EP3368645A1 - Granulates, method for the production and use thereof - Google Patents
Granulates, method for the production and use thereofInfo
- Publication number
- EP3368645A1 EP3368645A1 EP16785417.3A EP16785417A EP3368645A1 EP 3368645 A1 EP3368645 A1 EP 3368645A1 EP 16785417 A EP16785417 A EP 16785417A EP 3368645 A1 EP3368645 A1 EP 3368645A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- range
- alkyl
- general formula
- coom
- weight
- 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.)
- Granted
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 title claims description 30
- -1 alkali metal citrate Chemical class 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 18
- 238000009472 formulation Methods 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 13
- 238000004851 dishwashing Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000003599 detergent Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 5
- 239000002671 adjuvant Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005029 sieve analysis Methods 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- 238000011156 evaluation Methods 0.000 claims description 3
- 235000010603 pastilles Nutrition 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 229920000388 Polyphosphate Polymers 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 239000001205 polyphosphate Substances 0.000 claims 1
- 235000011176 polyphosphates Nutrition 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 239000013522 chelant Substances 0.000 abstract 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000007937 lozenge Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 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 4
- 239000000047 product Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003826 tablet Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003136 n-heptyl 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])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 229920006030 multiblock copolymer Polymers 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- KKVZONPEMODBBG-UHFFFAOYSA-N (1-hydroxydodecane-1,1-diyl)bis(phosphonic acid) Chemical compound CCCCCCCCCCCC(O)(P(O)(O)=O)P(O)(O)=O KKVZONPEMODBBG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 238000005406 washing 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
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids
-
- 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
-
- 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
- C11D1/721—End blocked ethers
-
- 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—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
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- 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
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
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- 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
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to a process for preparing a formulation which is solid up to a temperature of at least 60 ° C, characterized in that
- R 1 is selected from C 4 -C 20 -alkyl
- R 2 is selected from C 8 -C 20 -alkyl
- AO are in each case identical or different and selected from C 2 -C 4 -alkylene
- x is in the range of 5 to 100
- R 3 is -CH (COOM 1 ) -N (CH 2 COOM 1 ) 2 (II) in which the variables are defined as follows:
- R 3 is selected from C 1 -C 4 -alkyl, phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 ,
- M 1 is an alkali metal or a combination of at least two alkali metals, mixed in a mill and ground.
- the present invention relates to granules and their use.
- hydroxy mixed ethers are waxy-looking substances with a melting point below 60 ° C, below 50 ° C or even below 35 ° C. They are able to form supercooled melts, which show only a slight tendency to crystallize even after a long time. Some hydroxymix ethers are hygroscopic and, moreover, especially with small particle size, tend to stick. Although it is possible to improve the storage stability by adding a so-called anti-caking agent. However, these are in many cases incompatible with other ingredients of dishwasher formulations.
- Solid formulations for example powder granules containing hydroxy mixed ethers, may tend to stick or cake in some cases. With powders or granules serving as intermediates, such sticking or caking will make further processing difficult. In the case of powders or granules which serve as end products, that is to be delivered to the consumer, such sticking or baking leads to negative feedback.
- the process according to the invention is a process for the preparation of a formulation which is solid up to a temperature of at least 60 ° C.
- DSC differential scanning calorimetry
- the melting point for example by differential scanning calorimetry (DSC), advantageously with a heating rate of 10K / min ⁇ 1 K / min; Initial weight 6-7 mg; Purge gas 3 l IS / h, AI crucible, open).
- the method according to the invention comprises several steps.
- the method according to the invention is based on at least one nonionic surfactant of the general formula (I) which, in connection with the present invention, can also be called component (a),
- R is -CH (OH) -CH 2 - (AO) x R 2 (I) in which the variables are defined as follows:
- R 1 is selected from C 4 -C 20 -alkyl, preferably n-C 4 -C 20 -alkyl.
- Examples are n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, iso-dodecyl, n-tetradecyl, iso-tetradecyl, stearyl, palmityl, and n-eicosyl.
- Preferred examples are n-butyl, n-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, stearyl, palmityl, and n- eicosyl.
- Particularly preferred examples are n-octyl and n-decyl.
- R 2 is selected from C 8 -C 20 -alkyl, preferably n-C 2 -C 20 -alkyl, examples being n-octyl,
- Preferred examples are n-octyl, n-nonyl, n-decyl, n-undecyl, iso-Cn H23, n-dodecyl, is-dodecyl, n-tetradecyl, stearyl, palmityl and n-eicosyl.
- Particularly preferred examples are iso-Cn H 2 3-
- AO are each the same or different and selected from C 2 -C 4 -alkylene, for example
- AO is in each case identical and CH 2 -CH 2 -O, in short also "EO" x is in the range from 5 to 100, preferably 5 to 60, more preferably 10 to 50 and particularly preferably 20 to 40.
- (AO) x is selected from (CH 2 CH 2 O) xi, where x1 is in the range of 1 to 50.
- (AO) x is selected from
- (AO) x is selected from - (CH 2 CH 2 O) x 4 wherein x 4 is in the range of 10 to 50, AO is EO, and R 1 and R 2 are each selected from Ce-Cu-alkyl become.
