jet Mixers”.
- the objective of such mixers is to ensure a rapid and intimate mixing of the two solutions.
- Suitable disintegrators for use in reducing the particle size of the sodium aluminosilicate include devices designed to impart high shear, such as the Waring (Trade Mark) blender supplied by Waring Products Division, Dynamics Corporation of America, New Hartford, Connecticut, USA, and Greaves SM (Trade Mark) mixer, as supplied by Joshua Greaves & Sons Limited, Ramsbottom, Lancashire, England.
- Waring Trade Mark
- Greaves SM Trade Mark
- Various other devices can be used but it is believed that where the shear is provided by rotation of a stirrer blade in the reaction mixture, no such device will be satisfactory unless the tip speed of the rotor exceeds 300 m/min.
- the tip speed is in the range 1000-3000 m/min.
- the processing subsequent to the high shear treatment can comprise an ageing step for the free- flowing slurry which typically extends for a period of 1-2 hours, but can be longer.
- the precipitate formation and ageing can take place in the presence of an inert salt such as sodium sulphate.
- the aged slurry can also be treated with a dilute mineral acid such as sulphuric acid to reduce its pH to about 10.0 or 11.0 prior to washing and filtering.
- compositions of the invention necessarily contain a peroxygen bleach compound, preferably at a level of between 5% and 50% by weight of the composition, especially between 8% and 32% by weight.
- Suitable peroxygen bleaches include sodium perborate (for example as the tetrahydrate) arid sodium percarbonate.
- compositions of the invention may include an alkaline salt selected from alkalimetal silicates, carbonates and phosphates.
- the amount of sodium silicate used can vary widely according to the type of composition involved, that is from a minimum of 0.1% to 50% by weight of the resultant detergent composition. Normally, however, amounts in the range of from 0.5% to 20%, especially 1% to 15%, are used for conventional purposes, that is for corrosion inhibition, pH buffer control and powder structuring properties. Amounts of sodium silicate in excess of this up to 40% are sometimes used for supplementary detergency building properties in fabric washing compositions. Still higher levels of sodium silicate can be present in other types of powdered detergent compositions, for example for dishwashing or industrial purposes in which high alkalinity is usual.
- any normal type of sodium silicate can be used, preferably with a sodium oxide to silica ratio of from 2:1 to 1:4, for example sodium alkaline silicate (Na 2 0.2Si0 2 ) sodium neutral silicate (Na 2 O.3.3SiO 2 ), sodium metasilicate (Na 2 O.SiO 2 ) or sodium orthosilicate (2Na 2 0.Si0 2 ), or mixtures thereof, the less alkaline silicates (Na 2 0.1-4Si0 2 ) being preferred.
- sodium alkaline silicate Na 2 0.2Si0 2
- sodium neutral silicate Na 2 O.3.3SiO 2
- sodium metasilicate Na 2 O.SiO 2
- sodium orthosilicate 2Na 2 0.Si0 2
- the less alkaline silicates Na 2 0.1-4Si0 2
- alkaline materials examples include sodium carbonate, sodium tripolyphosphate, sodium orthophosphate and sodium pyrophbsphate. These alkaline materials will also add to the building capacity of the compositions.
- the use of sodium pyrophosphate may lead to unacceptably high levels of inorganic deposition on the fabrics and it is therefore preferred to include less than 5% pyrophosphate in the compositions, most preferably substantially no pyrophosphates.
- the detergent compositions made according to the invention can contain any of the conventional additives in the amounts in which such additives 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, powder flow aids such as finely divided silicas and other aluminosilicates, lather depressants, antiredeposition agents such as sodium carboxymethyl-cellulose, per-acid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softening agents such as clays of the smectite and illite types, anti-ashing aids, starches, soap scum dispersants, inorganic salts such as sodium sulphate, and usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.
- slurry stabilisers such as copoly-ethylene-maleic anhydride and copolyvinylmethylether-maleic anhydride, usually in salt form.
- zeolites crystalline aluminosilicates
- the invention necessarily requires that the base powder granules be made by spray-drying.
- the slurry making and spray drying steps in the process of the present invention may be accomplished using conventional equipment for this purpose, for example in crutcher, paddle or turbo mixers and spray drying towers.
- Normal temperatures may be used for these operations, for example from 30°C to 100°C, preferably 70°C to 90°C for the slurry making and 200°C to 450°C for the drying gas inlet in the spray drying process, with higher temperatures within this range being generally preferred for economic reasons.
- the base powder necessarily contains the detergent surfactant and the amorphous aluminosilicate.
- the peroxybleach, together with any other heat sensitive ingredients may be subsequently mixed with the base powder granules.
- the alkaline salt if present, may be included in the granules, mixed therewith subsequently or both. Where sodium silicate is the alkaline salt, it may be advantageous to add it subsequently to further reduce the risk of interaction with the sodium aluminosilicate in the slurry. It is preferred that any subsequently added materials be in their fully hydrated forms.
