EP0294694B1 - Aquoeus stable suspensions of water insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning compositions - Google Patents
Aquoeus stable suspensions of water insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning compositions Download PDFInfo
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- EP0294694B1 EP0294694B1 EP88108736A EP88108736A EP0294694B1 EP 0294694 B1 EP0294694 B1 EP 0294694B1 EP 88108736 A EP88108736 A EP 88108736A EP 88108736 A EP88108736 A EP 88108736A EP 0294694 B1 EP0294694 B1 EP 0294694B1
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- EP
- European Patent Office
- Prior art keywords
- component
- suspension
- ethylene oxide
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- suspension according
- Prior art date
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- 239000000725 suspension Substances 0.000 title claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title claims description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 16
- 238000005406 washing Methods 0.000 title description 7
- 238000004140 cleaning Methods 0.000 title description 6
- 150000004760 silicates Chemical class 0.000 title description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 239000003599 detergent Substances 0.000 claims description 20
- 239000004435 Oxo alcohol Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012459 cleaning agent Substances 0.000 claims description 16
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- -1 aluminum silicates Chemical class 0.000 description 30
- 239000000047 product Substances 0.000 description 16
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 5
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- RUYJNKYXOHIGPH-UHFFFAOYSA-N dialuminum;trioxido(trioxidosilyloxy)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] RUYJNKYXOHIGPH-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229920000847 nonoxynol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- DUUPDCPVCHSTFF-UHFFFAOYSA-N nonane Chemical compound [CH2]CCCCCCCC DUUPDCPVCHSTFF-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229940067739 octyl sulfate Drugs 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 239000001226 triphosphate 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
-
- 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
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- Sodium is preferred as the cation, but it can also be replaced by lithium, potassium, ammonium or magnesium.
- aluminum silicates The compounds defined above which are capable of binding calcium are referred to below as "aluminum silicates" for the sake of simplicity. This applies in particular to the sodium aluminum silicates to be used with preference; all statements made for their use according to the invention and all statements regarding their production and properties apply accordingly to the entirety of all the compounds defined above.
- the aluminum silicates particularly suitable for use in detergents and cleaning agents have a calcium binding capacity of preferably 50 to 200 mg CaO / g of the anhydrous aluminum silicate. If reference is made to anhydrous aluminum silicate in the following, it means the state of the aluminum silicate which is reached after drying for one hour at 800 ° C. During this drying, the adhering and bound water is practically completely removed.
- the aluminum silicates are used, for example, as an aqueous suspension delivered or used.
- suspension properties e.g. B. suspension stability and pumpability - the aluminum silicates dispersed in the aqueous phase still desirable.
- alkyl phenol ethylene adducts it is known to use alkyl phenol ethylene adducts to form aluminum silicate suspensions. For example, adducts with 6 to 7 moles of ethylene oxide are used (DE-OS 26 15 698).
- Both the primary and, in particular, the secondary degradation depend on the linearity of the carbon chain, which means that the degradation is generally worse the more branched the carbon chain is.
- nonylphenol ethoxylates used in DE-OS 32 09 631 are considered to be poorly biodegradable due to their benzene ring and their branched nonyl radical, there being in particular the risk that toxic nonylphenol is produced as a metastable degradation product. For this reason, the German detergent industry has decided not to use nonylphenol ethoxylates. In Switzerland, the use should be banned.
- the iso-tridecyl alcohol ethoxylates used in DE-OS 34 44 311, as the name suggests, are branched-chain oxo alcohols a degree of branching of at least 50%. These are unmanageable mixtures of isomers, often with all possible branches such as methyl, ethyl, propyl, iso-propyl and others
- component A can be crystalline.
- y can be a number from 1.3 to 4.
- the mixing ratio of the two components 1 and 2 can be 9 to 1 to 1 to 9.
- crystalline component A can be a type A zeolite.
- foam-suppressing additives or so-called solubilizers ie, compounds that improve the solubility of the added dispersant in the aqueous phase.
- foam-suppressing substances for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
- foam suppressors for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
- foam suppressors can be used as foam suppressors.
- foam suppressors for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
- foam suppressors for example foam-suppressing soap, silicone defoamers, foam-s
- solubilizing substances is generally not necessary, but it may be appropriate if the suspension according to the invention contains a hydrophilic, but sparingly water-soluble colloid, such as polyvinyl alcohol, as a stabilizing agent.
- Z is advantageous.
- B. a solubilizer - sodium toluenesulfonate or polyglycol ether are very suitable.
- the proportion of the solubilizer in the total suspension can, for example, be of the same order of magnitude as the proportion of the stabilizing agent.
- Other compounds suitable as solubilizers are generally known to the expert; Hydrotrophic agents such as, for example, benzenesulfonic acid, xylenesulfonic acid or their water-soluble salts or also octyl sulfate are suitable.
- the aluminum silicates of component A to be used can be amorphous or crystalline products, although mixtures of amorphous and crystalline products and also partially crystalline products can of course also be used.
- the aluminum silicates can be naturally occurring or else synthetically produced products, with the synthetically produced products being preferred.
- the production can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
- aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
- the desired aluminum silicates are also obtained by mixing the two components "in the solid state" in the presence of water.
- Aluminum silicates can also be prepared from Al (OH) 2, Al2O3 or SiO2 by reaction with alkali silicate or aluminate solutions
- the invention relates in particular to aluminum silicates which have a three-dimensional spatial lattice structure.
- the preferred calcium binding capacity which is approximately in the range from 100 to 200 mg CaO / g AS mostly around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition: 0.7 - 1.1 Na2O. Al2O3. 1.3-3.3 SiO2
- This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. These are: a) 0.7 - 1.1 Na2O. Al2O3. 1.3 - 2.4 SiO2 b) 0.7 - 1.1 Na2O. Al2O3. 2.4-3.3 SiO2
- the different crystal structures are shown in the X-ray diffraction diagram.
- the amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. B. dry 50 to 400 ° C. Depending on the drying conditions, the product contains more or less bound water.
- Such high drying temperatures are generally not recommended; expediently one does not go beyond 200 ° C if the aluminum silicate is intended for use in detergents and cleaning agents.
- the aluminum silicates do not need to be dried at all after their preparation in order to prepare a suspension according to the invention; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used.
- dried aluminum silicates can also be used to prepare suspensions according to the invention at medium temperatures, for example at 80 to 200 ° C., until the adhering liquid water has been removed.
- the particle size of the individual aluminum silicate particles can be different and z. B. are in the range between 0.1 ⁇ and 0.1 mm. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 ⁇ , in particular 8 to 0.1 ⁇ .
- These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 ⁇ m.
- Secondary particles are particles that are formed by aggregating the primary particles into larger structures.
- the use of the aluminum silicates which are still moist from their production for the production of the suspensions according to the invention has proven particularly useful since it has been found that the formation of agglomerates is practically completely prevented when these still moist products are used.
- powdered zeolite of type A with a particularly defined particle spectrum is used as component A.
- Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 are produced. They then have the particle distribution curves given there.
- a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.
- the concentration of component A can preferably be 44 to 55% by weight, in particular 46 to 52% by weight or more.
- the oxo alcohol ethoxylates can be mixed with one another in a ratio of 9: 1 to 1: 9, preferably 2: 3 to 3: 2, in particular 0.9: 1.1 to 1.1: 0.9.
- the concentration of this mixture in the aqueous suspension can preferably be from 1 to 2% by weight, in particular 1.4 to 1.6% by weight. This concentration is sufficient to stabilize a suspension with a solids content of 50% by weight or more.
- the suspension according to the invention has the advantage that it is stable to sedimentation in the temperature range from 10 to 50 ° C. and has a pumpable consistency.
- a further advantage is that the oxo alcohol ethoxylate is liquid at room temperature and therefore does not need to be heated.
- the known suspension according to DE-OS 26 15 698 has a lower sedimentation stability and, with the same type of incorporation, is not homogeneous at room temperature and is therefore more difficult to process.