- x, x1, x2, x3, x4 are each to be understood as average values, the number average being preferred. Therefore, x or x1 or x2 or x3 or x4, if present, may be a non-integer although individual molecules each have an integer number of AO units.
- R 1 is n-Cs-C-io-alkyl
- R 2 is Cs-C 12 -alkyl, straight-chain or iso-Cs-C 12 -alkyl
- x is in the range of 20 to 25.
- component (a) has a melting point in the range of 30 to 60 ° C, preferably 35 to 55 ° C.
- the melting point of component (a) can be measured as mentioned above.
- Component (a) is mixed with (B) at least one second substance, in the context of the present invention also called component (b), and which is selected from polyethylene glycol and nonionic surfactants, which are different from surfactants of the formula (I).
- polyethylene glycol are polyaddition products of ethylene oxide having an average molecular weight M w in the range of 1 .000 to 50,000 g / mol, preferably 2,000 to 20,000 g / mol.
- nonionic surfactants other than component (a) are alcohol alkoxylates, di- and multiblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitan with ethylene oxide or propylene oxide, and also alkyl glycosides.
- alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III)
- R 4 is selected from linear C 1 -C 4 -alkyl, preferably ethyl and more preferably methyl,
- R 5 selected from Cs-C22-alkyl, for example n-CsHiz, n-CioF i, n-Ci2H25, n-Ci4H29, n-Ci6H33
- R 6 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-
- Hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl, m and n are in the range of zero to 300, the sum of n and m is at least one.
- m is in the range of 1 to 100 and n is in the range of 0 to 30.
- Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
- Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (IV) where the variables are defined as follows:
- R 4 is identical or different and selected from linear C 1 -C 4 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
- R 7 is selected from C 6 -C 20 -alkyl, in particular n-CeHi 7, n-CioH 2 i, n-Ci 2 H 2 5, n-Ci4H 2 9, n-Ci6H 3 3,
- a is a number in the range of 1 to 6
- b is a number in the range of 4 to 20
- d is a number in the range of 4 to 25.
- these may be block copolymers or random copolymers, preference being given to block copolymers.
- suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
- suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters and isosorbitol esters.
- Further suitable nonionic surfactants are selected from di-fatty acid esters of polyethylene glycol, for example polyethyleneglycol esterified twice with stearic acid and having an average molecular weight M w in the range from 1500 to 2500 g / mol.
- alkyl polyglycosides are compounds of the general formula (VI)
- R 8 is hydrogen or C 1 -C 4 -alkyl, preferred are ethyl, n-propyl and isopropyl and also hydrogen,
- R 9 is - (CH 2 ) 2 -R 8
- G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, w is in the range of 1, 1 to 4, w being an average, in particular the number average.
- w is in the range of 1.1 to 2, and more preferably in the range of 1.2 to 1.8. It is preferred to determine w by high temperature gas chromatography (HTGC).
- HTGC high temperature gas chromatography
- component (b) has a melting point in the range of 35 to 70 ° C, preferably 50 to 65 ° C.
- the melting point of component (b) can also be measured by dynamic DSC.
- the melting point of component (a) is below that of component (b).
- component (a) and (b) are first mixed in the molten state.
- the temperature for mixing is chosen so that the lower-melting component - ie component (b) or preferably component (a) - is in the molten state.
- the higher melting component may be in the solid or molten state.
- Component (a) and component (b) are preferably mixed in the proportions intended for the formulation in question.
- component (a) is melted during mixing.
- Component (a) and component (b) are preferably mixed at a temperature which is at least 5 ° C. above the melting point of component (a), more preferably at least 10 ° C.
- component (a) and component (b) are mixed at a temperature at least 5 ° C above the temperature at which the higher melting component melts.
- mixing process one can proceed by introducing components (a) and (b) in solid form in a mixing vessel and heating with mixing, for example shaking or preferably with stirring, until the lower-melting component has melted. Thereafter, the mixing is continued until you perceive with unaided eye a homogeneous mixture, so neither separate particles nor streaks can recognize.
- suitable mixing vessels are stirred vessels such as stirred reactors and stirred tanks.
- the mixture obtained in the first step of the process according to the invention is prepared.
- this is understood to mean that the mixture from the first step is processed so that it is converted into solid particles having the desired dimensions.
- Preferred examples are pastilles, flakes, grindings, and combinations of at least two of the foregoing. If it is desired to ground the mixture obtainable in the first step of the process according to the invention, they are allowed to solidify first.
- Pastillation can be carried out, for example, by pouring a mixture obtained in the first step of the process according to the invention into a mold with corresponding wells and allowing the mixture to cool in the appropriate mold. Then remove the cooled mixture - just the lozenges - from the mold and poured again mixture into the mold.
- cooling belts are selected for pastillation.
- Pastilles may for example have a diameter in the range of 4 to 10 mm.
- Scaling can be done, for example, by using a flaking roller. The size of the flakes may vary depending on the product characteristics and the machine settings. As a rule, irregularly shaped scales are obtained. As average dimensions, for example, lengths in the range of 1 mm to 2 cm, widths of 1 mm to 1, 5 cm and thicknesses in the range of 0.5 mm to 3 mm are suitable.
- Examples of particularly suitable equipment for grinding are impact mills and cutting mills. When mixing in a mill you grind simultaneously.
