EP0022998B1 - Procédé de préparation d'un produit de lavage à faible pouvoir moussant - Google Patents
Procédé de préparation d'un produit de lavage à faible pouvoir moussant Download PDFInfo
- Publication number
- EP0022998B1 EP0022998B1 EP80104033A EP80104033A EP0022998B1 EP 0022998 B1 EP0022998 B1 EP 0022998B1 EP 80104033 A EP80104033 A EP 80104033A EP 80104033 A EP80104033 A EP 80104033A EP 0022998 B1 EP0022998 B1 EP 0022998B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- spray
- polysiloxane
- sodium
- anhydrous
- 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
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000005406 washing Methods 0.000 title description 15
- 238000005187 foaming Methods 0.000 title description 3
- -1 polysiloxane Polymers 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 239000003599 detergent Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000013530 defoamer Substances 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 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 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000007844 bleaching agent Substances 0.000 claims abstract description 7
- 150000004760 silicates Chemical class 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 6
- 239000004482 other powder Substances 0.000 claims abstract description 6
- 235000021317 phosphate Nutrition 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 5
- 239000002156 adsorbate Substances 0.000 claims abstract description 4
- 239000007900 aqueous suspension Substances 0.000 claims abstract 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000011833 salt mixture Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004687 hexahydrates Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000007046 ethoxylation reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical group CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 240000003834 Triticum spelta Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001414 amino alcohols Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 2
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- MOOUTZQHJHBHLT-UHFFFAOYSA-N 1-[2-[2-(1h-benzimidazol-2-yl)ethenyl]-1h-benzimidazol-4-yl]ethanol Chemical group C1=CC=C2NC(C=CC3=NC=4C=CC=C(C=4N3)C(O)C)=NC2=C1 MOOUTZQHJHBHLT-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- XBIPWOJKRZBTQK-UHFFFAOYSA-N 2-methylidenebut-3-enamide Chemical compound NC(=O)C(=C)C=C XBIPWOJKRZBTQK-UHFFFAOYSA-N 0.000 description 1
- QWZHDKGQKYEBKK-UHFFFAOYSA-N 3-aminochromen-2-one Chemical class C1=CC=C2OC(=O)C(N)=CC2=C1 QWZHDKGQKYEBKK-UHFFFAOYSA-N 0.000 description 1
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical class CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- GZEYLLPOQRZUDF-UHFFFAOYSA-N 7-(dimethylamino)-4-methylchromen-2-one Chemical group CC1=CC(=O)OC2=CC(N(C)C)=CC=C21 GZEYLLPOQRZUDF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
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- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
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- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 1
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 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
- 238000004090 dissolution Methods 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical group COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Chemical class 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Definitions
- the undesirable strong foaming of detergents can be suppressed by adding foam-suppressing mixtures of polydimethylsiloxane and finely divided silica. It is also known that the state of distribution of the siloxanes in the detergent plays an important role in the effectiveness. If the siloxanes are added to the slurry prior to spray drying, this results in a homogeneous distribution state in which the washing capacity is not impaired, but at the same time the foam-suppressing effect partially decreases.
- DE-B-23 38 468 describes a detergent in which the polysiloxane / silica mixture is incorporated into a carrier substance which is impenetrable to detergents.
- the purpose of this measure is to prevent an interaction between the detergents contained in the detergent and the polysiloxane and thus to prevent a drop in activity during mixing and storage.
- the polysiloxane-silica mixture is adsorbed on a solid carrier consisting of sodium carbonate, silicate, tripolyphosphate, clay, diatomaceous earth or fuller's earth or starch, polyglycols, highly ethoxylated fatty alcohols, gelatin or other gel-forming materials.
- the granular adsorbates are produced by spray drying, spray cooling or fluidizing liquid or molten mixtures of polysiloxane foam damper and carrier material.
- the prefabricated grains or prills are then coated with an upper coating material, which can consist of the compounds used as the carrier material.
- the coating is intended to counteract the sticking of the grains and to prevent interactions with other detergent components, in particular surfactants.
- the patent application advises against a method of production in which the polysiloxane component is sprayed onto a granular carrier, for example sodium tripolyphosphate, and incorporated into the detergent in this form, since this results in an unfavorable foam profile.
- the present invention is suitable for eliminating the disadvantages described.