- the aqueous suspensions can contain, in addition to the components A and B mentioned and, if appropriate, starting materials for the preparation of these components in comparatively small amounts. If the suspension is to be further processed into detergents and cleaning agents, the additional substances present are of course expediently substances which are suitable as constituents of detergents and cleaning agents.
- an indication of the stability of the suspension is provided by a simple test in which an aluminum silicate suspension of the desired concentration - e.g. B. 31% - is produced, which contains a dispersant according to the invention and optionally further substances, for example detergent components such as pentasodium triphosphate, in different amounts.
- a dispersant according to the invention e.g. B. 31% -
- further substances for example detergent components such as pentasodium triphosphate
- the amount of additives should be kept so that the suspension can still be pumped over again properly after 24 hours, preferably after 48 hours and in particular also after 72 hours in the storage container and pipe or hose lines.
- the settling behavior of the suspension which may also contain other constituents, is checked at room temperature. They are perfectly pumpable even after 4 or 8 days. This information on the stability of the suspension also only gives indications; It depends on the individual case which suspension stability is to be set.
- the suspensions can be prepared by simply mixing their components, the aluminum silicates e.g. B. as such or - if necessary from the manufacture - already moist or in aqueous suspension can be used. It is particularly advantageous to add component B to the aluminum silicates which are still moist from their manufacture, e.g. B. stir in as a filter cake.
- the suspensions according to the invention are distinguished by high stability and by further advantages. Their stabilizing effect is particularly valuable in the case of aluminum silicates with particle sizes of 5 to 30 ⁇ . They are pumpable so that they allow easy handling of moist aluminum silicates. Even after long interruptions in the pumping process, the suspensions can be pumped around perfectly. Because of their high stability, the suspensions can also be transported in conventional tank and tank wagons without fear of the formation of unusable or disruptive residues. This makes the suspensions ideal as a form of delivery of aluminum silicates for delivery to detergent manufacturers, for example.
- the suspensions can be stored at room temperature or at higher temperatures, pumped through pipes or transported in some other way.
- the suspensions are usually handled at temperatures between room temperature - usually preferred - and about 50 ° C.
- the suspensions according to the invention are particularly suitable for further processing to appear dry, pourable or free-flowing products, for example for the production of powdered aluminum silicates. There are no annoying residues when feeding the aqueous suspensions to the drying apparatus. It has also been shown that the suspensions of the invention enable processing to extremely dust-free products.
- suspensions of the invention are already as such, ie usable without further processing with or without further washing, bleaching and / or cleaning additives, for example as water softeners, detergents or cleaning agents and in particular as mild liquid abrasives with increased suspension stability.
- a particularly important use of the suspension is the further processing into dry-appearing, free-flowing or free-flowing detergents and cleaning agents which contain further compounds in addition to the suspension components.
- the suspensions according to the invention are particularly suitable for the production of powder detergents.
- an aqueous, flowable premix of the individual constituents of the agents is used and these are converted into a pourable product in the usual way.
- the aluminum silicates defined above are used in the form of the suspension according to the invention.
- the suspensions according to the invention can be processed into solid, pourable washing and cleaning agents by any known method.
- a suspension according to the invention - for example from a storage container - is mixed with at least one detergent, bleaching or cleaning component of the agent to be prepared, and the mixture is then mixed by any process converted into the powdered product.
- Complexing agent added ie a compound that is able to complexly bind the alkaline earth metal ions responsible for the water hardness, in particular magnesium and calcium ions.
- the suspension according to the invention is preferably combined with at least one water-soluble surfactant which does not belong to the possible components of component B.
- the suspensions according to the invention can be combined with substances capable of binding water of crystallization, expediently by spraying the suspension onto the compounds which are capable of binding water of crystallization and which are present in a mixer, so that a finally solid, dry-appearing product is obtained with constant mixing.
- the suspensions according to the invention mixed as a "slurry" are subjected to the atomization drying with at least one further washing, bleaching or cleaning compound.
- Detergents which have been produced using the suspension described above can be composed in various ways. In general, they contain at least one water-soluble surfactant which does not belong to the dispersants used according to the invention and which are present in the claimed aluminum silicate suspensions. In general, in addition to at least one further compound which has a washing, bleaching or cleaning action and is inorganic or organic, they contain an aluminum silicate as defined above as a calcium-binding compound. In addition, other customary auxiliaries and additives, which are usually present in smaller amounts, can be present in such agents.
- a Zeolit-A filter cake and stabilizer are stirred, optionally with the addition of water.
- oxo alcohols 23 the oxo alcohols with the carbon chains C12 / C13 are referred to as oxo alcohols 23.
- an oxo alcohol with C14 / C15 is an oxo alcohol 45 or an oxo alcohol with C12 / 15 an oxo alcohol 25.
- Oxo alcohol 23 - 4.5 / 5.5 denotes a 1: 1 mixture of the oxo alcohol C12 / C13 with 4.5 mol EO with an oxo alcohol C12 / C13 with 5.5 mol EO.
- the zeolite A concentration is 50% in all examples.
- Tridecyl alcohol ethoxylates with little branching which correspond in degree of branching to the oxo alcohol ethoxylates used according to the invention, are not suitable for slurry stabilization, as examples 9-33 show.
- the oxo alcohol ethoxylates used according to the invention are 80% linear and have only a methyl branch in the remaining 20%. For this reason, they have very good biodegradability.
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Description
Es wurden bereits Verfahren zum Waschen und Reinigen von festen Materialien, insbesondere von Textilien, sowie für die Durchführung der Verfahren geeignete Wasch- und Reinigungsmittel vorgeschlagen, bei welchen die Rolle der Calcium komplex bindenden Phosphate ganz oder teilweise von zum Binden von Calcium befähigten, feinverteilten, im allgemeinen gebundenes Wasser enthaltenden, wasserunlöslichen Aluminiumsilikaten übernommen wird (vgl. DE-OS 24 12 837).Processes for washing and cleaning solid materials, in particular textiles, and detergents and cleaning agents suitable for carrying out the processes have already been proposed, in which the role of the calcium complex-binding phosphates wholly or partly of finely divided, capable of binding calcium, water-insoluble aluminum silicates containing generally bound water is taken over (cf. DE-OS 24 12 837).
Es handelt sich dabei um Verbindungen der allgemeinen Formel I
(Kat2/nO)x . Me₂O₃ . (SiO₂)y (I)
in der Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5 Me Aluminium und y eine Zahl von 0,8 bis 6, vorzugsweise von 1,3 bis 4, bedeuten.These are compounds of the general formula I.
(Cat 2 / n O) x . Me₂O₃. (SiO₂) y (I)
in the cat a calcium-exchangeable cation of the valence n, x is a number from 0.7 to 1.5 Me aluminum and y is a number from 0.8 to 6, preferably from 1.3 to 4.
Als Kation kommt bevorzugt Natrium in Frage, es kann aber auch durch Lithium, Kalium, Ammonium oder Magnesium ersetzt sein.Sodium is preferred as the cation, but it can also be replaced by lithium, potassium, ammonium or magnesium.
Die oben definierten, zum Binden von Calcium befähigten Verbindungen werden im folgenden der Einfachheit halber als "Aluminiumsilikate" bezeichnet. Dies gilt insbesondere auch für die bevorzugt zu verwendenden Natriumaluminiumsilikate; alle für deren erfindungsgemäße Verwendung gemachten Angaben und sämtliche Angaben über deren Herstellung und Eigenschaften gelten entsprechend für die Gesamtheit aller oben definierten Verbindungen.The compounds defined above which are capable of binding calcium are referred to below as "aluminum silicates" for the sake of simplicity. This applies in particular to the sodium aluminum silicates to be used with preference; all statements made for their use according to the invention and all statements regarding their production and properties apply accordingly to the entirety of all the compounds defined above.