- silicic acid or silicate in the context of the present invention also silica (c) or silicate (c) or more generally called component (c), and
- component (d) at least one auxiliary, also referred to as auxiliary (d) or component (d), wherein component (d) is selected from alkali metal citrate, for example trisodium citrate, alkali metal carbonate such as potassium carbonate or sodium carbonate, or at least one chelating agent, selected from compounds of general formula (II) R 3 -CH (COOM) -N (CH 2 COOM) 2 (II) in which the variables are defined as follows:
- R 3 is selected from C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, preferred are methyl, sec-butyl and isobutyl and very particularly preferably R 3 Methyl; furthermore phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 , M 1 is an alkali metal or a combination of at least two alkali metals, for example lithium, sodium, potassium, preferred are potassium, sodium and combinations of potassium and sodium, for example in a molar ratio in the range of 1: 2 to 2: 1, and most preferably M 1 is sodium.
- Silica (c) can be selected from precipitated silicas and fumed silicas.
- silicates (c) are sodium disilicate and sodium metasilicate, zeolites and phyllosilicates, especially those of the formula a-Na 2 Si 2 0s, ⁇ -Na 2 Si 2 0s and 5-Na 2 Si 2 0s.
- the auxiliary (c) used is either two different silica gels or two different silicates. Different silica gels or different silicates can each differ in particle size, surface acidity or crystal structure.
- the auxiliary (c) used is a silica and a silicate.
- silica (c) has a mean particle diameter (volume average) in the range from 5 to 100 ⁇ m, preferably from 5 ⁇ m to at most 20 ⁇ m, determined by laser diffraction according to ISO 13320-1 (2009). In one embodiment of the present invention, silicate (c) has an average particle diameter (volume average) in the range of 5 ⁇ to at most 20 ⁇ , determined by laser diffraction according to ISO 13320-1 (2009).
- mills for the third step of the process according to the invention are selected from mills having a relatively low energy input. Preference is given to impact and cutting mills.
- the proportion of component (b) is at least as high as the proportion of nonionic surfactant of general formula (I).
- the proportions for the process according to the invention are selected as follows:
- (C) a total of 1 to 5 wt .-% silica or silicate, preferably 2 to 3 wt .-%, and
- component (d) overall in the range of from 40 to 70% by weight of component (d), preferably from 42 to 60% by weight.
- Granules obtainable by the process according to the invention are easy to process, for example to tablets ("tabs") for ADW and to clear rinse tablets for ADW granules obtainable by the process according to the invention are less hygroscopic and less prone to sticking or caking.
- Granules according to the invention have an average particle diameter in the range from 0.5 to 1.6 mm and contain (a) in the range from 15 to 25% by weight of nonionic surfactant of the general formula (I)
- R 1 is selected from C 4 -C 20 -alkyl
- R 2 is selected from C 8 -C 20 -alkyl
- AO are in each case identical or different and selected from C 2 -C 4 -alkylene
- x is in the range of 5 to 100
- R 3 is -CH (COOM) -N (CH 2 COOM) 2 (Ii) in which the variables are defined as follows: R 3 is selected from C 1 -C 4 -alkyl, phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 ,
- M 1 is an alkali metal or a combination of at least two alkali metals, granules according to the invention being solid at a temperature of up to 60 ° C.
- Components (a), (b), (c) and (d) are described in more detail above.
- granules according to the invention have a particle diameter distribution as follows: d m is in the range from 0.5 to 1.8 mm, d63.3 is in the range from 0.4 to 1.8 mm and n is in the range from 0.5 to 1.8 mm Range from 0.7 to 10, determined in each case with the aid of a sieve analysis according to DIN ISO 3310-1 (1992) and evaluation according to DIN 66145 (1976).
- Granules according to the invention can be made into dishwasher tablets and especially into rinse tablets, but also into rinse aid for an automatic dishwashing machine or as component for an x-in-1 ground dishwashing detergent, for example a 2-in-1 dishwashing detergent or a 3-in-1 detergent.
- the rinse aid is a rinse aid for an automatic dishwasher or a component for an x-in-1 dishwashing detergent, for example a 2-in-1 dishwashing or a 3-in-1 dishwashing detergent. 1 dishwashing detergent.
- granules according to the invention without further additives as a rinse aid in a dishwashing machine, in particular in x.in-1 dishwashers.
- at least one additive is added, selected from water and acids, for example citric acid.
- the components (a.1) and (b.1) were melted together in a beaker at 70 ° C and mixed with a propeller stirrer. Subsequently, the melt was poured onto aluminum foil (20 cm ⁇ 10 cm ⁇ 1 cm) and solidified at room temperature. Waxy plates were obtained.
- the lozenges thus produced were ground in a hammer mill (knife mill). For this purpose, the mill was operated with 2 knives and a peripheral speed of 14 m / s.
