EP0642573B1 - Powdery surfactants mixture - Google Patents
Powdery surfactants mixture Download PDFInfo
- Publication number
- EP0642573B1 EP0642573B1 EP93909976A EP93909976A EP0642573B1 EP 0642573 B1 EP0642573 B1 EP 0642573B1 EP 93909976 A EP93909976 A EP 93909976A EP 93909976 A EP93909976 A EP 93909976A EP 0642573 B1 EP0642573 B1 EP 0642573B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- alkyl
- alkali metal
- formula
- mixture
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 6
- -1 alkyl benzenesulfonates Chemical class 0.000 claims description 45
- 229930182470 glycoside Natural products 0.000 claims description 36
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 27
- 239000012876 carrier material Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000003599 detergent Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 230000009969 flowable effect Effects 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 2
- 229930182478 glucoside Natural products 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 15
- 239000012459 cleaning agent Substances 0.000 abstract description 11
- 239000004615 ingredient Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract 2
- 150000004996 alkyl benzenes Chemical class 0.000 abstract 1
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 239000008011 inorganic excipient Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000002269 spontaneous effect Effects 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000004435 Oxo alcohol Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 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 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- ZTGKHKPZSMMHNM-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1S(O)(=O)=O ZTGKHKPZSMMHNM-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- WQZGKKKJIJFFOK-VSOAQEOCSA-N L-altropyranose Chemical compound OC[C@@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-VSOAQEOCSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Polymers 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000003857 carboxamides Chemical group 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002951 idosyl group Chemical class C1([C@@H](O)[C@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the invention relates to powdery, pourable and free-flowing surfactant mixtures which contain alkyl sulfate, alkyl glycoside and inorganic carrier material, a process for their preparation and their use as premixes (compounds) for the production of particulate detergents and cleaning agents.
- a process for the production of particulate detergents by drying a 40 to 80 percent aqueous slurry is known, which, based on the resulting solid, 2 to 60 wt .-% surfactants, which are at least 0.1 wt. % consist of alkyl glycosides, the total amount of alkyl glycosides being at most 2% by weight, containing 5 to 70% by weight of builder substances and up to 40% by weight of water-soluble fillers.
- Preferred surfactants are anionic surfactants, especially those of the alkylbenzenesulfonate type, and nonionic surfactants, especially ethoxylated fatty alcohols.
- the removal of water from the slurry is preferably accomplished by spray drying.
- Modern powder detergents or cleaning agents generally consist of several separately manufactured powder components, which, depending on the nature of their ingredients, require different manufacturing processes.
- a preferred manufacturing process for the surfactant-containing component of such agents is because of its relative simplicity spray drying an aqueous solution or slurry of the ingredients.
- such a process requires a thermal load capacity of the surface-active ingredients, which is ensured when using anionic surfactants customary to date, in particular from the class of alkylbenzenesulfonates.
- alkylbenzenesulfonate in washing and cleaning agents has recently been increasingly questioned because of the petroleum base of this surfactant.
- sulfation products of compounds accessible from renewable raw materials, in particular fatty alcohols come into consideration as more environmentally compatible anionic surfactants with comparable good cleaning properties.
- aqueous slurries containing alkylbenzenesulfonate can be spray-dried without problems at the temperatures customary in such processes, normally from about 250 ° C. to 350 ° C., it has now been found that under these conditions the danger exists with aqueous slurries which contain the same amount of alkyl sulfates self-ignition exists.
- nonionic surfactants include, in particular, alkyl glycosides with long-chain alkyl groups, which have recently been used with preference because of their advantageous properties.
- alkyl glycosides are normally obtained as highly viscous pastes, which means that their use in relatively high concentrations in aqueous slurries intended for spray drying did not appear to be promising because of the high mechanical stress in such a process.
- alkyl sulfate, alkyl glycoside and inorganic carrier material which consists of at least 10% by weight of alkali silicate with a molar ratio of SiO 2 to alkali oxide above 2, which in a process for the production of alkylbenzenesulfonate-free powdered surfactant mixtures by drying while avoiding the problems mentioned and leading to storage-stable, pourable and free-flowing powder products which are known as premixes Compounds that can be used for the production of particulate detergents and cleaning agents.
- the process according to the invention for the preparation of powdered surfactant mixtures free of alkylbenzenesulfonate essentially consists in that 10 to 40 parts by weight of alkylglycoside of the formula I R 1 -O (G) n (I) in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, 5 to 20 parts by weight of alkyl sulfate of the formula II, R 2 -OSO 3 X (II) in which R 2 is an alkyl radical having 10 to 20 C atoms and X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion, the weight ratio of alkyl glycoside to alkyl sulfate being 5: 1 to 1: 2, preferably 3: 1 is up to 1: 1, and 40 to 80 parts by weight of an inorganic carrier material, which consists of at least 10 wt
- the water content in the powder product is not more than 15% by weight, in particular from 5% by weight to 15% by weight.
- the residual water content relates to the free water not bound in the crystal lattice.
- Flowable and pumpable in the context of the present invention are those aqueous slurries which can be handled without problems at temperatures below 80 ° C. by means of pumps and pipelines which are customarily used in spray drying processes.
- Those used in the process according to the invention Slurries therefore preferably have viscosities in the range from 3,000 mPas to 15,000 mPas, measured at 60 ° C. to 75 ° C. using conventional viscometers, for example a Brookfield viscometer with spindle No. 3 at 20 revolutions per minute.
- the process according to the invention is preferably carried out in such a way that 20 to 30 parts by weight of alkyl glycoside according to formula I, 8 to 15 parts by weight of alkyl sulfate according to formula II and 48 to 68 parts by weight of the inorganic carrier material are mixed with so much water that at least 35% by weight, in particular, a mixture containing 40% by weight to 50% by weight of water is formed.
- spray towers in the upper part of which the slurry is sprayed into fine droplets by pressure nozzles, which move under the action of gravity into the lower part of the spray tower and come into contact with hot drying gases which are guided in cocurrent or preferably in countercurrent to the particles to be dried.
- hot drying gases which are guided in cocurrent or preferably in countercurrent to the particles to be dried.
- the temperature of the drying gases is not so high that the temperature of the spray-dried particles rises above the self-ignition temperature of these particles. In the context of the invention, this means that the temperature of the drying gases does not exceed a value of 250 ° C. and preferably in the range from 120 ° C.
- the drying gas temperature is measured at the hottest point of the drying tower, the so-called ring channel.
- the temperatures mentioned the same also applies to the further configuration of the production process according to the invention, fluidized bed or fluidized bed drying.
- aqueous, generally 30 to 60 percent by weight alkyl glycoside pastes as are usually obtained in the course of alkyl glycoside production and, if appropriate, subsequent bleaching.
- the alkyl sulfate component and in particular the carrier component can be used as an aqueous solution or slurry.
- at least about 35% by weight, preferably 40 to 50% by weight, of water is present in the slurry to be dried .
- a further advantage of the process according to the invention is the surprisingly low viscosity of the slurries leading to the compounds according to the invention, which is in particular in the range from 3,000 mPa ⁇ s to 15,000 mPa ⁇ s at temperatures from 60 ° C to 75 ° C, compared to slurries that contain the same amount of alkylbenzenesulfonate instead of alkyl sulfate.