Die für den Einsatz in Wasch- und Reinigungsmitteln besonders geeigneten Aluminiumsilikate besitzen ein Calciumbindevermögen von vorzugsweise 50 bis 200 mg CaO/g des wasserfreien Aluminiumsilikates. Wenn im folgenden auf wasserfreies Aluminiumsilikat Bezug genommen wird, so ist damit der Zustand der Aluminiumsilikate gemeint, der nach einstündigem Trocknen bei 800 °C erreicht wird. Bei dieser Trocknung wird das anhaftende und das gebundene Wasser praktisch völlig entfernt.The aluminum silicates particularly suitable for use in detergents and cleaning agents have a calcium binding capacity of preferably 50 to 200 mg CaO / g of the anhydrous aluminum silicate. If reference is made to anhydrous aluminum silicate in the following, it means the state of the aluminum silicate which is reached after drying for one hour at 800 ° C. During this drying, the adhering and bound water is practically completely removed.
Bei der Herstellung von Wasch- oder Reinigungsmitteln, in denen neben üblichen Bestandteilen derartiger Mittel die oben definierten Aluminiumsilikate vorliegen, wird vorteilhaft von Aluminiumsilikaten ausgegangen, die feucht sind, beispielsweise noch von ihrer Herstellung her. Man vermischt dabei die feuchten Verbindungen wenigstens mit einem Teil der übrigen Bestandteile des herzustellenden Mittels und überführt das Gemisch durch bekannte Maßnahmen, wie zum Beispiel sprühtrocknen in das fertige Wasch- oder Reinigungsmittel als Endprodukt, beispielsweise in ein schüttfähiges Produkt.In the production of detergents or cleaning agents, in which the aluminum silicates defined above are present in addition to the usual constituents of such agents, aluminum silicates which are moist, for example still from their production, are advantageously used. The moist compounds are mixed with at least some of the other constituents of the agent to be prepared and the mixture is transferred by known measures, such as spray drying, into the finished washing or cleaning agent as the end product, for example into a pourable product.
Im Rahmen des vorstehend skizzierten Herstellungsverfahrens für Wasch- oder Reinigungsmittel werden die Aluminiumsilikate beispielsweise als wässrige Suspension angeliefert bzw. eingesetzt. Dabei wären gewisse Verbesserungen der Suspensionseigenschaften - z. B. Suspensionsstabilität und der Pumpbarkeit - der in wässriger Phase dispergierten Aluminiumsilikate noch erwünscht.As part of the manufacturing process for detergents or cleaning agents outlined above, the aluminum silicates are used, for example, as an aqueous suspension delivered or used. There would be certain improvements in suspension properties - e.g. B. suspension stability and pumpability - the aluminum silicates dispersed in the aqueous phase still desirable.
Es ist bekannt zur Bildung von Aluminiumsilikatsuspensionen Alkylphenoläthylenaddukte zu verwenden. Zum Beispiel werden Addukte mit 6 bis 7 Mol Äthylenoxid verwendet (DE-OS 26 15 698).It is known to use alkyl phenol ethylene adducts to form aluminum silicate suspensions. For example, adducts with 6 to 7 moles of ethylene oxide are used (DE-OS 26 15 698).
Aufgrund des steigenden ökologischen Bewußtseins wird zunehmendes Augenmerk auf die biologische Abbaubarkeit gelegt. Neben dem primärabbau, dem Verlust der grenzflächenaktiven Eigenschaften, steht immer mehr auch der Sekundärabbau, die Mineralisierung, im Vordergrund.Due to the increasing ecological awareness, increasing attention is being paid to biodegradability. In addition to primary mining, the loss of surface-active properties, secondary mining, mineralization, is becoming increasingly important.
Sowohl der primäre als auch insbesondere der sekundäre Abbau sind von der Linearität der Kohlenstoffkette abhängig, das heißt, daß der Abbau in der Regel um so schlechter ist, je verzweigter die Kohlenstoffkette ist.Both the primary and, in particular, the secondary degradation depend on the linearity of the carbon chain, which means that the degradation is generally worse the more branched the carbon chain is.
Die in DE-OS 32 09 631 eingesetzten Nonylphenolethoxylate gelten aufgrund ihres Benzolringes und ihres verzweigten Nonyl-Rests als schlecht abbaubar, wobei insbesondere-die Gefahr besteht, daß toxisches Nonylphenol als metastabiles Abbauprodukt entsteht. Auf die Verwendung von Nonylphenolethoxylaten wurde aus diesem Grund von der deutschen Waschmittelindustrie verzichtet. In der Schweiz soll die Verwendung verboten werden.The nonylphenol ethoxylates used in DE-OS 32 09 631 are considered to be poorly biodegradable due to their benzene ring and their branched nonyl radical, there being in particular the risk that toxic nonylphenol is produced as a metastable degradation product. For this reason, the German detergent industry has decided not to use nonylphenol ethoxylates. In Switzerland, the use should be banned.
Bei den in DE-OS 34 44 311 verwendeten iso-Tridecylalkoholethoxylaten handelt es sich, wie der Name schon sagt, um verzweigt-kettige Oxoalkohole mit einem Verzweigungsgrad von mindestens 50 %. Dabei handelt es sich um unüberschaubare Isomerengemische, oft mit allen möglichen Verzweigungen wie Methyl, Äthyl, Propyl, iso-Propyl u. a.The iso-tridecyl alcohol ethoxylates used in DE-OS 34 44 311, as the name suggests, are branched-chain oxo alcohols a degree of branching of at least 50%. These are unmanageable mixtures of isomers, often with all possible branches such as methyl, ethyl, propyl, iso-propyl and others
Es bestand somit das Vorurteil, daß sich bevorzugt nur solche verzweigten Tenside zur Zeolith-A-Slurry -Stabilisierung eignen.There was therefore the prejudice that preferably only such branched surfactants are suitable for stabilizing zeolite A slurry.
Es wurde nun gefunden, daß bestimmte Mischungen von weitgehend linearen Oxoalkoholethoxylaten in ganz besonderem Maße die Fähigkeit besitzen, Suspensionen der obigen Calcium bindenden Aluminiumsilikate derart zu stabilisieren, daß diese selbst bei hohem Feststoffgehalt lange Zeit stabil und auch nach langem Stehen noch einwandfrei pumpbar sind. Überraschenderweise hat sich gezeigt, daß diese bestimmten Mischungen in der Lage sind, sogar feuchte Aluminiumsilikate, die einen Wassergehalt von 70 % und weniger aufweisen, über längere Zeit ohne Rühren sedimentationsstabil zu halten.It has now been found that certain mixtures of largely linear oxoalcohol ethoxylates have a very particular ability to stabilize suspensions of the above calcium-binding aluminum silicates in such a way that they are stable for a long time even at a high solids content and can still be pumped perfectly even after standing for a long time. Surprisingly, it has been shown that these certain mixtures are capable of keeping even moist aluminum silicates, which have a water content of 70% and less, sedimentation-stable over a long period of time without stirring.
Gegenstand der Erfindung ist eine wässrige, pumpfähige, stabile Suspension eines wasserunlöslichen, zum Binden von Calciumionen befähigten Silikates die, bezogen auf das Gesamtgewicht der wäßrigen Suspension,
- A) als zum Binden von Calcium befähigtes Silikat 0,5 bis 80 Gewichtsprozent einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen Verbindung der allgemeinen Formel
(Kat2/nO)x · Me₂O₃ · (SiO₂)y (I),
in der Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5 Me Bor oder Aluminium und y eine Zahl von 0,8 bis 6 bedeuten, enthält, welche dadurch gekennzeichnet ist, daß sie - B) als dispergierend wirkenden Bestandteil 0,5 bis 6 Gewichtsprozent einer Mischung aus mindestens zwei Komponenten 1 und 2 der Formel II
R-(OCH₂CH₂)n-OH,
enthält,
wobei R = C₁₀-C₁₅ Alkyl mit einem Verzweigungsgrad von maximal 25 %, d. h., daß maximal 25 % des Fettalkoholethoxylates eine einfache Methylverzweigung aufweisen
n = 4 - 5,0 Mol EO bei Komponente 1
n = 5,5 - 7 Mol EO bei Komponente 2
bedeuten, die Komponente 1 eine Mischung zweier verschiedener Oxoalkoholethoxylate mit 4 bis 5 Mol Ethylenoxid und dem Trübungspunkt 62 bis 67 °C ist und die Kohlenstoffkette R 12 bis 13 C-Atome aufweist und die Komponente 2 eine Mischung zweier verschiedener Oxoalkoholethoxylate mit 5,5 bis 7 Mol Ethylenoxid und dem Trübungspunkt 70 bis 80 °C, bevorzugt mit 5,5 bis 6,5 Mol EO und dem Trübungspunkt 71 bis 79 °C ist und die Kohlenstoffkette R 10 bis 15, bevorzugt 12 bis 15 C-Atome aufweist.