- Mahlsieb was a Rundlochsieb with a hole diameter of 3.2 mm and a free
- the particle diameter distribution of the exemplary granules was determined as follows by sieve analysis: sieving machine: AS 200 control, Fa. Retsch, test sieves to DIN ISO 3310-1, height 25 mm; 0 200 mm
- V-G.3 received no measurable granules
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Abstract
The invention relates to a method for producing a formulation which is solid up to a temperature of at least 60 °C, characterised in that (a) at least one non-ionic surfactant is prepared of general formula (I) R1-CH(OH)-CH2-(AO)x-R2 (I) in which the variables are defined as follows: R1 is selected from C4-C20-alkyl, R2 is selected from C8-C20-alkyl, AO are respectively the same or different and selected from C2-C4-alkylene, x is in the range from 5 to 100, (b) mixed in the molten state with at least one second material, selected from polyethylene glycol and non-ionic surfactants, which are different from the surfactants of formula (I), mixed and ground in a mill in the solid-state with (c) silicic acid or silicate and (d) at least one additive, selected from alkali metal citrate, alkali metal carbonate or at least one chelate forming agent, selective from compounds of general formula (II) R3-CH(COOM1)-N(CH2COOM1)2 (II) in which the variables are defined as follows: R3 is selected from C1-C4-alkyl, phenyl, benzyl, CH2OH and CH2CH2COOM1, M1 is an alkali metal or a combination of at least two alkali metals. The invention also relates to granulates and the use thereof.
Description
Granulate, Verfahren zu ihrer Herstellung und ihre Verwendung Granules, process for their preparation and their use
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer bei bis zu einer Temperatur von mindestens 60°C festen Formulierung, dadurch gekennzeichnet, dass man The present invention relates to a process for preparing a formulation which is solid up to a temperature of at least 60 ° C, characterized in that
(a) mindestens ein nicht-ionisches Tensid der allgemeinen Formel (I) (a) at least one nonionic surfactant of the general formula (I)
R -CH(OH)-CH2-(AO)x-R2 (I) in dem die Variablen wie folgt definiert sind: R -CH (OH) -CH 2 - (AO) x R 2 (I) in which the variables are defined as follows:
R1 ist gewählt aus C4-C2o-Alkyl, R 1 is selected from C 4 -C 20 -alkyl,
R2 ist gewählt aus C8-C2o-Alkyl, R 2 is selected from C 8 -C 20 -alkyl,
AO sind jeweils gleich oder verschieden und gewählt aus C2-C4-Alkylen, AO are in each case identical or different and selected from C 2 -C 4 -alkylene,
x liegt im Bereich von 5 bis 100, x is in the range of 5 to 100,
(b) mit mindestens einem zweiten Stoff, gewählt aus Polyethylenglykol und nicht-ionischen Tensiden, die von Tensiden der Formel (I) verschieden sind, (b) at least one second substance selected from polyethylene glycol and nonionic surfactants other than surfactants of formula (I),
im aufgeschmolzenen Zustand mischt, in the molten state,
konfektioniert, im festen Zustand mit assembled, in the solid state with
(c) Kieselsäure oder Silikat und (d) mindestens einem Hilfsmittel, gewählt aus Alkalimetallzitrat, Alkalimetallcarbonat oder mindestens einem Chelatbildner, gewählt aus Verbindungen der allgemeinen Formel (II) (c) silicic acid or silicate and (d) at least one adjuvant selected from alkali metal citrate, alkali metal carbonate or at least one chelating agent selected from compounds of general formula (II)
R3-CH(COOM1)-N(CH2COOM1)2 (I I) in dem die Variablen wie folgt definiert sind: R 3 is -CH (COOM 1 ) -N (CH 2 COOM 1 ) 2 (II) in which the variables are defined as follows:
R3 ist gewählt aus Ci-C4-Alkyl, Phenyl, Benzyl, CH2OH und CH2CH2COOM1 , R 3 is selected from C 1 -C 4 -alkyl, phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 ,
M1 ist ein Alkalimetall oder eine Kombination von mindestens zwei Alkalimetallen, in einer Mühle vermischt und vermahlt. M 1 is an alkali metal or a combination of at least two alkali metals, mixed in a mill and ground.
Weiterhin betrifft die vorliegende Erfindung Granulate und ihre Verwendung. Furthermore, the present invention relates to granules and their use.
Tenside finden zahlreiche Anwendungen, beispielsweise auf dem Sektor der Wasch- und Rei- nigungsmittel. Bestimmte nicht-ionische Tenside haben dabei eine Bedeutung als sogenannte Klarspültenside gewonnen, beispielsweise für Maschinengeschirrspülmittel, kurz auch häufig als ADW für englisch„automatic dishwashing" bezeichnet. Darunter sind insbesondere zahlreiche Vertreter der sogenannten HME zu nennen, wobei HME für Hydroxy-Mischether steht. Die
Formulierung von Hydroxymischethern ist jedoch anspruchsvoll, insbesondere in festen Formulierungen, die als Zwischen- oder Endprodukte dienen. Surfactants find numerous applications, for example in the washing and cleaning agent sector. Certain non-ionic surfactants have gained importance as so-called rinse aid surfactants, for example for machine dishwashing detergents, in short also often referred to as ADW for English "automatic dishwashing." Of these, in particular numerous representatives of the so-called HME be mentioned, where HME stands for hydroxy mixed ethers. The However, formulation of hydroxy mixed ethers is demanding, especially in solid formulations serving as intermediates or final products.