- the powdery, alkylbenzenesulfonate-free, free-flowing and free-flowing surfactant mixtures produced by the process according to the invention preferably contain 10% by weight to 40% by weight of alkyl glycoside of the formula I, R 1 -O (G) n (I) in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, 5% by weight to 20% by weight of alkyl sulfate of the formula II, R 2 -OSO 3 X (II) in which R 2 is an alkyl radical having 10 to 20 C atoms and X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion, the weight ratio of alkyl glycoside to alkyl sulfate being 5: 1 to 1: 2, in particular 3: 1 is up to 1: 1, 40% by weight to 80% by weight of an inorganic support material which
- the inorganic carrier material present in the compounds according to the invention consists of at least 10% by weight, preferably 20 to 50% by weight. from alkali silicate with a molar ratio of SiO 2 to alkali oxide of at least 2, in particular from 2.0 to 3.5 and preferably from 2.5 to 3.5.
- the preferred alkali metal is sodium.
- the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof are particularly suitable as further water-soluble inorganic carrier materials which can be used in addition to alkali metal silicate after drying, and the sodium salts are also preferred in these cases. It is also possible to incorporate water-insoluble carrier materials, which include, in particular, layered silicates, for example bentonites or smectites, and aluminosilicates, for example zeolites.
- alkyl glycosides suitable for incorporation into the compounds according to the invention are compounds of the general formula I in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10.
- R 1 is an alkyl radical having 8 to 22 carbon atoms
- G is a glycose unit
- n is a number between 1 and 10.
- the glycoside component ((G) n in formula I) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose , Idose, ribose, arabinose, xylose and lyxose.
- the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
- the degree of oligomerization (n in formula I) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
- the preferred monomer building block is glucose because of its good availability.
- the alkyl part (R 1 in formula I) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, are also used to prepare usable alkyl glycosides can be. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
- the alkyl glycosides can contain small amounts, for example 1 to 2%, of unreacted free fatty alcohol, which does not have a disadvantageous effect on the properties of the compounds produced therewith.
- alkyl glycosides are preferably present in the compounds according to the invention in amounts of from 10% by weight to 40% by weight, in particular from 20% by weight to 30% by weight, the weight ratio of alkyl glycoside to alkyl sulfate being 5: 1 to 1 : 2, preferably 3: 1 to 1: 1.
- Suitable alkyl sulfates for use in the process according to the invention are the compounds of the formula II in which R 2 is an alkyl radical having 10 to 20 C atoms and X is an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion .
- R 2 is an alkyl radical having 10 to 20 C atoms
- X is an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion .
- the derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols are particularly suitable.
- the alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
- a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
- alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases are preferably present in the compounds according to the invention in amounts of 5% by weight to 20% by weight, in particular 8% by weight to 15% by weight.
- the mixtures according to the invention can contain further surfactants, preferably nonionic surfactants and / or anionic surfactants, and in particular those of the sulfate or sulfonate type, in amounts of preferably not more than 10% by weight, in particular from 1% by weight to 5% by weight .-%, contain.
- the sulfate-type surfactants which can also be used include, in particular, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
- Suitable anionic surfactants also include the ⁇ -sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 to 6 C atoms , preferably 1 to 4 carbon atoms, derivative sulfonation products and the sulfofatty acids or salts thereof which can be derived from them by formal saponification.
- the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
- the degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
- the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
- the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
- Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used.
- Carrier substances are contained in the powdery mixtures according to the invention in amounts of 40% by weight to 80% by weight, preferably from 48% by weight to 68% by weight, it being essential that at least 10% by weight of the carrier material , preferably 20 wt .-% to 50 wt .-%, consist of the alkali silicate mentioned.
- the compounds according to the invention can contain further constituents which are customary in washing and cleaning agents and are stable under the drying conditions.
- These optional components include, in particular, complexing agents for heavy metals, for example aminopolycarboxylic acids and / or polyphosphonic acids, graying inhibitors, for example cellulose ethers, cobuilders, for example polymer polycarboxylic acids, Foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives.
- Such additives are preferably present in the powdery surfactant mixtures in amounts not exceeding 5% by weight, in particular 0.5% by weight to 2% by weight.
- the powdered surfactant mixtures according to the invention are used in particular as pourable and free-flowing preliminary products (compounds) for the production of particulate detergents or cleaning agents.
- the components should have average grain sizes of preferably 0.2 mm to 0.4 mm and should be largely free of particles with a diameter of more than 2 mm or less than 50 ⁇ m. In this context, largely free means an amount of not more than 0.8% by weight. This limit is normally observed by the compounds according to the invention obtained by spray drying, otherwise particles outside this size range can be removed by simple sieving and returned to the production process.
- the bulk density of the compounds according to the invention is preferably between 200 and 500 grams per liter and can therefore certainly differ from that of the other powdery constituents of a finished washing or cleaning agent, normally without segregation occurring.
- the compounds according to the invention are free-flowing, free-flowing powders which do not lose their advantageous properties even after prolonged storage.
- the compounds according to the invention can be mixed in a manner known in principle with other pulverulent constituents customary in such agents, in particular abrasives, for example quartz powder, bleaching agents, for example perborates or percarbonates, and bleach activators, for example polyacylated alkylenediamines, Carboxylic anhydrides or polyacylated polyols.
- abrasives for example quartz powder
- bleaching agents for example perborates or percarbonates
- bleach activators for example polyacylated alkylenediamines, Carboxylic anhydrides or polyacylated polyols.
- the spraying of liquid, liquefied or dissolved ingredients, for example enzymes, dyes, fragrances or other surfactants, in particular nonionic surfactants, onto the compounds according to the invention is also possible in a manner known in principle.
- the alkyl glycoside component By heating the alkyl glycoside component to approx. 60 ° C., adding it to the aqueous alkyl sulfate solution and adding the other components with stirring, the sodium silicate being added as the last component in the form of an approx. 35% by weight water glass solution, from the Raw materials specified in Table 1 produced aqueous slurries containing 40 to 44 wt .-% water.
- the free-flowing powders M1 and M2 characterized in Table 1 by their composition were obtained with average grain sizes around 300 ⁇ m, which were free of particles over 1.6 mm in diameter, had dust contents of 0.1 to 0.65% by weight and Bulk densities of 240 to 300 grams per liter.
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Abstract
Description
Die Erfindung betrifft pulverförmige, schütt- und rieselfähige Tensidmischungen, die Alkylsulfat, Alkylglykosid und anorganisches Trägermaterial enthalten, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Vorgemische (Compounds) zur Herstellung von partikelförmigen Wasch-und Reinigungsmitteln.The invention relates to powdery, pourable and free-flowing surfactant mixtures which contain alkyl sulfate, alkyl glycoside and inorganic carrier material, a process for their preparation and their use as premixes (compounds) for the production of particulate detergents and cleaning agents.
Aus der internationalen Patentanmeldung WO 87/02053 ist ein Verfahren zur Herstellung teilchenförmiger Waschmittel durch Trocknen einer 40 bis 80 prozentigen wäßrigen Aufschlämmung bekannt, die, bezogen auf entstehenden Feststoff, 2 bis 60 Gew.-% Tenside, die zu mindestens 0,1 Gew.-% aus Alkylglykosiden bestehen, wobei die Gesamtmenge an Alkylglykosiden höchstens 2 Gew.-% beträgt, 5 bis 70 Gew.-% Buildersubstanzen und bis zu 40 Gew.-% wasserlösliche Füllstoffe enthält. Bevorzugt eingesetzte Tenside sind anionische Tenside, insbesondere solche vom Typ der Alkylbenzolsulfonate, und nichtionische Tenside, insbesondere ethoxylierte Fettalkohole. Der Entzug des Wassers aus der Aufschlämmung wird vorzugsweise durch Sprühtrocknen erreicht.From international patent application WO 87/02053 a process for the production of particulate detergents by drying a 40 to 80 percent aqueous slurry is known, which, based on the resulting solid, 2 to 60 wt .-% surfactants, which are at least 0.1 wt. % consist of alkyl glycosides, the total amount of alkyl glycosides being at most 2% by weight, containing 5 to 70% by weight of builder substances and up to 40% by weight of water-soluble fillers. Preferred surfactants are anionic surfactants, especially those of the alkylbenzenesulfonate type, and nonionic surfactants, especially ethoxylated fatty alcohols. The removal of water from the slurry is preferably accomplished by spray drying.