- A) as a silicate capable of binding calcium 0.5 to 80 percent by weight of a finely divided, bound water-containing, synthetically produced, water-insoluble compound of the general formula
(Kat 2 / n O) x · Me₂O₃ · (SiO₂) y (I),
in the cat a calcium-exchangeable cation of the valence n, x is a number from 0.7 to 1.5 Me boron or aluminum and y is a number from 0.8 to 6, which is characterized in that it - B) as a dispersing component 0.5 to 6 percent by weight of a mixture of at least two components 1 and 2 of the formula II
R- (OCH₂CH₂) n -OH,
contains
where R = C₁₀-C₁₅ alkyl with a degree of branching of at most 25%, ie that at most 25% of the fatty alcohol ethoxylate have a simple methyl branch
n = 4 - 5.0 mol EO for component 1
n = 5.5 - 7 mol EO for component 2
mean, component 1 is a mixture of two different oxo alcohol ethoxylates with 4 to 5 moles of ethylene oxide and the cloud point is 62 to 67 ° C and the carbon chain R has 12 to 13 carbon atoms and component 2 is a mixture of two different oxo alcohol ethoxylates with 5.5 to 7 moles of ethylene oxide and the cloud point is 70 to 80 ° C., preferably 5.5 to 6.5 moles of EO and the cloud point is 71 to 79 ° C., and the carbon chain R has 10 to 15, preferably 12 to 15, carbon atoms.
In der erfindungsgemäßen Suspension kann die Komponente A kristallin sein.In the suspension according to the invention, component A can be crystalline.
In der Formel I der Komponente A kann y eine Zahl von 1,3 bis 4 bedeuten. Das Mischungsverhältnis der beiden Komponenten 1 und 2 kann 9 zu 1 bis 1 zu 9 betragen.In formula I of component A, y can be a number from 1.3 to 4. The mixing ratio of the two components 1 and 2 can be 9 to 1 to 1 to 9.
Die kristalline Komponente A kann in einer bevorzugten Ausführung ein Zeolith des Typs A sein.In a preferred embodiment, crystalline component A can be a type A zeolite.
Die vorstehend genannten Verbindungen sind die wesentlichen Bestandteile der erfindungsgemäßen Suspension. Es können jedoch auch weitere Bestandteile enthalten sein, so z. B. schaumdämpfende Zusätze bzw. sogenannte Lösungsvermittler, d. h., Verbindungen, die die Löslichkeit der zugesetzten Dispergiermittel in der wässrigen Phase verbessern. Als Schaumdämpfer können die üblichen schaumdämpfenden Substanzen, beispielsweise schaumdämpfende Seife, Silikonentschäumer, schaumdämpfende Triazinderivate, die sämtlich der Fachwelt bekannt und geläufig sind, eingesetzt werden. Ein derartiger Zusatz ist im allgemeinen nicht erforderlich; bei schäumenden Dispergiermitteln kann er jedoch - insbesondere bei höheren Alkylbenzolsulfonsäure -Einsatzmengen - erwünscht sein.The above-mentioned compounds are the essential components of the suspension according to the invention. It can however, other ingredients may also be included, e.g. B. foam-suppressing additives or so-called solubilizers, ie, compounds that improve the solubility of the added dispersant in the aqueous phase. The usual foam-suppressing substances, for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors. Such an addition is generally not necessary; in the case of foaming dispersants, however, it may be desirable, especially when using higher amounts of alkylbenzenesulfonic acid.
Auch ein Zusatz von lösungsvermittelnden Substanzen ist im allgemeinen nicht erforderlich, kann jedoch angezeigt sein, wenn die erfindungsgemäße Suspension als stabilisierendes Mittel ein hydrophiles, aber wenig in Wasser lösliches Kolloid wie beispielsweise Polyvinylalkohol enthält. Vorteilhaft wird z. B. ein Lösungsvermittler - sehr geeignet sind Natriumtoluolsulfonat oder Polyglykoläther - eingesetzt.The addition of solubilizing substances is generally not necessary, but it may be appropriate if the suspension according to the invention contains a hydrophilic, but sparingly water-soluble colloid, such as polyvinyl alcohol, as a stabilizing agent. Z is advantageous. B. a solubilizer - sodium toluenesulfonate or polyglycol ether are very suitable.
Der Anteil des Lösungsvermittlers an der Gesamtsuspension kann beispielsweise in der gleichen Größenordnung wie der Anteil des Stabilisierungsmittels liegen. Weitere als Lösungsvermittler geeignete Verbindungen sind der Fachwelt allgemein bekannt; hydrotrophe Mittel wie beispielsweise Benzolsulfonsäure, Xylolsulfonsäure bzw. deren wasserlösliche Salze oder auch Octylsulfat sind geeignet.The proportion of the solubilizer in the total suspension can, for example, be of the same order of magnitude as the proportion of the stabilizing agent. Other compounds suitable as solubilizers are generally known to the expert; Hydrotrophic agents such as, for example, benzenesulfonic acid, xylenesulfonic acid or their water-soluble salts or also octyl sulfate are suitable.
Bei sämtlichen Angaben zur "Konzentration der Aluminiumsilikate" zum "Feststoffgehalt" oder zum Gehalt an "Aktivsubstanz" (=AS) wird auf den Zustand der Aluminiumsilikate Bezug genommen, der nach einstündigem Trocknen bei 800 °C erreicht wird. Bei dieser Trocknung wird das anhaftende und das gebundene Wasser praktisch völlig entfernt.With all information on the "concentration of aluminum silicates" on the "solids content" or on the content of "active substance" (= AS), reference is made to the state of the aluminum silicates, which is reached after drying for one hour at 800 ° C. During this drying practically completely removes the adhering and bound water.
Bei den einzusetzenden Aluminiumsilikaten der Komponente A kann es sich um amorphe oder um kristalline Produkte handeln, wobei selbstverständlich auch Mischungen von amorphen und kristallinen Produkten und auch teilkristalline Produkte einsetzbar sind. Die Aluminiumsilikate können natürlich vorkommende oder aber synthetisch hergestellte Produkte sein, wobei die synthetisch hergestellten Produkte bevorzugt sind. Die Herstellung kann z. B. durch Reaktion von wasserlöslichen Silikaten mit wasserlöslichen Aluminaten in Gegenwart von Wasser erfolgen. Zu diesem Zweck können wässrige Lösungen der Ausgansmaterialien miteinander vermischt oder eine in festem Zustand vorliegende Komponente mit der anderen, als wässrige Lösung vorliegenden Komponente umgesetzt werden. Auch durch Vermischen beider, in festem Zustand vorliegender Komponente" erhält man bei Anwesenheit von Wasser die gewünschten Aluminiumsilikate. Auch aus Al(OH)₂, Al₂O₃ oder SiO₂ lassen sich durch Umsetzen mit Alkalisilikat- bzw. aluminatlösungen Aluminiumsilikate herstellen. Die Herstellung kann auch nach weiteren bekannten Verfahren erfolgen. Insbesondere bezieht sich die Erfindung auf Aluminiumsilikate, die eine dreidimensionale Raumgitterstruktur aufweisen.The aluminum silicates of component A to be used can be amorphous or crystalline products, although mixtures of amorphous and crystalline products and also partially crystalline products can of course also be used. The aluminum silicates can be naturally occurring or else synthetically produced products, with the synthetically produced products being preferred. The production can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution. The desired aluminum silicates are also obtained by mixing the two components "in the solid state" in the presence of water. Aluminum silicates can also be prepared from Al (OH) ₂, Al₂O₃ or SiO₂ by reaction with alkali silicate or aluminate solutions The invention relates in particular to aluminum silicates which have a three-dimensional spatial lattice structure.