- the invention relates to a process for producing a foam-damped detergent, consisting of several powdery to granular components, one of the powder components consisting of a polysiloxane defoamer adsorbed on a carrier substance and the other powder components consisting of spray-dried or granulated detergents of conventional composition and, if appropriate, bleaching agents , characterized in that for the preparation of the powder component containing the polysiloxane defoamer, a 40 to 75 percent by weight (calculated as an anhydrous compound) of at least one compound from the class of polymer phosphates, silicates, carbonates and sulfates of sodium-containing aqueous slurry which is free of surfactants is and does not contain more than 0.3 percent, based on anhydrous salt, of polysiloxane defoamers, spray-dried using 120 ° to 300 ° C hot gases in a manner known per se, and so
- Salt mixtures which contain at least two of the aforementioned salts are preferably used.
- Such salt mixtures are sprayed from an aqueous slurry containing 50 to 70 percent by weight of anhydrous salt.
- the spraying can take place in conventional spray drying systems, for example in so-called spray towers, in which the slurry is sprayed by means of nozzles and dried with the aid of gases heated in cocurrent or preferably countercurrent, in particular air or combustion gases mixed with air.
- the inlet temperature of the dry air is 120 ° to 300 ° C, preferably 150 ° to 250 ° C, the outlet temperature is generally 75 ° to 95 ° C.
- Salt mixtures have proven to be particularly suitable, the proportion of sodium silicate of which is 3 to 75 percent by weight, in particular 5 to 15 percent by weight, based on anhydrous salt. Such salt mixtures result in a particularly abrasion-resistant and at the same time readily soluble granular carrier substance.
- sodium silicate used in the aforementioned weight ratios has a ratio of 1: 1.
- a further improvement in the grain structure is achieved if a salt mixture is used which, in addition to the aforementioned sodium silicate, also contains sodium tripolyphosphate and sodium sulfate in a weight ratio of 10: 1 to 1:10, in particular 5: 1 to 1: 5, based on anhydrous sodium tripolyphosphate and anhydrous sodium sulfate.
- the sodium tripolyphosphate is used - regardless of the calculated relationship - preferably as hexahydrate.
- the carrier substance preferably has the following composition (calculated as anhydrous salt)
- Carrier substances with a high tripolyphosphate content have a higher water content (10-20%), those with a high sodium sulfate have a lower water content (5-8%).
- the water content is about 8-12 percent.
- up to 0.3% by weight, preferably 0.05 to 0.2% by weight, of the mixture of polysiloxane and silica can be added to the aqueous slurry, based on anhydrous salts.
- this portion added before spraying loses a certain part of its foam-suppressing effect, as stated at the beginning, this loss can be accepted, since it affects only a small percentage of the total polysiloxane defoamer to be used.
- this additive significantly improves the sprayability of the concentrates, the grain structure of the carrier grains in the sense of an improved absorption capacity for polysiloxanes, and in particular the wettability of the powder component loaded with further polysiloxane defoamer when used later in the washing bath. If instead, as suggested in the previous literature, the entire amount of the polysiloxane-silica mixture is incorporated into the concentrate and sprayed with it, the wettability in the washing bath deteriorates and residue formation can result from undissolved particles. In addition, the foam-suppressing effect is reduced overall.
- the carrier should be free of surfactants because surfactants also weaken the foam-suppressing effect. In addition, it should be free of water-insoluble or sparingly soluble compounds, such as the clays, diatomaceous earth, fuller's earth and cellulose recommended in the previous literature, since these substances also lead to a loss of activity, which may be due to a partial separation of the polysiloxane from the silica.
- the carrier substance produced in the manner indicated is of a granular nature and has a particle size range from 0.05 to 2.5 mm, preferably from 0.1 to 1.6 mm with an average particle size of 0.2 to 0.8 mm. It is characterized by a good absorption capacity for the polysiloxane-silica component on the one hand and for a quick and complete dissolution in the wash bath even at low wash bath temperatures.
- the granular carrier substance is mixed with conventional polysiloxane-silica mixtures, the weight ratio of carrier substance (calculated as anhydrous salt) to polysiloxane-silica mixture 50: 1 to 6: 1, preferably 25: 1 to 8: Is 1.
- Suitable polysiloxanes are conventional compounds such as dimethyl, diethyl, dipropyl, dibutyl, methylethyl, methylphenyl, methylcyclohexyl and hydroxyalkyl polysiloxanes.
- Crosslinked polysiloxanes are also suitable.
- the polysiloxanes are used in a mixture with finely divided silica, for example Aerosil, it also being possible to use silanized silica which can be obtained by reacting silica containing hydroxyl groups with chlorosilanes.
- the weight ratio of polysiloxane to silica is 50: 1 to 5: 1, preferably 25: 1 to 7: 1.