In der US-amerikanischen Patentschrift US 4 536 319 werden granulare Waschmittel beschrieben, die Alkylglykoside, wasserlösliche Salze und gegebenenfalls wasserunlösliche Buildersubstanzen sowie zusätzliche Tenside enthalten. Die dort beschriebenen Mittel enthalten bis zu 3 Gew.-% eines speziellen Alkalisilikats. Derartige Mittel weisen allerdings in der Regel ein unbefriedigendes Rieselverhalten auf und neigen insbesondere bei der Lagerung zum Verklumpen.US Pat. No. 4,536,319 describes granular detergents which contain alkyl glycosides, water-soluble salts and optionally water-insoluble builder substances and additional surfactants. The agents described therein contain up to 3% by weight of a special alkali silicate. However, such agents generally have an unsatisfactory flow behavior and tend to clump, particularly during storage.
Moderne pulverförmige Wasch- oder Reinigungsmittel bestehen in der Regel aus mehreren separat hergestellten Pulverkomponenten, die je nach Art ihrer Inhaltsstoffe verschiedene Herstellungsverfahren erforderlich machen. Ein bevorzugtes Herstellungsverfahren für die oberflächenaktivsubstanzhaltige Komponente solcher Mittel ist wegen seiner relativen Unkompliziertheit die Sprühtrocknung einer wäßrigen Lösung oder Aufschlämmung der Inhaltsstoffe. Ein derartiges Verfahren setzt allerdings eine thermische Belastbarkeit der oberflächenaktiven Inhaltsstoffe voraus, die bei Verwendung bisher üblicher Aniontenside insbesondere aus der Klasse der Alkylbenzolsulfonate gewährleistet ist.Modern powder detergents or cleaning agents generally consist of several separately manufactured powder components, which, depending on the nature of their ingredients, require different manufacturing processes. A preferred manufacturing process for the surfactant-containing component of such agents is because of its relative simplicity spray drying an aqueous solution or slurry of the ingredients. However, such a process requires a thermal load capacity of the surface-active ingredients, which is ensured when using anionic surfactants customary to date, in particular from the class of alkylbenzenesulfonates.
Der Einsatz von Alkylbenzolsulfonat in Wasch- und Reinigungsmitteln wird in neuerer Zeit wegen der Erdöl-Basis dieses Tensids zunehmend in Frage gestellt. Als umweltverträglichere Aniontenside mit vergleichbar guten Reinigungseigenschaften kommen zum Beispiel Sulfatierungsprodukte von aus nachwachsenden Rohstoffen zugänglichen Verbindungen, insbesondere Fettalkoholen, in Betracht. Während allerdings alkylbenzolsulfonathaltige wäßrige Aufschlämmungen problemlos bei den in derartigen Verfahren üblichen Temperaturen, normalerweise etwa 250 °C bis 350 °C, sprühgetrocknet werden können, wurde nun gefunden, daß unter diesen Bedingungen bei wäßrigen Aufschlämmungen, welche die gleiche Menge an Alkylsulfaten enthalten, die Gefahr der Selbstentzündung besteht. Diese Problematik wird noch verstärkt bei Anwesenheit von nichtionischen Tensiden in der zu versprühenden Aufschlämmung, deren Einsatz in Wasch- oder Reinigungsmitteln allerdings oft erwünscht ist. Zu derartigen nichtionischen Tensiden gehören insbesondere Alkylglykoside mit langkettigen Alkylgruppen, die wegen ihrer vorteilhaften Eigenschaften in neuerer Zeit bevorzugt eingesetzt werden. Derartige Alkylglykoside fallen normalerweise als hochviskose Pasten an, was ihren Einsatz in relativ hohen Konzentrationen in für die Sprühtrocknung vorgesehenen wäßrigen Aufschlämmungen wegen der hohen mechanischen Beanspruchung in einem solchen Verfahren nicht aussichtsreich erscheinen ließ.The use of alkylbenzenesulfonate in washing and cleaning agents has recently been increasingly questioned because of the petroleum base of this surfactant. For example, sulfation products of compounds accessible from renewable raw materials, in particular fatty alcohols, come into consideration as more environmentally compatible anionic surfactants with comparable good cleaning properties. However, while aqueous slurries containing alkylbenzenesulfonate can be spray-dried without problems at the temperatures customary in such processes, normally from about 250 ° C. to 350 ° C., it has now been found that under these conditions the danger exists with aqueous slurries which contain the same amount of alkyl sulfates self-ignition exists. This problem is exacerbated in the presence of nonionic surfactants in the slurry to be sprayed, but their use in detergents or cleaning agents is often desirable. Such nonionic surfactants include, in particular, alkyl glycosides with long-chain alkyl groups, which have recently been used with preference because of their advantageous properties. Such alkyl glycosides are normally obtained as highly viscous pastes, which means that their use in relatively high concentrations in aqueous slurries intended for spray drying did not appear to be promising because of the high mechanical stress in such a process.
Um so überraschender war es, daß man aus bestimmten Mengen an Alkylsulfat, Alkylglykosid und anorganischem Trägermaterial, das zu mindestens 10 Gew.-% aus Alkalisilikat mit einem Molverhältnis SiO2 zu Alkalioxid über 2 besteht, fließfähige und pumpbare wäßrige Aufschlämmungen erzeugen kann, welche in einem Verfahren zur Herstellung alkylbenzolsulfonatfreier pulverförmiger Tensidmischungen durch Trocknen unter Vermeidung der genannten Probleme eingesetzt werden können und zu lagerstabilen, schütt-und rieselfähigen Pulverprodukten führen, die als Vorgemische, sogenannte Compounds, für die Herstellung partikelförmiger Wasch- und Reinigungsmittel verwendet werden können.It was all the more surprising that it is possible to produce flowable and pumpable aqueous slurries from certain amounts of alkyl sulfate, alkyl glycoside and inorganic carrier material, which consists of at least 10% by weight of alkali silicate with a molar ratio of SiO 2 to alkali oxide above 2, which in a process for the production of alkylbenzenesulfonate-free powdered surfactant mixtures by drying while avoiding the problems mentioned and leading to storage-stable, pourable and free-flowing powder products which are known as premixes Compounds that can be used for the production of particulate detergents and cleaning agents.