Zahlreiche Hydroxymischether sind wachsartig aussehende Substanzen mit einem Schmelz- punkt von unter 60°C, unter 50°C oder sogar unter 35°C. Sie sind in der Lage, unterkühlte Schmelzen zu bilden, die auch nach langer Zeit nur eine geringe Neigung zum Kristallisieren zeigen. Einige Hydroxymischether sind hygroskopisch zeigen und darüber hinaus - insbesondere bei geringer Partikelgröße - eine Tendenz zum Kleben. Zwar kann man die Lagerstabilität durch Zugabe eines sogenannten Anti-Caking-Mittels verbessern. Diese sind aber in vielen Fäl- len nicht kompatibel mit anderen Ingredienzien von Spülmaschinenformulierungen. Many hydroxy mixed ethers are waxy-looking substances with a melting point below 60 ° C, below 50 ° C or even below 35 ° C. They are able to form supercooled melts, which show only a slight tendency to crystallize even after a long time. Some hydroxymix ethers are hygroscopic and, moreover, especially with small particle size, tend to stick. Although it is possible to improve the storage stability by adding a so-called anti-caking agent. However, these are in many cases incompatible with other ingredients of dishwasher formulations.
Feste Formulierungen, beispielsweise Pulver Granulate, die Hydroxymischether enthalten, können in einigen Fällen zum Verkleben oder Verbacken neigen. Bei Pulvern oder Granulaten, die als Zwischenprodukte dienen, führt ein derartiges Verkleben oder Verbacken dazu, dass die Weiterverarbeitung schwierig wird. Bei Pulvern oder Granulaten, die als Endprodukte dienen, also an den Verbraucher geliefert werden sollen, führt ein derartiges Verkleben oder Verbacken zu negativen Rückmeldungen. Solid formulations, for example powder granules containing hydroxy mixed ethers, may tend to stick or cake in some cases. With powders or granules serving as intermediates, such sticking or caking will make further processing difficult. In the case of powders or granules which serve as end products, that is to be delivered to the consumer, such sticking or baking leads to negative feedback.
Es bestand also die Aufgabe, ein Verfahren bereit zu stellen, durch das feste Formulierungen hergestellt werden können, die einen Hydroxymethylmischether enthalten und die leicht weiter- zuverarbeiten sind. Es bestand weiterhin die Aufgabe, feste Formulierungen hergestellt werden können, die einen Hydroxymethylmischether enthalten und die leicht weiterzuverarbeiten sind. It was therefore the object to provide a process by which solid formulations can be prepared which contain a hydroxymethyl mixed ether and which are easy to process further. It was a further object to be able to produce solid formulations which contain a hydroxymethyl mixed ether and which are easy to process further.
Dementsprechend wurde das eingangs definierte Verfahren gefunden, das im Zusammenhang mit der vorliegenden Erfindung auch als erfindungsgemäßes Verfahren bezeichnet wird. Das erfindungsgemäße Verfahren ist ein Verfahren zur Herstellung einer bei bis zu einer Temperatur von mindestens 60°C festen Formulierung. Dabei kann man den Schmelzpunkt beispielsweise durch Dynamische Differenzkalorimetrie (DSC) bestimmen, vorteilhaft mit einer Aufheizgeschwindigkeit von 10K/min ±1 K/min; Einwaage 6-7 mg; Spülgas 3 I IS /h, AI-Messtiegel, of- fen). Accordingly, the method defined above was found, which is also referred to in the context of the present invention as a method according to the invention. The process according to the invention is a process for the preparation of a formulation which is solid up to a temperature of at least 60 ° C. In this case, one can determine the melting point, for example by differential scanning calorimetry (DSC), advantageously with a heating rate of 10K / min ± 1 K / min; Initial weight 6-7 mg; Purge gas 3 l IS / h, AI crucible, open).