- the carrier substance (hereinafter called powder component A) loaded with the polysiloxane / silica mixture has a bulk density of 450 to 700, preferably 500 to 650 g / l. It is of the same order of magnitude as the bulk density of spray-dried detergent powder, which is why the powder mixtures cannot separate during transport and storage.
- the powder component A is mixed with further powdery to granular detergent components in a manner known per se, the proportions being such that - depending on the strength of the desired effect - 0.01 to 0.5, preferably 0.05 to 0.2 percent by weight Polysiloxane-silica mixture contained in the detergent.
- the detergent component (hereinafter called powder component B) containing surfactants and skeletal salts should have a grain size of 0.05 to 2.5 mm, preferably 0.1 to 1.6 mm. It contains at least one anionic, nonionic or zwitterionic surfactant, skeletal salts and other non-bleaching detergent components, which include washing alkalis, graying inhibitors, optical brighteners, stabilizers, neutral salts and dyes, but not per compounds or bleaches containing active chlorine, bleach activators and enzymes that spray under the conditions of a hot spray are not stable.
- Anionic surfactants suitable for the preparation of component (B) are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkylsulfonates and ⁇ -sulfofatty acid esters, primary alkyl sulfates and the sulfates of ethoxylated, 2 to 3 glycol ether groups having higher molecular weight alcohols.
- Alkaline soaps of fatty acids of natural or synthetic origin are also suitable, for example the sodium soaps of coconut, palm kernel or tallow fatty acids.
- the anionic surfactants are preferably in the form of the sodium salts.
- anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22, preferably 12 to 18, carbon atoms.
- the preferably unbranched alkyl chains contain 6 to 16, in particular 10 to 14, carbon atoms.
- Suitable nonionic surfactants are, in particular, ethoxylation products of saturated or monounsaturated aliphatic primary alcohols having 12 to 24, preferably 12 to 18 carbon atoms and 3 to 20, in particular 4 to 15, ethylene glycol ether groups.
- Suitable alcohols from which the present ethoxylation products are derived are, for example, those of natural origin, such as coconut oil or tallow fatty alcohols or oleyl alcohol, furthermore oxo alcohols or synthetic alcohols obtained by ethylene polymerization.
- nonionic surfactants are ethoxylation products of secondary alcohols, vicinal diols and amino alcohols each having 12 to 18 carbon atoms and alkylphenols with 6 to 12 carbon atoms in the alkyl radical, the number of glycol ether groups also being 3 to 20, preferably 4 to 15.
- the abovementioned ethoxylated alcohols, amino alcohols and alkylphenols can also be replaced in whole or in part by those which are prepared with 0.5 to 3 moles of propylene oxide per mole of starting compound and only in the second stage the envisaged amount of ethylene oxide is added.
- nonionic surfactants can also be present which are derived from the abovementioned compounds and which have ethylene glycol and propylene glycol ether groups in a different order, for example alcohols with 10 to 30 ethylene glycol ether groups and 3 to 30 propylene glycol ether groups; also ethoxylation products of mercaptans, fatty acid amides and fatty acids.
- the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain can also be used.
- the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
- Nonionic compounds of the amine oxide and sulfoxide type which can optionally also be ethoxylated, can also be used.
- Suitable builder substances are the polymer phosphates, carbonates, silicates and sulfates of potassium and in particular of sodium, the silicates having a ratio of SiO 2 to Na 2 O of 1: 1 to 3.5: 1.
- the pentasodium triphosphate is suitable as the polymer phosphate, which can be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates.
- aluminosilicates generally have a grain size of 0.1 to 20 11 m and are preferably crystalline.
- the skeletal salts also include salts of complexing aminopolycarboxylic acids, in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
- the higher homologues of the aminopolycarboxylic acids mentioned are also suitable.
- Salts of nitrogen-free polycarboxylic acids which form complex salts with calcium ions, including polymers containing carboxyl groups, are also suitable. Examples are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid.
- Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and polyhydric alcohols partially or completely etherified with glycolic acid or hydroxycarboxylic acids, for example triscarboxymethylglycerol, biscarboxymethylglyceric acid, carboxymethyloxysuccinic acid and carboxymethylaccharated or oxidized polysaccharide.
- the polymeric carboxylic acids with a molecular weight of at least 350 are suitable in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.
- the water-soluble sodium or potassium salts such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene,
- complexing polyphosphonic acid salts may be present, e.g. the alkali metal salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, phenylhydroxymethane diphosphonic acid, methylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned.
- aminopolyphosphonic acids in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, phenylhydroxymethane diphosphonic acid, methylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned.