Das erfindungsgemäße Verfahren zur Herstellung alkylbenzolsulfonatfreier pulverförmiger Tensidmischungen besteht im wesentlichen darin, daß man 10 bis 40 Gewichtsteile Alkylglykosid der Formel I,
R1-O(G)n (I)
in der R1 einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und
n eine Zahl von 1 bis 10 bedeuten,
5 bis 20 Gewichtsteile Alkylsulfat der Formel II,
R2-OSO3X (II)
in der R2 einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, wobei das Gewichtsverhältnis von Alkylglykosid zu Alkylsulfat 5:1 bis 1:2, vorzugsweise 3:1 bis 1:1 beträgt, und 40 bis 80 Gewichtsteile eines anorganischen Trägermaterials, das zu mindestens 10 Gew.-% aus Alkalisilikat mit einem Molverhältnis SiO2 zu Alkalioxid von mindestens 2 besteht, mit so viel Wasser mischt, daß eine bei Temperaturen unter 80 °C fließfähige und pumpbare Mischung entsteht, und dieser durch Sprühtrocknung oder Wirbelbett- bzw. Wirbelschichttrocknung unter Verwendung von Trocknungsgasen mit Temperaturen unter 250 °C das Wasser soweit entzieht, daß ein pulverförmiges, rieselfähiges Produkt entsteht. Dies ist in der Regel bei Wassergehalten im Pulverprodukt von nicht mehr als 15 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-% der Fall. In Formulierungen, in denen das Trägermaterial einen Teil des Wassers als Kristallwasser bindet, bezieht sich der Rest-Wassergehalt auf das freie, nicht im Kristallgitter gebundene Wasser.The process according to the invention for the preparation of powdered surfactant mixtures free of alkylbenzenesulfonate essentially consists in that 10 to 40 parts by weight of alkylglycoside of the formula I
R 1 -O (G) n (I)
in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and
n is a number from 1 to 10,
5 to 20 parts by weight of alkyl sulfate of the formula II,
R 2 -OSO 3 X (II)
in which R 2 is an alkyl radical having 10 to 20 C atoms and X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion, the weight ratio of alkyl glycoside to alkyl sulfate being 5: 1 to 1: 2, preferably 3: 1 is up to 1: 1, and 40 to 80 parts by weight of an inorganic carrier material, which consists of at least 10 wt .-% of alkali silicate with a molar ratio of SiO 2 to alkali oxide of at least 2, mixed with so much water that one at temperatures below 80 ° C flowable and pumpable mixture is formed, and this is removed by spray drying or fluidized bed or fluidized bed drying using drying gases at temperatures below 250 ° C. to the extent that a powdery, free-flowing product is formed. This is usually the case when the water content in the powder product is not more than 15% by weight, in particular from 5% by weight to 15% by weight. In formulations in which the carrier material binds part of the water as crystal water, the residual water content relates to the free water not bound in the crystal lattice.
Fließfähig und pumpbar im Rahmen der vorliegenden Erfindung sind solche wäßrige Aufschlämmungen, die sich problemlos mittels üblicher in Sprühtrocknungsverfahren eingesetzter Pumpen und Rohrleitungen bei Temperaturen unter 80 °C handhaben lassen. Die in dem erfindungsgemäßen Verfahren eingesetzten Aufschlämmungen besitzen daher vorzugsweise Viskositäten im Bereich von 3 000mPa·s bis 15 000mPa·s, gemessen bei 60 °C bis 75 °C mittels üblicher Viskosimeter, beispielsweise einem Brookfield-Viskosimeter mit Spindel Nr. 3 bei 20 Umdrehungen pro Minute.Flowable and pumpable in the context of the present invention are those aqueous slurries which can be handled without problems at temperatures below 80 ° C. by means of pumps and pipelines which are customarily used in spray drying processes. Those used in the process according to the invention Slurries therefore preferably have viscosities in the range from 3,000 mPas to 15,000 mPas, measured at 60 ° C. to 75 ° C. using conventional viscometers, for example a Brookfield viscometer with spindle No. 3 at 20 revolutions per minute.
Vorzugsweise wird das erfindungsgemäße Verfahren derart ausgeführt, daß man 20 bis 30 Gewichtsteile Alkylglykosid gemäß Formel I, 8 bis 15 Gewichtsteile Alkylsulfat gemäß Formel II und 48 bis 68 Gewichtsteile des anorganischen Trägermaterials mit so viel Wasser mischt, daß eine mindestens 35 Gew.-%, insbesondere 40 Gew.-% bis 50 Gew.-% Wasser enthaltende Mischung entsteht.The process according to the invention is preferably carried out in such a way that 20 to 30 parts by weight of alkyl glycoside according to formula I, 8 to 15 parts by weight of alkyl sulfate according to formula II and 48 to 68 parts by weight of the inorganic carrier material are mixed with so much water that at least 35% by weight, in particular, a mixture containing 40% by weight to 50% by weight of water is formed.
Die Sprühtrocknung der wäßrigen Aufschlämmungen erfolgt in üblicherweise dafür vorgesehenen Anlagen, sogenannten Sprühtürmen, in deren oberem Teil die Aufschlämmung durch Druckdüsen zu feinen Tröpfchen versprüht wird, die sich unter Einwirkung der Schwerkraft in den unteren Teil des Sprühturms bewegen und dabei mit heißen Trocknungsgasen in Kontakt kommen, die im Gleichstrom oder vorzugsweise im Gegenstrom zu den zu trocknenden Partikeln geführt werden. Dabei ist darauf zu achten, daß die Temperatur der Trocknungsgase nicht so hoch liegt, daß die Temperatur der sprühgetrockneten Partikel über die Selbstentzündungstemperatur dieser Partikel steigt. Im Rahmen der Erfindung bedeutet dies, daß die Temperatur der Trocknungsgase einen Wert von 250 °C nicht überschreitet und vorzugsweise im Bereich von 120 °C bis 240 °C, insbesondere von 140 °C bis 210 °C und besonders bevorzugt von 150 °C bis 190 °C liegt, wobei die Trocknungsgastemperatur an der heißesten Stelle des Trockenturms, dem sogenannten Ringkanal, gemessen wird. Bezüglich der genannten Temperaturen gilt das gleiche auch für die weitere Ausgestaltung des erfindungsgemäßen Herstellungsverfahrens, die Wirbelbett- bzw. Wirbelschichttrocknung.The spray-drying of the aqueous slurries takes place in systems usually provided for this purpose, so-called spray towers, in the upper part of which the slurry is sprayed into fine droplets by pressure nozzles, which move under the action of gravity into the lower part of the spray tower and come into contact with hot drying gases which are guided in cocurrent or preferably in countercurrent to the particles to be dried. It should be ensured that the temperature of the drying gases is not so high that the temperature of the spray-dried particles rises above the self-ignition temperature of these particles. In the context of the invention, this means that the temperature of the drying gases does not exceed a value of 250 ° C. and preferably in the range from 120 ° C. to 240 ° C., in particular from 140 ° C. to 210 ° C. and particularly preferably from 150 ° C. to 190 ° C, the drying gas temperature is measured at the hottest point of the drying tower, the so-called ring channel. With regard to the temperatures mentioned, the same also applies to the further configuration of the production process according to the invention, fluidized bed or fluidized bed drying.