- the filter cake was processed so as to produce a stable, pumpable aqueous suspension by incorporating a suitable dispersing agent and reducing the particle size of the aluminosilicate to between 4.0 and 6.0 micrometers by milling or grinding the aluminosilicate in an aqueous medium containing the said dispersing agent, all in accordance with the teaching of British Patent Specification No 1 051 336 (MOBIL OIL CORPORATION).
- the filter cake, or the suspension as prepared above can be converted into dry powder form by a variety of drying techniques.
- the residual moisture content (loss of ignition) of the aluminosilicate is not less than 20% by weight.
- Filter cakes can be conveniently dried in an oven at a temperature of 50°C for the purpose of testing the preservation of the ion exchange properties and the determination of the k d value.
- the mixer used was a Greaves SM mixer, having a high speed impeller rotating at 3000 rpm with a tip speed of 1975 m/min.
- Intense stirring is required to (a) prevent gelation which would lead to low solids content filter cakes and (b) control the particle size of the aluminosilicate.
- a Waring blender (Model CB 6 "1 gallon (4.5 dm 3 ) capacity") having a high speed impeller, 13000.rpm, producing a tip speed of 2800 m/min may be used.
- Ion exchange performance - Ca electrode method (°HCa)
- particulate detergent compositions were prepared by spray-drying a base powder and adding thereto a number of post-dosed ingredients.
- the base powders had the following formulations, in parts by weight expressed as anhydrous material.
- the ion exchange properties of these powders after storage was determined by washing the powders with de-ionised water on a filter cake to extract the insoluble aluminosilicate material and drying. 0.5 g of the dried material was then added to 200 ml of water having a hardness of 30°FH (equivalent to a calcium ion concentration of 3 x 10- 3 molar). The free calcium ion concentration was measured after 1 minute.
- the powders were stored for 6 weeks at 37°C and 70% relative humidity (Examples 4, 4A and 4B) or for 12 weeks at 28°C and 70% relative humidity (Examples 1, 2, 2A, 3 and 3A). In the same manner, the ion exchange properties of the base powders were measured immediately after spray drying. The results were as follows:
- Example 1 to 4 The powders of Examples 1 to 4 were stored under various conditions after which the percentage of perborate which had decomposed was measured. Similar powders were produced in which the amorphous aluminosilicate was replaced by Zeolite-4A, of similar particle size, to provide control Examples. With the zeolite containing powders the moisture content was lower, namely between about 4.5% and 8% of the base powders. Moisture contents identical to Examples 1 to 4 lead to poor powder properties and even more perborate decomposition on storage. The results were as follows:
- Example 5 and 6 After storage at 37°C and 70% relative humidity for 4 weeks, 39% and 28% of the sodium perborate in Example 5 and 6 respectively had decomposed.
- zeolite 4A of similar particle size
- a base powder was spray dried having a composition identical to Example 4, but in which no sodium silicate was included.
- the water level was 9.7 parts and the total base powder weight was 53.4 parts.
- the moisture content was 7.1 parts (13.3%), giving a value of y equal to 0.42.
- a number of detergent compositions was prepared by spray-drying an aqueous slurry containing the following ingredients: This slurry was spray-dried to give detergent base powders of the following moisture contents:
- Example B The powders of Examples B and 10 were stored for 12 weeks at 28°C and 70% relative humidity. After this storage the ion-exchange rate was again measured. In the case of Example B the time taken to reach 3.3°FH was greater than 10 minutes and in the case of Example 10, 0.9 minutes.
- Example 10 shows improved bleach stability over the comparison compositioon, Example B.
- Example B approximates to that disclosed in Example 1 of British Patent Specification GB 2 013 707.