- component (B) includes washing alkalis, neutral salts, graying inhibitors, optical brighteners, stabilizers such as magnesium silicate, substances which have an aerating effect and dyes, and further additives which improve the sprayability, e.g. Alkali salts of toluene, xylene or cumene sulfonic acid.
- Suitable washing alkalis are alkali carbonates, bicarbonates, borates and silicates with a Na 2 0: Si0 2 ratio of 1: 1 to 1: 3.5.
- Sodium sulfate and sodium chloride are suitable as neutral salts.
- Suitable graying inhibitors are, in particular, carboxymethyl cellulose and cellulose mixed ethers which have varying amounts of carboxymethyl, methyl and / or hydroxyethyl, hydroxypropyl and hydroxybutyl groups, in particular methyl hydroxypropyl cellulose and methyl hydroxybutyl cellulose, furthermore colloidally water-soluble polymers or copolymers of vinyl alcohol and vinyl alcohol and vinyl alcohol, vinyl acrylamide, vinyl alcohol Acrylonitrile.
- Suitable optical brighteners are the alkali salts of 4,4-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group or a .beta.-methoxyethylamino group instead of the morpholino group.
- Further possible brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (p-sulfonamidophenyl) -3- (p-chlorophenyl) -A ' -pyrazoline and compounds of the same structure which carry a carboxymethyl or acetylamino group instead of the sulfonamido group.
- Substituted aminocoumarins for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin, can also be used.
- the compounds are also polyamide brighteners 1- (2-Benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl can be used.
- the compounds 2.5 are brighteners for polyester and polyamide fibers -Di- (2-benzoxaz olyl) thiophene, 2- (2-benzoxazolyl) naphto [2,3-b] thiophene and 1,2-di (5-methyl-2-benzoxyzolyl) ethylene are suitable.
- Brighteners of the substituted diphenylstyryl type may also be present. Mixtures of the aforementioned brighteners can also be used.
- Any further powder component (C) which is present preferably contains a per compound, for example sodium percarbonate, but in particular sodium perborate tetrahydrate.
- Additional powder components may also be present, which may contain enzymes or bleach activators, for example.
- the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.
- the powder component (B) is advantageously produced by spray drying in a known manner from an aqueous slurry.
- Such spray powders usually have a liter weight of 300 to 600 g and, after mixing with the component (A) produced by spraying, do not tend to separate during filling and during transport. If necessary, component (B) can also be prepared by known granulation processes.
- the various powder components are combined by mixing in conventional mixing devices, which preferably operate continuously or on the free-fall principle. Before or during the mixing process, further constituents, for example fragrances, can also be introduced or sprayed onto one of the powder components or the powder mixture. Finally, one of the powder components (B) or (C), but especially the sodium perbo rat (component C) - as described in DE-A-27 48 970 and 27 53 680 - with nonionic surfactants to improve the washing behavior of the washing powder.
- the spray products according to Examples 4, 5 and in particular 6 show very favorable grain spectra. Grain fractions over 1.6 mm in diameter were sieved out before further processing.
- the spray products (temperature 20 ° C.) were mixed in a drum mixer with step by step with a homogeneous mixture of 6 parts by weight of polydimethylsiloxane and 1 part by weight of silanized silica heated to 50 ° C.
- the viscosity of the polysiloxane-silica mixture was 1300 cP at 20 ° C and 750 cP at 50 ° C.
- examples 1, 2, 4 and 5, 5 parts by weight of polysiloxane-silica mixture per 95 parts by weight of carrier were used. In Example 3 this ratio was 10 to 90 and in Example 6 (spray product containing 0.2 percent by weight polysiloxane) 4.8 to 95.2 parts by weight.
- the polysiloxane / silica mixture was completely absorbed by the carrier substance.
- the impregnated granules proved to be dry, pourable, non-sticky and non-greasy.
- the literge the weight of the granules was between 560 and 590 g / l.
- composition of the spray-dried detergent (component B) was (in percent by weight):
- the powder components (A) and (B) were mixed with the addition of sodium perborate tetrahydrate (component C) in the mixing ratios given in Table 2.
- the foam behavior was tested after 10 days of storage of the mixture in a commercial washing machine with a horizontally arranged drum at temperatures of 30 °, 60 ° and 95 ° C. For this purpose, the machine was loaded with 3.5 kg of clean laundry (cotton).
- the detergent concentration was 7.5 g and the water hardness was 16 ° dH.
- the respective foam height was checked through the sight glass of the front door and graded as follows:
- 5 wt .-% polydimethylsiloxane were mixed according to the procedure according to DE-A-23 38 468, Example 1 with 5 wt .-% silica and 40 wt .-% of an ethoxylated tallow alcohol (25 EO) at 50 ° C and a fluidized Sprayed bed of 50 wt .-% sodium sulfate.