Bei der Zubereitung der zu den erfindungsgemäßen Mischungen führenden Aufschlämmungen ist die Einarbeitung wäßriger, in der Regel 30- bis 60-gewichtsprozentiger Alkylglykosid-Pasten, wie sie im Rahmen der Alkylglykosid-Herstellung und gegebenenfalls anschließendem Bleichen üblicherweise anfallen, möglich. Ebenso kann die Alkylsulfat-Komponente und insbesondere die Träger-Komponente als wäßrige Lösung oder Aufschlämmung eingesetzt werden. Um die leichte Fließ- und Pumpfähigkeit der Aufschlämmung bei Temperaturen unter 80 °C zu gewährleisten, hat es sich als vorteilhaft erwiesen, wenn mindestens etwa 35 Gew.-%, vorzugsweise 40 bis 50 Gew.-% Wasser in der zu trocknenden Aufschlämmung vorhanden ist. Dabei ist als weiterer Vorteil des erfindungsgemäßen Verfahrens die überraschend niedrige Viskosität der zu den erfindungsgemäßen Compounds führenden Aufschlämmungen, die insbesondere im Bereich von 3 000 mPa·s bis 15 000 mPa·s bei Temperaturen von 60 °C bis 75 °C liegt, gegenüber Aufschlämmungen, die statt Alkylsulfat die gleiche Menge Alkylbenzolsulfonat enthalten, zu werten.In the preparation of the slurries leading to the mixtures according to the invention, it is possible to incorporate aqueous, generally 30 to 60 percent by weight alkyl glycoside pastes, as are usually obtained in the course of alkyl glycoside production and, if appropriate, subsequent bleaching. Likewise, the alkyl sulfate component and in particular the carrier component can be used as an aqueous solution or slurry. In order to ensure the easy flow and pumpability of the slurry at temperatures below 80 ° C., it has proven to be advantageous if at least about 35% by weight, preferably 40 to 50% by weight, of water is present in the slurry to be dried . A further advantage of the process according to the invention is the surprisingly low viscosity of the slurries leading to the compounds according to the invention, which is in particular in the range from 3,000 mPa · s to 15,000 mPa · s at temperatures from 60 ° C to 75 ° C, compared to slurries that contain the same amount of alkylbenzenesulfonate instead of alkyl sulfate.
Die durch das erfindungsgemäße Verfahren hergestellten erfindungsgemäßen pulverförmigen, alkylbenzolsulfonatfreien schütt- und rieselfähigen Tensidmischungen enthalten vorzugsweise
10 Gew.-% bis 40 Gew.-% Alkylglykosid der Formel I,
R1-O(G)n (I)
in der R1 einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und
n eine Zahl von 1 bis 10 bedeuten,
5 Gew.-% bis 20 Gew.-% Alkylsulfat der Formel II,
R2-OSO3X (II)
in der R2 einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, wobei das Gewichtsverhältnis von Alkylglykosid zu Alkylsulfat 5:1 bis 1:2, insbesondere 3:1 bis 1:1 beträgt, 40 Gew.-% bis 80 Gew.-% eines anorganischen Trägermaterials, das zu mindestens 10 Gew.-%, bezogen auf gesamtes Trägermaterial, aus Alkalisilikat mit einem Molverhältnis SiO2 zu Alkalioxid von mindestens 2 besteht, und bis zu 15 Gew.-%, insbesondere 5 Gew.-% bis 15 Gew.-% Wasser.The powdery, alkylbenzenesulfonate-free, free-flowing and free-flowing surfactant mixtures produced by the process according to the invention preferably contain
10% by weight to 40% by weight of alkyl glycoside of the formula I,
R 1 -O (G) n (I)
in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and
n is a number from 1 to 10,
5% by weight to 20% by weight of alkyl sulfate of the formula II,
R 2 -OSO 3 X (II)
in which R 2 is an alkyl radical having 10 to 20 C atoms and X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion, the weight ratio of alkyl glycoside to alkyl sulfate being 5: 1 to 1: 2, in particular 3: 1 is up to 1: 1, 40% by weight to 80% by weight of an inorganic support material which consists of at least 10% by weight, based on the total support material, of alkali silicate with a molar ratio of SiO 2 to alkali oxide of at least 2, and up to 15% by weight, in particular 5% by weight to 15% by weight of water.
Das in den erfindungsgemäßen Compounds vorhandene anorganische Trägermaterial besteht zu mindestens 10 Gew.-%, vorzugsweise zu 20 bis 50 Gew.-% aus Alkalisilikat mit einem Molverhältnis SiO2 zu Alkalioxid von mindestens 2, insbesondere von 2,0 bis 3,5 und vorzugsweise von 2,5 bis 3,5. Bevorzugtes Alkalimetall ist hierbei Natrium. Als zusätzlich zu Alkalisilikat einsetzbare weitere wasserlösliche und nach dem Trocknen partikelförmige anorganische Trägermaterialien sind die Alkalicarbonate, Alkalihydrogencarbonate und Alkalisulfate sowie deren Gemische besonders geeignet, wobei auch in diesen Fällen die Natriumsalze bevorzugt sind. Auch die Einarbeitung wasserunlöslicher Trägermaterialien, zu denen insbesondere Schichtsilikate, beispielsweise Bentonite oder Smectite, und Alumosilikate, beispielsweise Zeolithe, gehören, ist möglich.The inorganic carrier material present in the compounds according to the invention consists of at least 10% by weight, preferably 20 to 50% by weight. from alkali silicate with a molar ratio of SiO 2 to alkali oxide of at least 2, in particular from 2.0 to 3.5 and preferably from 2.5 to 3.5. The preferred alkali metal is sodium. The alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof are particularly suitable as further water-soluble inorganic carrier materials which can be used in addition to alkali metal silicate after drying, and the sodium salts are also preferred in these cases. It is also possible to incorporate water-insoluble carrier materials, which include, in particular, layered silicates, for example bentonites or smectites, and aluminosilicates, for example zeolites.
Die zur Einarbeitung in die erfindungsgemäßen Compounds geeigneten Alkylglykoside sind Verbindungen der allgemeinen Formel I, in der R1 einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl zwischen 1 und 10 bedeuten. Derartige Alkylglykoside und ihre Herstellung werden zum Beispiel in den europäischen Patentanmeldungen EP 92 355, EP 301 298, EP 357 969 und EP 362 671 oder der US-amerikanischen Patentschrift US 3 547 828 beschrieben. Bei der Glykosidkomponente ((G)n in Formel I) derartiger Alkylglykoside handelt es sich um Oligo- oder Polymere aus natürlich vorkommenden Aldose- oder Ketose-Monomeren, zu denen insbesondere Glucose, Mannose, Fruktose, Galaktose, Talose, Gulose, Altrose, Allose, Idose, Ribose, Arabinose, Xylose und Lyxose gehören. Die aus derartigen glykosidisch verknüpften Monomeren bestehenden 0ligomere werden außer durch die Art der in ihnen enthaltenen Zucker durch deren Anzahl, den sogenannten Oligomerisierungsgrad, charakterisiert. Der Oligomerisierungsgrad (n in Formel I) nimmt als analytisch zu ermittelnde Größe im allgemeinen gebrochene Zahlenwerte an; er liegt bei Werten zwischen 1 und 10, bei den vorzugsweise eingesetzten Alkylglykosiden unter einem Wert von 1,5, insbesondere zwischen 1,2 und 1,4. Bevorzugter Monomer-Baustein ist wegen der guten Verfügbarkeit Glucose.The alkyl glycosides suitable for incorporation into the compounds according to the invention are compounds of the general formula I in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10. Such alkyl glycosides and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or the US Pat. No. 3,547,828. The glycoside component ((G) n in formula I) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose , Idose, ribose, arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization (n in formula I) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability.
Der Alkylteil (R1 in Formel I) der in den erfindungsgemäßen Tensidmischungen enthaltenen Alkylglykoside stammt bevorzugt ebenfalls aus leicht zugänglichen Derivaten nachwachsender Rohstoffe, insbesondere aus Fettalkoholen, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkylglykoside eingesetzt werden können. Brauchbar sind demgemäß insbesondere die primären Alkohole mit linearen Octyl-, Decyl-, Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Besonders geeignete Alkylglykoside enthalten einen Kokosfettalkylrest, das heißt Mischungen mit im wesentlichen R1=Dodecyl und R1=Tetradecyl. Die Alkylglykoside können herstellungsbedingt geringe Mengen, beispielsweise 1 bis 2 %, an nicht umgesetztem freiem Fettalkohol enthalten, was sich nicht nachteilig auf die Eigenschaften der damit hergestellten Compounds auswirkt.The alkyl part (R 1 in formula I) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, are also used to prepare usable alkyl glycosides can be. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly suitable alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R 1 = dodecyl and R 1 = tetradecyl. The alkyl glycosides can contain small amounts, for example 1 to 2%, of unreacted free fatty alcohol, which does not have a disadvantageous effect on the properties of the compounds produced therewith.