Das bevorzugte, etwa im Bereich von 100 bis 200 mg CaO/g AS meist bei etwa 100 bis 180 mg CaO/g AS liegende Calciumbindevermögen findet sich vor allem bei Verbindungen der Zusammensetzung:
0,7 - 1,1 Na₂O . Al₂O₃ . 1,3 - 3,3 SiO₂
Diese Summenformel umfaßt zwei Typen verschiedener Kristallstrukturen (bzw. deren nicht kristalline Vorprodukte), die sich auch durch ihre Summenformeln unterscheiden. Es sind dies:
a) 0,7 - 1,1 Na₂O . Al₂O₃ . 1,3 - 2,4 SiO₂
b) 0,7 - 1,1 Na₂O . Al₂O₃ . 2,4 - 3,3 SiO₂
Die unterschiedlichen Kristallstrukturen zeigen sich im Röntgenbeugungsdiagramm.The preferred calcium binding capacity, which is approximately in the range from 100 to 200 mg CaO / g AS mostly around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition:
0.7 - 1.1 Na₂O. Al₂O₃. 1.3-3.3 SiO₂
This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. These are:
a) 0.7 - 1.1 Na₂O. Al₂O₃. 1.3 - 2.4 SiO₂
b) 0.7 - 1.1 Na₂O. Al₂O₃. 2.4-3.3 SiO₂
The different crystal structures are shown in the X-ray diffraction diagram.
Das in wässriger Suspension vorliegende amorphe oder kristalline Aluminiumsilikat läßt sich durch Filtration von der verbleibenden wässrigen Lösung abtrennen und bei Temperaturen von z. B. 50 bis 400 °C trocknen. Je nach den Trocknungsbedingungen enthält das Produkt mehr oder weniger gebundenes Wasser.The amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. B. dry 50 to 400 ° C. Depending on the drying conditions, the product contains more or less bound water.
Derart hohe Trocknungstemperaturen sind im allgemeinen nicht zu empfehlen; zweckmäßigerweise geht man nicht über 200 °C hinaus, wenn das Aluminiumsilikat für den Einsatz in Wasch- und Reinigungsmitteln vorgesehen ist. Die Aluminiumsilikate brauchen jedoch nach ihrer Herstellung zur Bereitung einer erfindungsgemäßen Suspension überhaupt nicht getrocknet zu werden; vielmehr kann - und dies ist besonders vorteilhaft - ein von der Herstellung noch feuchtes Aluminiumsilikat verwendet werden. Es lassen sich jedoch auch bei mittleren Temperaturen, beispielsweise bei 80 bis 200 °C, bis zur Entfernung des anhaftenden flüssigen Wassers getrocknete Aluminiumsilikate zur Bereitung erfindungsgemäßer Suspensionen verwenden.Such high drying temperatures are generally not recommended; expediently one does not go beyond 200 ° C if the aluminum silicate is intended for use in detergents and cleaning agents. However, the aluminum silicates do not need to be dried at all after their preparation in order to prepare a suspension according to the invention; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used. However, dried aluminum silicates can also be used to prepare suspensions according to the invention at medium temperatures, for example at 80 to 200 ° C., until the adhering liquid water has been removed.
Die Teilchengröße der einzelnen Aluminiumsilikatpartikel kann verschieden sein und z. B. im Bereich zwischen 0,1 µ und 0,1 mm liegen. Mit besonderem Vorteil verwendet man Aluminiumsilikate, die zu wenigstens 80 Gew.-% aus Teilchen einer Größe von 10 bis 0,01 µ, insbesondere von 8 bis 0,1 µ bestehen.The particle size of the individual aluminum silicate particles can be different and z. B. are in the range between 0.1 μ and 0.1 mm. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 μ, in particular 8 to 0.1 μ.
Vorzugsweise einthalten diese Aluminiumsilikate keine Primär- bzw. Sekundärteilchen mehr mit Durchmessern oberhalb von 45 µ. Als Sekundärteilchen werden Teilchen, die durch Aggregation der Primärteilchen zu größeren Gebilden entstanden sind, bezeichnet.These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 μm. Secondary particles are particles that are formed by aggregating the primary particles into larger structures.
Im Hinblick auf die Agglomeration der primärteilchen zu größeren Gebilden hat sich die Verwendung der von ihrer Herstellung noch feuchten Aluminiumsilikate zur Herstellung der erfindungsgemäßen Suspensionen besonders bewährt, da sich herausgestellt hat, daß bei Verwendung dieser noch feuchten Produkte eine Bildung von Agglomeraten praktisch vollständig unterbunden wird.With regard to the agglomeration of the primary particles into larger structures, the use of the aluminum silicates which are still moist from their production for the production of the suspensions according to the invention has proven particularly useful since it has been found that the formation of agglomerates is practically completely prevented when these still moist products are used.
In einer besonders bevorzugten Ausführungsvorm der Erfindung wird als Komponente A pulverförmiger Zeolith des Typs A mit besonders definiertem Teilchespektrum eingesetzt.In a particularly preferred embodiment of the invention, powdered zeolite of type A with a particularly defined particle spectrum is used as component A.
Derartige Zeolithpulver können gemäß DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 hergestellt werden. Sie weisen dann die dort angegebenen Teilchenverteilungskurven auf.Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 are produced. They then have the particle distribution curves given there.
In einer besonders bevorzugten Ausführungsform kann ein pulverförmiger Zeolith des Typs A verwendet werden, der die in der DE-OS 26 51 485 beschriebene Teilchengrößenverteilung aufweist.In a particularly preferred embodiment, a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.
Die Konzentration an Komponente A kann bevorzugt 44 bis 55 Gew.-%, insbesondere 46 bis 52 Gewichtsprozent und mehr betragen.The concentration of component A can preferably be 44 to 55% by weight, in particular 46 to 52% by weight or more.
Die Oxoalkoholethoxylate können in einem Verhältnis von 9 : 1 bis 1 : 9, vorzugsweise 2 : 3 bis 3 : 2, insbesondere 0,9 : 1,1 bis 1,1 : 0,9 miteinander vermischt sein.The oxo alcohol ethoxylates can be mixed with one another in a ratio of 9: 1 to 1: 9, preferably 2: 3 to 3: 2, in particular 0.9: 1.1 to 1.1: 0.9.
Die Konzentration dieser Mischung in der wässrigen Suspension kann vorzugsweise von 1 bis 2 Gew.-%, insbesondere 1,4 bis 1,6 Gew.-% betragen. Diese Konzentration ist ausreichend, eine Suspension mit einem Feststoffgehalt von 50 Gew.-% und mehr zu stabilisieren.The concentration of this mixture in the aqueous suspension can preferably be from 1 to 2% by weight, in particular 1.4 to 1.6% by weight. This concentration is sufficient to stabilize a suspension with a solids content of 50% by weight or more.
Die erfindungsgemäße Suspension weist den Vorteil auf, daß sie in dem Temperaturbereich von 10 bis 50 °C sedimentationsstabil ist und eine pumpfähige Konsistenz aufweist.The suspension according to the invention has the advantage that it is stable to sedimentation in the temperature range from 10 to 50 ° C. and has a pumpable consistency.
Von weiterem Vorteil ist, daß das Oxoalkoholethoxylat bei Raumtemperatur flüssig ist und daher nicht aufgeheizt werden braucht.A further advantage is that the oxo alcohol ethoxylate is liquid at room temperature and therefore does not need to be heated.
Von besonderem Vorteil ist, daß in der erfindungsgemäßen Suspension deutlich höhere Feststoffgehalte von 50 Gew.-% und mehr erreicht werden können.It is particularly advantageous that significantly higher solids contents of 50% by weight and more can be achieved in the suspension according to the invention.