Das erfindungsgemäße Verfahren umfasst mehrere Schritte. Dazu geht das erfindungsgemäße Verfahren aus von mindestens einem nicht-ionischen Tensid der allgemeinen Formel (I), das im Zusammenhang mit der vorliegenden Erfindung auch Komponente (a) genannt werden kann, The method according to the invention comprises several steps. For this purpose, the method according to the invention is based on at least one nonionic surfactant of the general formula (I) which, in connection with the present invention, can also be called component (a),
R -CH(OH)-CH2-(AO)x-R2 (I) in dem die Variablen wie folgt definiert sind: R1 ist gewählt aus C4-C2o-Alkyl, vorzugsweise n-C4-C2o-Alkyl. Beispiele sind n-Butyl, sec.-Butyl, iso-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl, n-Dodecyl, iso-Dodecyl,
n-tetradecyl, iso-tetradecyl, stearyl, palmityl, und n-Eicosyl. Bevorzugte Beispiele sind n-Butyl, n-Pentyl, iso-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-tetradecyl, stearyl, palmityl, und n-Eicosyl. Besonders bevorzugte Beispiele sind n-Octyl und n-Decyl. R2 ist gewählt aus C8-C2o-Alkyl, bevorzugt n-Cs-C2o-Alkyl, wobei als Beispiele n-Octyl, 2-R is -CH (OH) -CH 2 - (AO) x R 2 (I) in which the variables are defined as follows: R 1 is selected from C 4 -C 20 -alkyl, preferably n-C 4 -C 20 -alkyl. Examples are n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, iso-dodecyl, n-tetradecyl, iso-tetradecyl, stearyl, palmityl, and n-eicosyl. Preferred examples are n-butyl, n-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, stearyl, palmityl, and n- eicosyl. Particularly preferred examples are n-octyl and n-decyl. R 2 is selected from C 8 -C 20 -alkyl, preferably n-C 2 -C 20 -alkyl, examples being n-octyl,
Ethylhexyl, n-Nonyl, n-Decyl, n-Undecyl, iso-Cn H23, n-Dodecyl, iso-Dodecyl, n-tetradecyl, iso- tetradecyl, stearyl, palmityl, und n-Eicosyl genannt seien. Bevorzugte Beispiele sind n-Octyl, n- Nonyl, n-Decyl, n-Undecyl, iso-Cn H23, n-Dodecyl, is-Dodecyl, n-Tetradecyl, Stearyl, Palmityl und n-Eicosyl. Besonders bevorzugte Beispiele sind iso-Cn H23- Ethylhexyl, n-nonyl, n-decyl, n-undecyl, iso-Cn H23, n-dodecyl, iso-dodecyl, n-tetradecyl, isotetradecyl, stearyl, palmityl, and n-eicosyl. Preferred examples are n-octyl, n-nonyl, n-decyl, n-undecyl, iso-Cn H23, n-dodecyl, is-dodecyl, n-tetradecyl, stearyl, palmityl and n-eicosyl. Particularly preferred examples are iso-Cn H 2 3-
AO sind jeweils gleich oder verschieden und gewählt aus C2-C4-Alkylen, beispielsweise AO are each the same or different and selected from C 2 -C 4 -alkylene, for example
CH2-CH2-O, (CH2)3-0, (CH2)4-0, CH2CH(CH3)-0, CH(CH3)-CH2-0- und CH2CH(n-C3H7)-0. Besonders bevorzugt ist AO jeweils gleich und CH2-CH2-O, kurz auch„EO". x liegt im Bereich von 5 bis 100, bevorzugt 5 bis 60, noch mehr bevorzugt 10 bis 50 und besonders bevorzugt 20 bis 40. CH 2 -CH 2 -O, (CH 2 ) 3-0, (CH 2 ) 4-O, CH 2 CH (CH 3 ) -O, CH (CH 3 ) -CH 2 -O- and CH 2 CH (nC 3 H 7 ) -0. Particularly preferably, AO is in each case identical and CH 2 -CH 2 -O, in short also "EO" x is in the range from 5 to 100, preferably 5 to 60, more preferably 10 to 50 and particularly preferably 20 to 40.
In einer Ausführungsform der vorliegenden Erfindung ist (AO)x gewählt aus (CH2CH20)xi , wobei x1 im Bereich von 1 bis 50 liegt. In one embodiment of the present invention, (AO) x is selected from (CH 2 CH 2 O) xi, where x1 is in the range of 1 to 50.
In einer Ausführungsform der vorliegenden Erfindung ist (AO)x gewählt aus In one embodiment of the present invention, (AO) x is selected from
-(CH2CH20)x2-(CH2CH(CH3)-0)x3 und -(CH2CH20)x2-(CH(CH3)CH2-0)x3, wobei x2 und x3 gleich oder verschieden sein können und jeweils im Bereich von 1 bis 30 liegen. In einer Ausführungsform der vorliegenden Erfindung ist (AO)x gewählt aus -(CH2CH20)x4, wobei x4 im Bereich von 10 bis 50 liegt, AO jeweils EO ist, und R1 und R2 jeweils aus Ce-C-u-Alkyl gewählt werden. - (CH2 CH20) x2 (CH 2 CH (CH3) -0) x3, and - (CH 2 CH 2 0) x2 (CH (CH3) CH2-0) x3, where X2 and X3 may be the same or different and each range from 1 to 30. In one embodiment of the present invention, (AO) x is selected from - (CH 2 CH 2 O) x 4 wherein x 4 is in the range of 10 to 50, AO is EO, and R 1 and R 2 are each selected from Ce-Cu-alkyl become.
Im Zusammenhang mit der vorliegenden Erfindung sind x bzw. x1 bzw. x2 bzw. x3 bzw. x4 jeweils als Mittelwerte zu verstehen, wobei das Zahlenmittel bevorzugt ist. Daher können sich x oder x1 oder x2 oder x3 oder x4 - so vorhanden - eine nicht-ganze Zahl sein, obwohl einzelne Moleküle jeweils eine ganze Zahl an AO-Einheiten aufweisen. In the context of the present invention, x, x1, x2, x3, x4 are each to be understood as average values, the number average being preferred. Therefore, x or x1 or x2 or x3 or x4, if present, may be a non-integer although individual molecules each have an integer number of AO units.
In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung sind die Variablen wie folgt gewählt: R1 ist n-Cs-C-io-Alkyl, R2 ist Cs-Ci2-Alkyl, geradkettig oder als iso-Cs-Ci2-Alkyl, x ist im Bereich von 20 bis 25. In a particularly preferred embodiment of the present invention, the variables are chosen as follows: R 1 is n-Cs-C-io-alkyl, R 2 is Cs-C 12 -alkyl, straight-chain or iso-Cs-C 12 -alkyl, x is in the range of 20 to 25.