Derartige Alkylglykoside sind in den erfindungsgemäßen Compounds vorzugsweise in Mengen von 10 Gew.-% bis 40 Gew.-%, insbesondere von 20 Gew.-% bis 30 Gew.-% enthalten, wobei das Gewichtsverhältnis von Alkylglykosid zu Alkylsulfat 5:1 bis 1:2, vorzugsweise 3:1 bis 1:1 beträgt.Such alkyl glycosides are preferably present in the compounds according to the invention in amounts of from 10% by weight to 40% by weight, in particular from 20% by weight to 30% by weight, the weight ratio of alkyl glycoside to alkyl sulfate being 5: 1 to 1 : 2, preferably 3: 1 to 1: 1.
Als für den Einsatz in dem erfindungsgemäßen Verfahren geeignete Alkylsulfate kommen die Verbindungen der Formel II, in der R2 einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, in Frage. Besonders geeignet sind die Derivate der Fettalkohole mit insbesondere 12 bis 18 C-Atomen und deren verzweigtkettiger Analoga, der sogenannten Oxoalkohole. Die Alkylsulfate können in bekannter Weise durch Reaktion der entsprechenden Alkoholkomponente mit einem üblichen Sulfatierungsreagenz, insbesondere Schwefeltrioxid oder Chlorsulfonsäure, und anschließende Neutralisation mit Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituierten Ammoniumbasen hergestellt werden. Derartige Alkylsulfate sind in den erfindungsgemäßen Compounds vorzugsweise in Mengen von 5 Gew.-% bis 20 Gew.-%, insbesondere von 8 Gew.-% bis 15 Gew.-% enthalten.Suitable alkyl sulfates for use in the process according to the invention are the compounds of the formula II in which R 2 is an alkyl radical having 10 to 20 C atoms and X is an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion . The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Such alkyl sulfates are preferably present in the compounds according to the invention in amounts of 5% by weight to 20% by weight, in particular 8% by weight to 15% by weight.
Darüberhinaus können die erfindungsgemäßen Gemische weitere Tenside, vorzugsweise nichtionische Tenside und/oder Aniontenside und unter diesen insbesondere solche des Sulfat- oder Sulfonat-Typs, in Mengen von vorzugsweise nicht über 10 Gew.-%, insbesondere von 1 Gew.-% bis 5 Gew.-%, enthalten. Zu den zusätzlich brauchbaren Tensiden vom Sulfat-Typ gehören insbesondere die sulfatierten Alkoxylierungsprodukte der genannten Alkohole, sogenannte Ethersulfate. Vorzugsweise enthalten derartige Ethersulfate 2 bis 30, insbesondere 4 bis 10, Ethylenglykol-Gruppen pro Molekül. Zu den geeigneten Aniontensiden gehören auch die durch Umsetzung von Fettsäureestern mit Schwefeltrioxid und anschließender Neutralisation erhältlichen α-Sulfoester, insbesondere die sich von Fettsäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, und linearen Alkoholen mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C-Atomen, ableitenden Sulfonierungsprodukte sowie die durch formale Verseifung von diesen herleitbaren Sulfofettsäuren beziehungsweise deren Salze.In addition, the mixtures according to the invention can contain further surfactants, preferably nonionic surfactants and / or anionic surfactants, and in particular those of the sulfate or sulfonate type, in amounts of preferably not more than 10% by weight, in particular from 1% by weight to 5% by weight .-%, contain. The sulfate-type surfactants which can also be used include, in particular, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. To the Suitable anionic surfactants also include the α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 to 6 C atoms , preferably 1 to 4 carbon atoms, derivative sulfonation products and the sulfofatty acids or salts thereof which can be derived from them by formal saponification.
Zu den in Frage kommenden nichtionischen Tensiden gehören die Alkoxylate, insbesondere die Ethoxylate und/oder Propoxylate von linearen oder verzweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Umsetzung der entsprechenden Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalkohole, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß insbesondere die Ethoxylate primärer Alkohole mit linearen Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Außerdem sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen, verwendbar.The nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used.
Trägersubstanzen sind in den erfindungsgemäßen pulverförmigen Mischungen in Mengen von 40 Gew.-% bis 80 Gew.-%, vorzugsweise von 48 Gew.-% bis 68 Gew.-% enthalten, wobei wesentlich ist, daß mindestens 10 Gew.-% des Trägermaterials, vorzugsweise 20 Gew.-% bis 50 Gew.-%, aus dem genannten Alkalisilikat bestehen.Carrier substances are contained in the powdery mixtures according to the invention in amounts of 40% by weight to 80% by weight, preferably from 48% by weight to 68% by weight, it being essential that at least 10% by weight of the carrier material , preferably 20 wt .-% to 50 wt .-%, consist of the alkali silicate mentioned.
Zusätzlich können die erfindungsgemäßen Compounds weitere in Wasch- und Reinigungsmitteln übliche Bestandteile enthalten, die unter den Trocknungsbedingungen stabil sind. Zu diesen fakultativen Bestandteilen gehören insbesondere Komplexbildner für Schwermetalle, beispielsweise Aminopolycarbonsäuren und/oder Polyphosphonsäuren, Vergrauungsinhibitoren, beispielsweise Celluloseether, Cobuilder, beispielsweise Polymerpolycarbonsäuren, Schauminhibitoren, beispielsweise Organopolysiloxane oder Paraffine, und optische Aufheller, beispielsweise Stilbendisulfonsäurederivate. Derartige Zusatzstoffe sind vorzugsweise in Mengen nicht über 5 Gew.-%, insbesondere 0,5 Gew.-% bis 2 Gew.-%, in den pulverförmigen Tensidmischungen vorhanden.In addition, the compounds according to the invention can contain further constituents which are customary in washing and cleaning agents and are stable under the drying conditions. These optional components include, in particular, complexing agents for heavy metals, for example aminopolycarboxylic acids and / or polyphosphonic acids, graying inhibitors, for example cellulose ethers, cobuilders, for example polymer polycarboxylic acids, Foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives. Such additives are preferably present in the powdery surfactant mixtures in amounts not exceeding 5% by weight, in particular 0.5% by weight to 2% by weight.
Die erfindungsgemäßen pulverförmigen Tensidmischungen werden insbesondere als schütt- und rieselfähige Vorprodukte (Compounds) für die Herstellung von partikelförmigen Wasch- oder Reinigungsmitteln verwendet.The powdered surfactant mixtures according to the invention are used in particular as pourable and free-flowing preliminary products (compounds) for the production of particulate detergents or cleaning agents.