Die bekannte Suspension gemäß DE-OS 26 15 698 weist eine geringere Sedimentationsstabilität auf und ist bei gleicher Einarbeitungsart bei Raumtemperatur nicht homogen und deshalb schlechter verarbeitbar.The known suspension according to DE-OS 26 15 698 has a lower sedimentation stability and, with the same type of incorporation, is not homogeneous at room temperature and is therefore more difficult to process.
Grundsätzlich können die wässrigen Suspensionen außer den genannten Bestandteilen A und B und außer gegebenenfalls von Ausgangsmaterialien für die Herstellung dieser Bestandteile in vergleichsweise geringen Mengen enthalten. Ist eine Weiterverarbeitung der Suspension zu Wasch- und Reinigungsmitteln vorgesehen, so handelt es sich bei den zusätzlich vorliegenden Stoffen natürlich zweckmäßigerweise um Stoffe, die als Bestandteile von Wasch- und Reinigungsmitteln geeignet sind.In principle, the aqueous suspensions can contain, in addition to the components A and B mentioned and, if appropriate, starting materials for the preparation of these components in comparatively small amounts. If the suspension is to be further processed into detergents and cleaning agents, the additional substances present are of course expediently substances which are suitable as constituents of detergents and cleaning agents.
Einen Anhaltspunkt über die Stabilität der Suspension gibt ein einfacher Test, bei welchem eine Aluminiumsilikatsuspension der gewünschten Konzentration - z. B. 31 %ig - hergestellt wird, die ein erfindungsgemäßes Dispergiermittel und gegebenenfalls weitere Stoffe, beispielsweise Waschmittelbestandteile wie Pentanatriumtriphosphat, in verschiedenen Mengen enthält. Der Einfluß des zugesetzten Stoffes kann dann im Absetzverhalten der Suspension visuell beobachtet werden. Nach 72stündigem Stehen soll eine bevorzugte Suspension im allgemeinen höchstens so weit abgesetzt sein, daß die überstehende klare bzw. von Silikatteilchen freie Lösung nicht mehr als 20 %, vorzugsweise nicht mehr als 10 %, insbesondere nicht mehr als 6 % der Gesamthöhe ausmacht.An indication of the stability of the suspension is provided by a simple test in which an aluminum silicate suspension of the desired concentration - e.g. B. 31% - is produced, which contains a dispersant according to the invention and optionally further substances, for example detergent components such as pentasodium triphosphate, in different amounts. The influence of the added substance can then be visually observed in the settling behavior of the suspension. After standing for 72 hours, a preferred suspension should generally be at most so far removed that the protruding clear or silicate-free solution does not make up more than 20%, preferably not more than 10%, in particular not more than 6% of the total height.
Im allgemeinen soll die Menge der Zusatzstoffe so gehalten werden, daß die Suspension nach 24stündigem, vorzugsweise nach 48stündigem und insbesondere auch nach 72stündigem Stehen in Vorratsbehälter und Rohr- bzw. Schlauchleitungen noch einwandfrei wieder umgepumpt werden kann. Das Absetzverhalten der gegebenenfalls noch weitere Bestandteile enthaltenden Suspension wird bei Raumtemperatur geprüft. Sie sind auch nach 4 bzw. 8 Tagen einwandfrei pumpfähig. Auch diese Angaben zur Suspensionsstabilität geben nur Anhaltspunkte; es hängt vom jeweiligen Einzelfall ab, welche Suspensionsstabilität einzustellen ist. Bei Verwendung der erfindungsgemäßen Suspension als Stammsuspension zur längeren Lagerung in einem Reservoir, aus welchem sie nach Bedarf durch Pumpen abgezogen werden kann, kann es zweckmäßig sein, den Anteil sonstiger Bestandteile beispielsweise von Wasch- und Feinigungsmitteln gering zu halten oder auf diese ganz zu verzichten.In general, the amount of additives should be kept so that the suspension can still be pumped over again properly after 24 hours, preferably after 48 hours and in particular also after 72 hours in the storage container and pipe or hose lines. The settling behavior of the suspension, which may also contain other constituents, is checked at room temperature. They are perfectly pumpable even after 4 or 8 days. This information on the stability of the suspension also only gives indications; It depends on the individual case which suspension stability is to be set. When using the suspension according to the invention as a stock suspension for longer storage in a reservoir, from which it can be drawn off by pumping as required, it may be expedient to keep the proportion of other constituents, for example detergents and cleaning agents, low or to dispense with them entirely.
Die Suspensionen können durch einfaches Vermischen ihrer Bestandteile hergestellt werden, wobei die Aluminiumsilikate z. B. als solche oder - gegebenenfalls von der Herstellung her - bereits feucht bzw. in wässriger Suspension befindlich eingesetzt werden könnnen. Besonders vorteilhaft ist es, die Komponente B in die von ihrer Herstellung her noch feuchten Aluminiumsilikate z. B. als Filterkuchen einzurühren.The suspensions can be prepared by simply mixing their components, the aluminum silicates e.g. B. as such or - if necessary from the manufacture - already moist or in aqueous suspension can be used. It is particularly advantageous to add component B to the aluminum silicates which are still moist from their manufacture, e.g. B. stir in as a filter cake.
Es können aber selbstverständlich auch bereits getrocknete, d. h. von anhaftendem Wasser befreite, gegebenenfalls noch gebundenes Wasser aufweisende Aluminiumsilikate eingesetzt werden.However, it is of course also possible to use aluminum silicates which have already been dried, that is to say freed from adhering water and which may still have bound water.
Die erfindungsgemäßen Suspensionen zeichnen sich durch hohe Stabilität und durch weitere Vorteile aus. Ihre stabilisierende Wirkung ist insbesondere bei Aluminiumsilikaten mit Teilchengrößen von 5 bis 30 µ besonders wertvoll. Sie sind pumpbar, so daß sie eine einfache Handhabung feuchter Aluminiumsilikate ermöglichen. Selbstnnach längeren Unterbrechungen im Pumpvorgang sind die Suspensionen einwandfrei umpumpbar. Aufgrund ihrer hohen Stabilität sind die Suspensionen auch in üblichen Tank- und Kesselwagen transportierbar, ohne daß dabei eine Bildung unbrauchbarer bzw. störender Rückstände zu befürchten ist. Damit sind die Suspensionen hervorragend als eine Lieferform von Aluminiumsilikaten für die Lieferung an beispielsweise Waschmittelhersteller geeignet.The suspensions according to the invention are distinguished by high stability and by further advantages. Their stabilizing effect is particularly valuable in the case of aluminum silicates with particle sizes of 5 to 30 µ. They are pumpable so that they allow easy handling of moist aluminum silicates. Even after long interruptions in the pumping process, the suspensions can be pumped around perfectly. Because of their high stability, the suspensions can also be transported in conventional tank and tank wagons without fear of the formation of unusable or disruptive residues. This makes the suspensions ideal as a form of delivery of aluminum silicates for delivery to detergent manufacturers, for example.
Die Suspensionen lassen sich bei Raumtemperatur oder auch bei höheren Temperaturen aufbewahren, durch Rohrleitungen pumpen oder auf andere Weise transportieren. Meist erfolgt die Handhabung der Suspensionen bei Temperaturen zwischen Raumtemperatur - meist bevorzugt - und etwa 50 °C.The suspensions can be stored at room temperature or at higher temperatures, pumped through pipes or transported in some other way. The suspensions are usually handled at temperatures between room temperature - usually preferred - and about 50 ° C.
Besonders geeignet sind die erfindungsgemäßen Suspensionen für die Weiterverarbeitung zu trocken erscheinenden, schütt- bzw. rieselfähigen Produkten, also beispielsweise zur Herstellung von pulverförmigen Aluminiumsilikaten. Es treten keine lästigen Rückstände bei der Zufuhr der wäßrigen Suspensionen zur Trocknungsapparatur auf. Ferner hat sich gezeigt, daß die Suspensionen der Erfindung eine Verarbeitung zu außerordentlich staubfreien Produkten ermöglichen.The suspensions according to the invention are particularly suitable for further processing to appear dry, pourable or free-flowing products, for example for the production of powdered aluminum silicates. There are no annoying residues when feeding the aqueous suspensions to the drying apparatus. It has also been shown that the suspensions of the invention enable processing to extremely dust-free products.