- Comparative experiment V was repeated with the modification that instead of the sodium sulfate a crystalline powdered sodium aluminum silicate of the composition 0.9 Na 2 0.Al 2 O 3 .2 Si0 2 .3 H 2 0 was used, the particle size of which was 1-15 ⁇ m.
- the solution behavior of the siloxane-containing powder component was determined as follows.
- a beaker volume 500 cm 3
- 200 ml of a solution of 1 g of sodium dodecylbenzenesulfonate in 1 liter of water at a temperature of 22 ° C are mixed with a motorized stirrer equipped with 4 stirring blades that are bent downwards at an angle of 30 ° a constant number of revolutions of 700 rpm. stirred.
- the distance between the agitator blades and the bottom of the vessel is 2.5 cm.
- 1 g of the sample is carefully poured into the stirring cone, avoiding lumps.
- the solution is poured through a tared sieve with a mesh size of 0.1 mm and a diameter of 7 cm and sucked off using a suction bottle. Remnants of substance remaining in the beaker are transferred onto the sieve using as little water as possible.
- the sieve is weighed back in air after a drying time of 24 hours. The results of 10 experiments are averaged.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80104033T ATE1911T1 (de) | 1979-07-20 | 1980-07-12 | Verfahren zur herstellung eines schaumgedaempften waschmittels. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19792929359 DE2929359A1 (de) | 1979-07-20 | 1979-07-20 | Verfahren zur herstellung eines schaumgedaempften waschmittels |
DE2929359 | 1979-07-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0022998A1 EP0022998A1 (fr) | 1981-01-28 |
EP0022998B1 true EP0022998B1 (fr) | 1982-12-01 |
Family
ID=6076230
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80104033A Expired EP0022998B1 (fr) | 1979-07-20 | 1980-07-12 | Procédé de préparation d'un produit de lavage à faible pouvoir moussant |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0022998B1 (fr) |
AT (1) | ATE1911T1 (fr) |
DE (2) | DE2929359A1 (fr) |
DK (1) | DK154828C (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3128631A1 (de) * | 1981-07-20 | 1983-02-03 | Henkel Kgaa | "verfahren zur herstellung eines schaumgedaempften, silikone enthaltenden waschmittels" |
GB8619634D0 (en) * | 1986-08-12 | 1986-09-24 | Unilever Plc | Antifoam ingredient |
DE4113783C1 (fr) * | 1991-04-26 | 1992-11-19 | Rudolf Gmbh & Co Kg Chemische Fabrik, 8192 Geretsried, De | |
GB9410677D0 (en) | 1994-05-27 | 1994-07-13 | Unilever Plc | Detergent compositions |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1407997A (en) * | 1972-08-01 | 1975-10-01 | Procter & Gamble | Controlled sudsing detergent compositions |
SE427757B (sv) * | 1975-10-14 | 1983-05-02 | Procter & Gamble | Fast rengorande komposition och sett att framstella denna samt medel for framstellningen bestaende av alkoxylerad nonjontensid och sjelvemulgerad silikonskumdempare |
US4136045A (en) * | 1976-10-12 | 1979-01-23 | The Procter & Gamble Company | Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents |
DE2748970C2 (de) * | 1977-11-02 | 1979-12-20 | Henkel Kgaa, 4000 Duesseldorf | Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften |
DE2753680C2 (de) * | 1977-12-02 | 1986-06-26 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften |
CH636123A5 (de) * | 1978-06-07 | 1983-05-13 | Ciba Geigy Ag | Verfahren zur herstellung schaumregulierter waschmittel. |
-
1979
- 1979-07-20 DE DE19792929359 patent/DE2929359A1/de not_active Withdrawn
-
1980
- 1980-06-23 DK DK267280A patent/DK154828C/da not_active IP Right Cessation
- 1980-07-12 EP EP80104033A patent/EP0022998B1/fr not_active Expired
- 1980-07-12 DE DE8080104033T patent/DE3061216D1/de not_active Expired
- 1980-07-12 AT AT80104033T patent/ATE1911T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DK154828B (da) | 1988-12-27 |
EP0022998A1 (fr) | 1981-01-28 |
DE2929359A1 (de) | 1981-02-12 |
ATE1911T1 (de) | 1982-12-15 |
DE3061216D1 (en) | 1983-01-05 |
DK154828C (da) | 1989-05-16 |
DK267280A (da) | 1981-01-21 |
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