Zur Verwendung als Vorgemische für die Herstellung pulverförmiger Wasch-und Reinigungsmittel sollten die Komponenten mittlere Korngrößen von vorzugsweise 0,2 mm bis 0,4 mm aufweisen und weitgehend frei von Teilchen mit Durchmessern über 2 mm oder unter 50 µm sein. Weitgehend frei bedeutet in diesem Zusammenhang eine Menge von nicht über 0,8 Gew.-%. Diese Grenze wird von den durch Sprühtrocknen erhaltenen erfindungsgemäßen Compounds normalerweise eingehalten, ansonsten können Partikel außerhalb dieses Größenbereichs durch einfaches Aussieben entfernt und in den Herstellungsprozeß zurückgeführt werden. Vorzugsweise liegt die Schüttdichte der erfindungsgemäßen Compounds zwischen 200 und 500 Gramm pro Liter und kann damit durchaus von derjenigen der übrigen pulverförmigen Bestandteile eines fertigen Wasch- oder Reinigungsmittels abweichen, normalerweise ohne Auftreten von Entmischung.For use as premixes for the production of powdered detergents and cleaning agents, the components should have average grain sizes of preferably 0.2 mm to 0.4 mm and should be largely free of particles with a diameter of more than 2 mm or less than 50 μm. In this context, largely free means an amount of not more than 0.8% by weight. This limit is normally observed by the compounds according to the invention obtained by spray drying, otherwise particles outside this size range can be removed by simple sieving and returned to the production process. The bulk density of the compounds according to the invention is preferably between 200 and 500 grams per liter and can therefore certainly differ from that of the other powdery constituents of a finished washing or cleaning agent, normally without segregation occurring.
Die erfindungsgemäßen Compounds sind rieselfähige, freifließende Pulver, die ihre vorteilhaften Eigenschaften auch bei längerer Lagerung nicht verlieren. Zur Herstellung von Reinigungs- oder Waschmitteln können die erfindungsgemäßen Compounds in im Prinzip bekannter Weise mit sonstigen in derartigen Mitteln üblichen pulverförmigen Bestandteilen vermischt werden, zu denen insbesondere Abrasivstoffe, beispielsweise Quarzmehl, Bleichmittel, beispielsweise Perborate oder Percarbonate, und Bleichaktivatoren, beispielsweise mehrfach acylierte Alkylendiamine, Carbonsäureanhydride oder mehrfach acylierte Polyole, gehören. Auch das Aufsprühen von flüssigen, verflüssigten oder gelösten Inhaltsstoffen, beispielsweise Enzymen, Farbstoffen, Duftstoffen oder weiteren Tensiden, insbesondere nichtionischen Tensiden, auf die erfindungsgemäßen Compounds ist in im Prinzip bekannter Weise möglich.The compounds according to the invention are free-flowing, free-flowing powders which do not lose their advantageous properties even after prolonged storage. To produce cleaning agents or detergents, the compounds according to the invention can be mixed in a manner known in principle with other pulverulent constituents customary in such agents, in particular abrasives, for example quartz powder, bleaching agents, for example perborates or percarbonates, and bleach activators, for example polyacylated alkylenediamines, Carboxylic anhydrides or polyacylated polyols. The spraying of liquid, liquefied or dissolved ingredients, for example enzymes, dyes, fragrances or other surfactants, in particular nonionic surfactants, onto the compounds according to the invention is also possible in a manner known in principle.
Durch Erwärmen der Alkylglykosid-Komponente auf ca. 60°C, Zugabe zur wäßrigen Alkylsulfat-Lösung und Zugabe der weiteren Komponenten unter Rühren, wobei das Natriumsilikat in Form einer ca. 35-gewichtsprozentigen Wasserglas-Lösung als letzte Komponente zugegeben wurde, wurden aus den in Tabelle 1 angegebenen Rohstoffen wäßrige Aufschlämmungen erzeugt, die 40 bis 44 Gew.-% Wasser enthielten. Diese Slurries, die bei 65 °C die in Tabelle 2 angegebenen Viskositäten aufwiesen, wurden auf Temperaturen von etwa 60 °C bis 80 °C erwärmt und unter einem Druck von 40 bar in einem Trockenturm versprüht, wobei Heißluft (Temperatur 150 °C bis 190 °C im Ringkanal)
Claims (14)
- A powder-form, pourable and free-flowing surfactant mixture free from alkyl benzenesulfonates which is obtained by drying of a pourable aqueous mixture of its constituents and which contains
10% to 40% by weight of alkyl glycoside corresponding to formula I:
R1-O(G)n (I)
in which R1 is a C8-22 alkyl radical, G is a glycose unit and
n is an integer of 1 to 10,
5% to 20% by weight of alkyl sulfate corresponding to formula II:
R2-OSO3X (II)
in which R2 is a C10-20 alkyl radical and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion,
40% to 80% by weight of an inorganic carrier material and up to 15% by weight of water, characterized in that at least 10% by weight of the inorganic carrier material, based on the carrier material as a whole, consists of alkali metal silicate with a molar ratio of SiO2 to alkali metal oxide of at least 2 and the ratio by weight of alkyl glycoside to alkyl sulfate is 5:1 to 1:2 and preferably 3:1 to 1:1. - A surfactant mixture as claimed in claim 1, characterized in that it contains 20% by weight to 30% by weight of alkyl glycoside corresponding to formula I, 8% by weight to 15% by weight of alkyl sulfate corresponding to formula II, 48 to 68% by weight of inorganic carrier material, not more than 10% by weight and, more particularly, 1% to 5% by weight of additional anionic and/or nonionic surfactant and 5% by weight to 15% by weight of water.
- A surfactant mixture as claimed in claim 1 or 2, characterized in that 20% by weight to 50% by weight of the inorganic carrier material consists of alkali metal silicate with a molar ratio of SiO2 to alkali metal oxide of at least 2 and, more particularly, 2.0 to 3.5:1.
- A surfactant mixture as claimed in any of claims 1 to 3, characterized in that the alkyl glycoside corresponding to formula I is an alkyl glucoside and has a degree of oligomerization n below 1.5 and, more particularly, from 1.2 to 1.4.
- A surfactant mixture as claimed in any of claims 1 to 4, characterized in that the alkyl sulfate corresponding to formula II contains a C12-18 alkyl group R2.
- The use of the powder-form surfactant mixture claimed in any of claims 1 to 5 as a pourable and free-flowing compound for the production of particulate detergents or cleaning products.
- A process for the production of powder-form surfactant mixtures free from alkyl benzenesulfonates by drying of flowable, aqueous surfactant-containing mixtures, in which 10 to 40 parts by weight of alkyl glycoside corresponding to formula I:
R1-O(G)n (I)
in which R1 is a C8-22 alkyl radical, G is a glycose unit and
n is an integer of 1 to 10,
5 to 20 parts by weight of alkyl sulfate corresponding to formula II:
R2-OSO3X (II)
in which R2 is a C10-20 alkyl radical and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion,
and 40 to 80 parts by weight of an inorganic carrier material,
are mixed with water in such a quantity that a mixture flowable and pumpable at temperatures below 80°C is formed and the water is removed from this mixture by spray drying using drying gases having temperatures below 250°C to such an extent that a powder-form, free-flowing product is formed, characterized in that at least 10% by weight of the inorganic carrier material consists of alkali metal silicate with a molar ratio of SiO2 to alkali metal oxide of at least 2 and the ratio by weight of alkyl glycoside to alkyl sulfate is 5:1 to 1:2. - A process as claimed in claim 7, characterized in that 20 to 30 parts by weight of alkyl glycoside corresponding to formula I, 8 to 15 parts by weight of alkyl sulfate corresponding to formula II and 48 to 68 parts by weight of the inorganic carrier material are mixed with water in such a quantity that a mixture containing at least 35% by weight and, more particularly, 40% by weight to 50% by weight of water is formed.