- the detergent actives used in the foregoing examples were approximately:
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Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT84308962T ATE52537T1 (de) | 1983-12-21 | 1984-12-20 | Reinigungsmittelzusammensetzungen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB8334017 | 1983-12-21 | ||
GB838334017A GB8334017D0 (en) | 1983-12-21 | 1983-12-21 | Detergent composition |
Publications (3)
Publication Number | Publication Date |
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EP0150613A2 EP0150613A2 (de) | 1985-08-07 |
EP0150613A3 EP0150613A3 (en) | 1987-08-05 |
EP0150613B1 true EP0150613B1 (de) | 1990-05-09 |
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ID=10553626
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Application Number | Title | Priority Date | Filing Date |
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EP84308962A Expired - Lifetime EP0150613B1 (de) | 1983-12-21 | 1984-12-20 | Reinigungsmittelzusammensetzungen |
Country Status (10)
Country | Link |
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EP (1) | EP0150613B1 (de) |
JP (1) | JPS60155296A (de) |
AT (1) | ATE52537T1 (de) |
AU (1) | AU560739B2 (de) |
CA (1) | CA1227100A (de) |
DE (1) | DE3482190D1 (de) |
ES (1) | ES8608037A1 (de) |
GB (1) | GB8334017D0 (de) |
NO (1) | NO163140C (de) |
ZA (1) | ZA849950B (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8525269D0 (en) * | 1985-10-14 | 1985-11-20 | Unilever Plc | Detergent composition |
GB8603667D0 (en) * | 1986-02-14 | 1986-03-19 | Unilever Plc | Detergent composition |
GB8810193D0 (en) * | 1988-04-29 | 1988-06-02 | Unilever Plc | Detergent compositions & process for preparing them |
GB9008013D0 (en) * | 1990-04-09 | 1990-06-06 | Unilever Plc | High bulk density granular detergent compositions and process for preparing them |
DD295186B5 (de) * | 1990-06-13 | 1994-01-27 | Leuna Werke Ag | Reinigungsmittelkomposition und verfahren zur herstellung |
DE4031910A1 (de) * | 1990-10-08 | 1992-04-09 | Henkel Kgaa | Percarbonathaltiges waschmittel |
DE4106880A1 (de) * | 1991-03-05 | 1992-09-10 | Henkel Kgaa | Waschmittel |
GB9112384D0 (en) * | 1991-06-10 | 1991-07-31 | Unilever Plc | Detergent compositions |
FR2691715A1 (fr) * | 1992-05-26 | 1993-12-03 | Rhone Poulenc Chimie | Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques. |
JP4385981B2 (ja) | 2005-03-30 | 2009-12-16 | オンキヨー株式会社 | 動電型スピーカー |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2013707A (en) * | 1978-02-01 | 1979-08-15 | Unilever Ltd | Preparation of Spray-Dryed Detergent Compositions |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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DK151231C (da) * | 1973-04-13 | 1988-07-04 | Henkel Kgaa | Fremgangsmaade til rensning, herunder vask, forvask og blegende vask, affaste materialer, isaer tekstiler, samt middel til udoevelse af fremgangsmaaden og fremgamgsmaade til fremstiling af midlet |
JPS5416521B2 (de) * | 1973-07-05 | 1979-06-22 | ||
DE2433485A1 (de) * | 1973-07-16 | 1975-02-06 | Procter & Gamble | Zur verwendung in waschmitteln geeignete aluminosilikat-ionenaustauscher |
US4180485A (en) * | 1977-11-02 | 1979-12-25 | The Procter & Gamble Company | Spray-dried detergent compositions |
BE874420A (fr) * | 1978-03-02 | 1979-08-23 | Unilever Nv | Procede de production de compositions detergentes |
FI822428L (fi) * | 1981-07-15 | 1983-01-16 | Unilever Nv | Rengoeringsblandning |
JPS5821497A (ja) * | 1981-07-31 | 1983-02-08 | ライオン株式会社 | 嵩密度の小さい洗剤用添加物の製造法 |
US4539131B1 (en) * | 1982-06-25 | 1990-09-04 | Lever Brothers Ltd | Solid detergent composition containing sodium perborate monohydrate having specified surface area |
-
1983
- 1983-12-21 GB GB838334017A patent/GB8334017D0/en active Pending
-
1984
- 1984-12-17 CA CA000470346A patent/CA1227100A/en not_active Expired
- 1984-12-18 AU AU36889/84A patent/AU560739B2/en not_active Ceased
- 1984-12-18 ES ES538769A patent/ES8608037A1/es not_active Expired
- 1984-12-19 NO NO845109A patent/NO163140C/no unknown
- 1984-12-20 AT AT84308962T patent/ATE52537T1/de not_active IP Right Cessation
- 1984-12-20 ZA ZA849950A patent/ZA849950B/xx unknown
- 1984-12-20 EP EP84308962A patent/EP0150613B1/de not_active Expired - Lifetime
- 1984-12-20 DE DE8484308962T patent/DE3482190D1/de not_active Expired - Fee Related
- 1984-12-20 JP JP59269614A patent/JPS60155296A/ja active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2013707A (en) * | 1978-02-01 | 1979-08-15 | Unilever Ltd | Preparation of Spray-Dryed Detergent Compositions |
Also Published As
Publication number | Publication date |
---|---|
ZA849950B (en) | 1986-08-27 |
EP0150613A3 (en) | 1987-08-05 |
NO163140B (no) | 1990-01-02 |
ATE52537T1 (de) | 1990-05-15 |
ES538769A0 (es) | 1986-06-01 |
EP0150613A2 (de) | 1985-08-07 |
AU3688984A (en) | 1985-07-04 |
CA1227100A (en) | 1987-09-22 |
NO845109L (no) | 1985-06-24 |
ES8608037A1 (es) | 1986-06-01 |
JPS60155296A (ja) | 1985-08-15 |
NO163140C (no) | 1990-04-11 |
JPH0457718B2 (de) | 1992-09-14 |
AU560739B2 (en) | 1987-04-16 |
GB8334017D0 (en) | 1984-02-01 |
DE3482190D1 (de) | 1990-06-13 |
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