In einer Ausführungsform der vorliegenden Erfindung hat Komponente (a) einen Schmelzpunkt im Bereich von 30 bis 60°C, bevorzugt 35 bis 55°C. Den Schmelzpunkt von Komponente (a) kann man wie oben genannt messen. In one embodiment of the present invention, component (a) has a melting point in the range of 30 to 60 ° C, preferably 35 to 55 ° C. The melting point of component (a) can be measured as mentioned above.
Komponente (a) mischt man mit
(b) mindestens einem zweiten Stoff, im Rahmen der vorliegenden Erfindung auch Komponente (b) genannt, und der gewählt ist aus Polyethylenglykol und nicht-ionischen Tensiden, die von Tensiden der Formel (I) verschieden sind. Beispiele für Polyethylenglykol sind Polyadditionsprodukte von Ethylenoxid mit einem mittleren Molekulargewicht Mw im Bereich von 1 .000 bis 50.000 g/mol, bevorzugt 2.000 bis 20.000 g/mol. Component (a) is mixed with (B) at least one second substance, in the context of the present invention also called component (b), and which is selected from polyethylene glycol and nonionic surfactants, which are different from surfactants of the formula (I). Examples of polyethylene glycol are polyaddition products of ethylene oxide having an average molecular weight M w in the range of 1 .000 to 50,000 g / mol, preferably 2,000 to 20,000 g / mol.
Beispiele für nicht-ionische Tenside, die von Komponente (a) verschieden sind, sind Alkohol- alkoxylate, Di- und Multiblockcopolymerisate von Ethylenoxid und Propylenoxid und Umset- zungsprodukte von Sorbitan mit Ethylenoxid oder Propylenoxid, weiterhin Alkylglycoside. Examples of nonionic surfactants other than component (a) are alcohol alkoxylates, di- and multiblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitan with ethylene oxide or propylene oxide, and also alkyl glycosides.
Bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispiel Verbindungen der allgemeinen Formel (III) Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III)
in der die Variablen wie folgt definiert sind: where the variables are defined as follows:
R4 gewählt aus linearem d-C4-Alkyl, bevorzugt Ethyl und besonders bevorzugt Methyl, R 4 is selected from linear C 1 -C 4 -alkyl, preferably ethyl and more preferably methyl,
R5 gewählt aus Cs-C22-Alkyl, beispielsweise n-CsHiz, n-CioF i , n-Ci2H25, n-Ci4H29, n-Ci6H33
R 5 selected from Cs-C22-alkyl, for example n-CsHiz, n-CioF i, n-Ci2H25, n-Ci4H29, n-Ci6H33
R6 gewählt aus Ci-Cio-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-R 6 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-
Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl oder iso- Decyl, m und n liegen im Bereich von null bis 300, wobei die Summe von n und m mindestens eins beträgt. Bevorzugt ist m im Bereich von 1 bis 100 und n im Bereich von 0 bis 30. Hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl, m and n are in the range of zero to 300, the sum of n and m is at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.
Dabei kann es sich bei Verbindungen der allgemeinen Formel (I) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere. Andere bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (IV)
in der die Variablen wie folgt definiert sind: Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers. Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (IV) where the variables are defined as follows:
R4 gleich oder verschieden und gewählt aus linearem Ci-C4-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl, R 4 is identical or different and selected from linear C 1 -C 4 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
R7 gewählt aus C6-C2o-Alkyl, insbesondere n-CeHi7, n-CioH2i, n-Ci2H25, n-Ci4H29, n-Ci6H33, R 7 is selected from C 6 -C 20 -alkyl, in particular n-CeHi 7, n-CioH 2 i, n-Ci 2 H 2 5, n-Ci4H 2 9, n-Ci6H 3 3,
a ist eine Zahl im Bereich von 1 bis 6, b ist eine Zahl im Bereich von 4 bis 20, d ist eine Zahl im Bereich von 4 bis 25. a is a number in the range of 1 to 6, b is a number in the range of 4 to 20, d is a number in the range of 4 to 25.
Dabei kann es sich bei Verbindungen der allgemeinen Formel (IV) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere. Weitere geeignete nicht-ionische Tenside sind gewählt aus Di- und Multiblockcopolymeren, aufgebaut aus Ethylenoxid und Propylenoxid. Weitere geeignete nicht-ionische Tenside sind gewählt aus ethoxylierten oder propoxylierten Sorbitanestern und Isosorbitestern. Weitere geeignete nicht-ionische Tenside sind gewählt aus Di-Fettsäureestern von Polyethylenglykol, beispielsweise zweifach mit Stearinsäure verestertes Polyethylenglykol mit einen mittleren Moleku- largewicht Mw im Bereich von 1500 bis 2500 g/mol. In the case of compounds of the general formula (IV), these may be block copolymers or random copolymers, preference being given to block copolymers. Other suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters and isosorbitol esters. Further suitable nonionic surfactants are selected from di-fatty acid esters of polyethylene glycol, for example polyethyleneglycol esterified twice with stearic acid and having an average molecular weight M w in the range from 1500 to 2500 g / mol.