- A process for the production of powder-form surfactant mixtures free from alkyl benzenesulfonates by drying of flowable, aqueous surfactant-containing mixtures, characterized in that
10 to 40 parts by weight of alkyl glycoside corresponding to formula I:
R1-O(G)n (I)
in which R1 is a C8-22 alkyl radical, G is a glycose unit and
n is an integer of 1 to 10,
5 to 20 parts by weight of alkyl sulfate corresponding to formula II:
R2-OSO3X (II)
in which R2 is a C10-20 alkyl radical and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion,
and 40 to 80 parts by weight of an inorganic carrier material are mixed with water in such a quantity that a mixture flowable and pumpable at temperatures below 80°C is formed and in that the water is removed from this mixture by fluidized-bed drying using drying gases having temperatures below 250°C to such an extent that a powder-form, free-flowing product is formed, characterized in that at least 10% by weight of the inorganic carrier material consists of alkali metal silicate with a molar ratio of SiO2 to alkali metal oxide of at least 2 and the ratio by weight of alkyl glycoside to alkyl sulfate is 5:1 to 1:2. - A process as claimed in any of claims 7 to 9, characterized in that the ratio by weight of alkyl glycoside to alkyl sulfate is 3:1 to 1:1.
- A process as claimed in any of claims 7 to 10, characterized in that 20 to 50% by weight of the inorganic carrier material consists of alkali metal silicate with a molar ratio of SiO2 to alkali metal oxide of at least 2 and, more particularly, 2.0 to 3.5:1 and in that, in addition to the alkali metal silicate, the inorganic carrier material contains an alkali metal carbonate, an alkali metal hydrogen carbonate, an alkali metal sulfate, a layer silicate or alumosilicate or a mixture thereof.
- A process as claimed in any of claims 7 to 11, characterized in that drying gases having temperatures of 120°C to 240°C and, more particularly, 140 to 210°C are used.
- A process as claimed in any of claims 7 to 12, characterized in that the aqueous mixture to be dried has a viscosity of 3,000 mPa·s to 15,000 mPa·s, as measured at 60°C to 75°C.
- The use of the powder-form surfactant mixture produced by the process claimed in any of claims 7 to 13 as a pourable and free-flowing compound for the production of particulate detergents or cleaning products.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4216775 | 1992-05-21 | ||
| DE4216775A DE4216775A1 (en) | 1992-05-21 | 1992-05-21 | Powdery surfactant mixture |
| PCT/EP1993/001192 WO1993023514A1 (en) | 1992-05-21 | 1993-05-13 | Powdery surfactants mixture |
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| Publication Number | Publication Date |
|---|---|
| EP0642573A1 EP0642573A1 (en) | 1995-03-15 |
| EP0642573B1 true EP0642573B1 (en) | 1996-06-19 |
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| EP93909976A Expired - Lifetime EP0642573B1 (en) | 1992-05-21 | 1993-05-13 | Powdery surfactants mixture |
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|---|---|
| EP (1) | EP0642573B1 (en) |
| JP (1) | JP3565842B2 (en) |
| KR (1) | KR100278221B1 (en) |
| AT (1) | ATE139559T1 (en) |
| DE (2) | DE4216775A1 (en) |
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| DE4329389A1 (en) * | 1993-09-01 | 1995-03-02 | Henkel Kgaa | Spray-dried washing or cleaning agent or component therefor |
| GB9424444D0 (en) * | 1994-12-02 | 1995-01-18 | Unilever Plc | Detergent compositions |
| DE19501269A1 (en) | 1995-01-18 | 1996-07-25 | Henkel Kgaa | Amorphous alkali silicate compound |
| DE19524464C2 (en) * | 1995-07-10 | 2000-08-24 | Cognis Deutschland Gmbh | Process for the production of sugar surfactant granules |
| FR2743085B1 (en) * | 1995-12-29 | 1999-02-26 | Rhone Poulenc Chimie | DETERGENT COMPOSITION FOR THE WASHING OF LAUNDRY CONTAINING SODIUM SILICATE AS A MAIN DETERGENCE ADJUVANT |
| GB2318584A (en) * | 1996-10-25 | 1998-04-29 | Procter & Gamble | Process for preparing detergent compositions by spray drying |
| GB9711356D0 (en) | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
| GB9825560D0 (en) | 1998-11-20 | 1999-01-13 | Unilever Plc | Particulate laundry detergent compositons containing nonionic surfactant granules |
| GB9825563D0 (en) | 1998-11-20 | 1999-01-13 | Unilever Plc | Particulate laundry detergent compositions containing anionic surfactant granules |
| GB9825558D0 (en) * | 1998-11-20 | 1999-01-13 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
| DE19923626A1 (en) * | 1999-05-22 | 2000-11-23 | Henkel Kgaa | Production of surfactant granulates, useful for making laundry tablets, involves converting sugar surfactant to compound with water-soluble carrier material and granulating with non-aqueous solvent |
| DE10212169A1 (en) * | 2002-03-19 | 2003-10-02 | Sued Chemie Ag | Detergent additive with a high content of non-ionic surfactants and quick dissolving power |
| TWI247798B (en) * | 2003-06-06 | 2006-01-21 | Kao Corp | Detergent composition for hard surface |
| ATE501243T1 (en) * | 2006-10-16 | 2011-03-15 | Procter & Gamble | SPRAY DRYING METHOD FOR PRODUCING SPRAY DRIED, HIGHLY WATER SOLUBLE, LOW DENSITY AND LOW BUILDER CONTENT DETERGENTS. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536319A (en) * | 1983-10-04 | 1985-08-20 | The Procter & Gamble Company | Compositions comprising alkylpolysaccharide detergent surfactant |
| US4675127A (en) * | 1985-09-26 | 1987-06-23 | A. E. Staley Manufacturing Company | Process for preparing particulate detergent compositions |
| WO1990004630A1 (en) * | 1988-10-21 | 1990-05-03 | Henkel Corporation | A process for preparing a detergent slurry and particulate detergent composition |
| DE3838808A1 (en) * | 1988-11-17 | 1990-05-23 | Henkel Kgaa | DETERGENT AND CLEANING AGENT, CONTAINING A TENSIDE MIXTURE OF ALKYL GLYCOSIDES AND ANIONSIDE |
| DE4102745A1 (en) * | 1991-01-30 | 1992-08-06 | Henkel Kgaa | POWDERED SURFACE BLEND |
-
1992
- 1992-05-21 DE DE4216775A patent/DE4216775A1/en not_active Withdrawn
-
1993
- 1993-05-13 ES ES93909976T patent/ES2088673T3/en not_active Expired - Lifetime
- 1993-05-13 EP EP93909976A patent/EP0642573B1/en not_active Expired - Lifetime
- 1993-05-13 JP JP51988693A patent/JP3565842B2/en not_active Expired - Lifetime
- 1993-05-13 WO PCT/EP1993/001192 patent/WO1993023514A1/en active IP Right Grant
- 1993-05-13 DE DE59303031T patent/DE59303031D1/en not_active Expired - Lifetime
- 1993-05-13 AT AT93909976T patent/ATE139559T1/en not_active IP Right Cessation
- 1993-05-13 KR KR1019940704187A patent/KR100278221B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE4216775A1 (en) | 1993-11-25 |
| KR100278221B1 (en) | 2001-04-02 |
| KR950701677A (en) | 1995-04-28 |
| ATE139559T1 (en) | 1996-07-15 |
| WO1993023514A1 (en) | 1993-11-25 |
| ES2088673T3 (en) | 1996-08-16 |
| JPH07508773A (en) | 1995-09-28 |
| DE59303031D1 (en) | 1996-07-25 |
| EP0642573A1 (en) | 1995-03-15 |
| JP3565842B2 (en) | 2004-09-15 |
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