Aufgrund ihrer besonderen Stabilität sind die erfindungsgemäßen Suspensionen bereits als solche, d. h. ohne weitere Verarbeitung mit oder ohne weitere waschend, bleichend und/oder reinigend wirkende Zusätze, beispielsweise als Wasserenthärtungsmittel, Wasch- oder Reinigungsmittel und insbesondere als milde flüssige Scheuermittel mit erhöhter Suspensionsstabilität verwendbar.Because of their particular stability, the suspensions of the invention are already as such, ie usable without further processing with or without further washing, bleaching and / or cleaning additives, for example as water softeners, detergents or cleaning agents and in particular as mild liquid abrasives with increased suspension stability.
Eine besonders wichtige Verwendung der Suspension ist die Weiterverarbeitung zu trocken erscheinenden, schütt- bzw. rieselfähigen Wasch- und Reinigungsmitteln, die neben den Suspensionsbestandteilen weitere Verbindungen enthalten.A particularly important use of the suspension is the further processing into dry-appearing, free-flowing or free-flowing detergents and cleaning agents which contain further compounds in addition to the suspension components.
Die erfindungsgemäßen Suspensionen sind insbesondere zur Herstellung von pulverförmigen Wasch- und Reinigungsmitteln geeignet.The suspensions according to the invention are particularly suitable for the production of powder detergents.
Zur Herstellung dieser Mittel geht man von einer wäßrigen, fließfähigen Vormischung der einzelnen Bestandteile der Mittel aus und führt diese auf übliche Weise in ein schüttfähiges Produkt über. Dabei werden die oben definierten Aluminiumsilikate in From der erfindungsgemäßen Suspension eingesetzt. Die erfindungsgemäßen Suspensionen können nach beliebigen bekannten Verfahren zu den festen, schüttfähigen Wasch- und Reinigungsmitteln verarbeitet werden.To prepare these agents, an aqueous, flowable premix of the individual constituents of the agents is used and these are converted into a pourable product in the usual way. The aluminum silicates defined above are used in the form of the suspension according to the invention. The suspensions according to the invention can be processed into solid, pourable washing and cleaning agents by any known method.
Insbesondere geht man bei der Herstellung von pulverförmigen, rieselfähigen Wasch- und Reinigungsmitteln so vor, daß man eine erfindungsgemäße Suspension - beispielsweise aus einem Vorratsbehälter - mit wenigstens einem waschend, bleichend oder reinigend wirkenden Bestandteil des herzustellenden Mittels vermischt und das Gemisch anschließend nach einem beliebigen Verfahren in das pulverförmige Produkt überführt. Vorteilhaft wird ein Komplexbildner zugesetzt, d. h. eine Verbindung, die die für die Wasserhärte verantwortlichen Erdalkalimetallionen, insbesondere Magnesium- und Calciumionen komplex zu binden vermag.In particular, in the production of powdery, free-flowing detergents and cleaning agents, a suspension according to the invention - for example from a storage container - is mixed with at least one detergent, bleaching or cleaning component of the agent to be prepared, and the mixture is then mixed by any process converted into the powdered product. One will be advantageous Complexing agent added, ie a compound that is able to complexly bind the alkaline earth metal ions responsible for the water hardness, in particular magnesium and calcium ions.
Im allgemeinen wird bei der Herstellung von Wasch- und Reinigungsmitteln die erfindungsgemäße Suspension vorzugsweise mit wenigstens einem nicht zu den möglichen Bestandteilen der Komponente B gehörenden wasserlöslichen Tensid vereinigt.In general, in the production of detergents and cleaning agents, the suspension according to the invention is preferably combined with at least one water-soluble surfactant which does not belong to the possible components of component B.
Bei der Herstellung von Wasch- und Reinigungsmitteln gibt es verschiedene Varianten.There are different variants in the manufacture of detergents and cleaning agents.
Beispielsweise können die erfindungsgemäßen Suspensionen mit zur Bindung von Kristallwasser befähigten Substanzen vereinigt werden, zweckmäßigerweise durch Aufspühren der Suspension auf die in einem Mischer vorgelegten, zur Bindung von Kristallwasser befähigten Verbindungen, so daß bei ständigem Durchmischen ein schließlich festes, trocken erscheinendes Produkt erhalten wird. Vorzugsweise werden die erfindungsgemäßen Suspensionen jedoch, als "Slurry" vermischt, mit wenigstens einer weiteren waschend, bleichend oder reinigend wirkenden Verbindung der Zerstäubungstrocknung unterworfen. Hierbei zeigen sich weitere überraschende Vorteile der beanspruchten Aluminiumsilikat-Suspension. Es hat sich nämlich gezeigt, daß bei Einsatz erfindungsgemäßer Suspensionen bei der Zerstäubungstrocknung sehr staubarme Produkte erhalten werden können. Die durch Zerstäubungstrocknung erhaltenen Produkte weisen ein hohes Calciumbindevermögen auf und sind gut benetzbar.For example, the suspensions according to the invention can be combined with substances capable of binding water of crystallization, expediently by spraying the suspension onto the compounds which are capable of binding water of crystallization and which are present in a mixer, so that a finally solid, dry-appearing product is obtained with constant mixing. Preferably, however, the suspensions according to the invention, mixed as a "slurry", are subjected to the atomization drying with at least one further washing, bleaching or cleaning compound. This shows further surprising advantages of the claimed aluminum silicate suspension. It has been shown that very low-dust products can be obtained when using suspensions according to the invention in the spray drying. The products obtained by spray drying have a high calcium binding capacity and are easily wettable.
Waschmittel, die unter Verwendung der oben beschriebenen Suspension hergestellt worden sind, können auf verschiedenste Weise zusammengesetzt sein. Im allgemeinen enthalten sie wenigstens ein nicht zu den erfindungsgemäß eingesetzten Dispergiermitteln, die in den beanspruchten Aluminiumsilikat-Suspensionen vorliegen, gehörendes wasserlösliches Tensid. Allgemein enthalten sie neben wenigstens einer weiteren Verbindung, die waschend, bleichend oder reinigend wirkt und anorganisch oder organisch ist, als Calcium bindende Verbindung ein wie oben definiertes Aluminiumsilikat. Darüber hinaus können in derartigen Mitteln sonstige übliche, meist in geringeren Mengen anwesende Hilfs- und Zusatzstoffe vorhanden sein.Detergents which have been produced using the suspension described above can be composed in various ways. In general, they contain at least one water-soluble surfactant which does not belong to the dispersants used according to the invention and which are present in the claimed aluminum silicate suspensions. In general, in addition to at least one further compound which has a washing, bleaching or cleaning action and is inorganic or organic, they contain an aluminum silicate as defined above as a calcium-binding compound. In addition, other customary auxiliaries and additives, which are usually present in smaller amounts, can be present in such agents.
Es wird ein Zeolit-A-Filterkuchen und Stabilisator verrührt, gegebenenfalls unter Zusatz von Wasser.A Zeolit-A filter cake and stabilizer are stirred, optionally with the addition of water.
Als Stabilisator werden Verbindungen entsprechend der Formel II verwendet. Angegeben wird der Ethoxylierungsgrad EO. Der eingesetzte Zeolith-A-Filterkuchen wird gemäß DE-OS 26 51 485 hergestellt und weist das dort angegebene Teilchenspektrum auf.Compounds corresponding to formula II are used as stabilizers. The degree of ethoxylation EO is given. The zeolite A filter cake used is produced according to DE-OS 26 51 485 and has the particle spectrum specified there.
Für die Durchführung der Beispiele werden 50 kg unstabilisierter Zeolithsuspension mit einem Ekato -Standardmix-Rührer, ausgerüstet mit einer Flügelscheibe, eine Stunde bei 500 µ/min, gegebenenfalls unter Zusatz von Wasser, aufgerührt.To carry out the examples, 50 kg of unstabilized zeolite suspension are stirred with an Ekato standard mix stirrer, equipped with a wing disc, for one hour at 500 μ / min, if appropriate with the addition of water.
Nach Zugabe von 1,5 Gew.-% Stabilisatorgemisch wird 10 Minuten bei gleicher Geschwindigkeit weitergerührt.After adding 1.5% by weight of stabilizer mixture, stirring is continued for 10 minutes at the same rate.
Die Auswertung erfolgt, wie die Tabelle I veranschaulicht, nach 3 Tagen.As Table I illustrates, the evaluation is carried out after 3 days.
Die Trübungspunkte der eingesetzten Stabilisatoren sind in der Tabelle I beschrieben.
In den nachfolgenden Tabellen II bis VIII werden die Oxoalkohole mit den Kohlenstoffketten C₁₂/C₁₃ als Oxoalkohole 23 bezeichnet.In the following tables II to VIII, the oxo alcohols with the carbon chains C₁₂ / C₁₃ are referred to as oxo alcohols 23.
Entsprechend ist ein Oxoalkohol mit C₁₄/C₁₅ ein Oxoalkohol 45 bzw. ein Oxoalkohol mit C₁₂/₁₅ ein Oxoalkohol 25.Correspondingly, an oxo alcohol with C₁₄ / C₁₅ is an oxo alcohol 45 or an oxo alcohol with C₁₂ / ₁₅ an oxo alcohol 25.
Oxoalkohol 23 - 4,5/5,5 bezeichnet eine 1 : 1-Mischung des Oxoalkoholes C₁₂/C₁₃ mit 4,5 Mol EO mit einem Oxoalkohol C₁₂/C₁₃ mit 5,5 Mol EO.Oxo alcohol 23 - 4.5 / 5.5 denotes a 1: 1 mixture of the oxo alcohol C₁₂ / C₁₃ with 4.5 mol EO with an oxo alcohol C₁₂ / C₁₃ with 5.5 mol EO.
Die Zeolith-A-Konzentration beträgt bei allen Beispielen 50 %.The zeolite A concentration is 50% in all examples.
Die mit dem Hinweis 
Wenig verzweigte Tridecylalkoholethoxylate, die im Verzweigungsgrad den erfindungsgemäß eingesetzten Oxoalkoholethoxylaten entsprechen, sind nicht zur Slurry-Stabilisierung geeignet, wie die Beispie 9 - 33 belegen.Tridecyl alcohol ethoxylates with little branching, which correspond in degree of branching to the oxo alcohol ethoxylates used according to the invention, are not suitable for slurry stabilization, as examples 9-33 show.
Aus diesem Grund war es überraschend, daß eine Kombination aus eben diesen wenig verzweigten Produkten, wie die erfindungsgemäß eingesetzten, einen Zeolith A-Slurry hervorragend stabilisieren kann.For this reason, it was surprising that a combination of precisely these little branched products, such as those used according to the invention, can excellently stabilize a zeolite A slurry.
Die erfindungsgemäß eingesetzten Oxoalkoholethoxylaten sind zu 80 % linear und weisen bei den restlichen 20 % nur eine Methyl-Verzweigung auf. Sie besitzen aus diesem Grund eine sehr gute biologische Abbaubarkeit.The oxo alcohol ethoxylates used according to the invention are 80% linear and have only a methyl branch in the remaining 20%. For this reason, they have very good biodegradability.
Claims (6)
- Aqueous pumpable stable suspension of a water-insoluble silicate capable of binding calcium ions, which contains, based on the total weight of the aqueous suspensionA) as the silicate capable of binding calcium, 0.5 to 80 per cent by weight of a finely divided synthetically produced water-insoluble compound, containing bound water, of the general formula
(Cat2/nO)x·Me₂O₃·(SiO₂)y (I),
in which Cat denotes a cation, of valency n, capable of replacement by calcium, x denotes a number from 0.7 to 1.5, Me denotes boron or aluminium and y denotes a number from 0.8 to 6, characterised in that it containsB) as the constituent having a dispersing action, 0.5 to 6 per cent by weight of a mixture of at least two components 1 and 2 of the formula II
R-(OCH₂CH₂)n-OH
where R is C₁₀-C₁₅-alkyl having a degree of branching of at most 25 %, i.e. at most 25 % of the fatty alcohol ethoxylate have a simple methyl branch,
n = 4 - 5.0 moles of ethylene oxide in component 1
and
n = 5.5 - 7 moles of ethylene oxide in component 2,
component 1 is a mixture of two different oxoalcohol ethoxylates containing 4 to 5 mol of ethylene oxide and the cloud point is 62 to 67°C and the carbon chain R has 12 to 13 C atoms and component 2 is a mixture of two different oxoalcohol ethoxylates containing 5.5 to 7 mol of ethylene oxide and the cloud point is 70 to 80°C, preferably containing 5.5 to 6.5 mol of ethylene oxide, and the cloud point is 71 to 79°C and the carbon chain R has 10 to 15, preferably 12 to 15 C atoms. - Suspension according to Claim 1, characterised in that component A is crystalline.
- Suspension according to Claims 1 or 2, characterised in that in formula I of component A, y denotes a number from 1.3 to 4.
- Suspension according to Claims 1 to 3, characterised in that component A is a zeolite A.
- Suspension according to Claims 1 to 4, characterised in that the ratio in which the two components 1 and 2 are mixed is from 9:1 to 1:9.
- Use of the aqueous suspension according to Claims 1 to 5 for the preparation of pulverulent detergents and cleaning agents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88108736T ATE97156T1 (en) | 1987-06-06 | 1988-06-01 | AQUEOUS STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF BINDING CALCIUM IONS AND THEIR USE IN THE MANUFACTURE OF DETERGENT AND CLEANING AGENTS. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3719042 | 1987-06-06 | ||
| DE3719042 | 1987-06-06 | ||
| EP88106557A EP0294574A3 (en) | 1987-06-06 | 1988-04-23 | Aqueous stable suspensions of water insoluble silicates capable of binding calcium ions, and their use in the production of washing and cleaning compositions |
| EP88106557 | 1988-04-23 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0294694A2 EP0294694A2 (en) | 1988-12-14 |
| EP0294694A3 EP0294694A3 (en) | 1989-05-10 |
| EP0294694B1 true EP0294694B1 (en) | 1993-11-10 |
Family
ID=25856395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88108736A Expired - Lifetime EP0294694B1 (en) | 1987-06-06 | 1988-06-01 | Aquoeus stable suspensions of water insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning compositions |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0294694B1 (en) |
| ES (1) | ES2045012T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4109501A1 (en) * | 1991-03-22 | 1992-09-24 | Degussa | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
| IT1250437B (en) * | 1991-07-01 | 1995-04-07 | Paolo Colombo | STABLE AND EASILY PUMPABLE ZEOLITE SUSPENSIONS |
| DE4124247A1 (en) * | 1991-07-22 | 1993-01-28 | Henkel Kgaa | METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT335035B (en) * | 1974-10-10 | 1977-02-25 | Henkel & Cie Gmbh | STABLE SUSPENSIONS OF WATER-INSOLUBLE, SILICATES CAPABLE OF BINDING CALCIUMIONS AND THEIR USE FOR THE MANUFACTURE OF DETERGENTS AND DETERGENTS |
| EP0015024A1 (en) * | 1979-02-16 | 1980-09-03 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing binary builder system |
| DE3444311A1 (en) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
-
1988
- 1988-06-01 EP EP88108736A patent/EP0294694B1/en not_active Expired - Lifetime
- 1988-06-01 ES ES88108736T patent/ES2045012T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0294694A2 (en) | 1988-12-14 |
| EP0294694A3 (en) | 1989-05-10 |
| ES2045012T3 (en) | 1994-01-16 |
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