Beispiele für Alkylpolyglykoside sind Verbindungen der allgemeinen Formel (VI) Examples of alkyl polyglycosides are compounds of the general formula (VI)
wobei die Variablen wie folgt definiert sind: where the variables are defined as follows:
R8 ist Wasserstoff oder Ci-C4-Alkyl, bevorzugt sind Ethyl, n-Propyl und Isopropyl sowie Wasserstoff, R 8 is hydrogen or C 1 -C 4 -alkyl, preferred are ethyl, n-propyl and isopropyl and also hydrogen,
R9 ist -(CH2)2-R8,
G1 ist gewählt aus Monosacchariden mit 4 bis 6 Kohlenstoffatomen, insbesondere Glucose und Xylose, w ist im Bereich von 1 ,1 bis 4, wobei w ein Mittelwert ist, insbesondere das Zahlenmittel. R 9 is - (CH 2 ) 2 -R 8 , G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, w is in the range of 1, 1 to 4, w being an average, in particular the number average.
Bevorzugt liegt w im Bereich von 1 ,1 bis 2 und besonders bevorzugt im Bereich von 1 ,2 bis 1 ,8. Es ist bevorzugt, w durch Hochtemperatur-Gaschromatography (HTGC) zu bestimmen. Preferably, w is in the range of 1.1 to 2, and more preferably in the range of 1.2 to 1.8. It is preferred to determine w by high temperature gas chromatography (HTGC).
In einer Ausführungsform der vorliegenden Erfindung hat Komponente (b) einen Schmelzpunkt im Bereich von 35 bis 70°C, bevorzugt 50 bis 65°C. Den Schmelzpunkt von Komponente (b) kann man ebenfalls durch dynamische DSC messen. In one embodiment of the present invention, component (b) has a melting point in the range of 35 to 70 ° C, preferably 50 to 65 ° C. The melting point of component (b) can also be measured by dynamic DSC.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung liegt der Schmelzpunkt von Komponente (a) unter demjenigen der Komponente (b). In a preferred embodiment of the present invention, the melting point of component (a) is below that of component (b).
Zur Durchführung des erfindungsgemäßen Verfahrens mischt man zunächst Komponente (a) und (b) im aufgeschmolzenen Zustand. Die Temperatur zum Mischen wählt man so, dass die niedriger schmelzende Komponente - also Komponente (b) oder vorzugsweise Komponente (a) - im geschmolzenen Zustand vorliegt. Die jeweils höher schmelzende Komponente kann im festen oder geschmolzenen Zustand vorliegen. Bevorzugt mischt man Komponente (a) und Komponente (b) in den Anteilen, die für betreffende Formulierung vorgesehen sind. To carry out the process according to the invention, component (a) and (b) are first mixed in the molten state. The temperature for mixing is chosen so that the lower-melting component - ie component (b) or preferably component (a) - is in the molten state. The higher melting component may be in the solid or molten state. Component (a) and component (b) are preferably mixed in the proportions intended for the formulation in question.
In einer besonderen Ausführungsform der vorliegenden Erfindung ist Komponente (a) während des Mischens aufgeschmolzen. In a particular embodiment of the present invention, component (a) is melted during mixing.
Man mischt Komponente (a) und Komponente (b) so lange, bis man optisch - mit dem unbewaffneten Auge, also ohne optische Hilfsmittel - eine homogene Mischung wahrnimmt. Mix component (a) and component (b) until optically - with the unaided eye, ie without optical aids - perceives a homogeneous mixture.
Vorzugsweise mischt man Komponente (a) und Komponente (b) bei einer Temperatur, die min- destens 5 °C oberhalb des Schmelzpunkts von Komponente (a) liegt, besonders bevorzugt mindestens 10°C. Component (a) and component (b) are preferably mixed at a temperature which is at least 5 ° C. above the melting point of component (a), more preferably at least 10 ° C.
In einer besonderen Ausführungsform der vorliegenden Erfindung mischt man Komponente (a) und Komponente (b) bei einer Temperatur, die mindestens 5°C oberhalb derjenigen Temperatur liegt, bei der die höherschmelzende Komponente schmilzt. In a particular embodiment of the present invention, component (a) and component (b) are mixed at a temperature at least 5 ° C above the temperature at which the higher melting component melts.
Zur Bewirkung des Mischvorgangs kann man so vorgehen, dass man Komponenten (a) und (b) in fester Form in einem Mischgefäß vorlegt und unter Mischen - beispielsweise Schütteln oder vorzugsweise unter Rühren - aufheizt, bis die jeweils niedriger schmelzende Komponente auf- geschmolzen ist. Danach setzt man das Mischen fort, bis man mit unbewaffnetem Auge eine homogene Mischung wahrnimmt, also weder separate Partikel noch Schlieren erkennen kann.
Beispiele für geeignete Mischgefäße sind Rührgefäße wie beispielsweise Rührreaktoren und Rührkessel. To effect the mixing process, one can proceed by introducing components (a) and (b) in solid form in a mixing vessel and heating with mixing, for example shaking or preferably with stirring, until the lower-melting component has melted. Thereafter, the mixing is continued until you perceive with unaided eye a homogeneous mixture, so neither separate particles nor streaks can recognize. Examples of suitable mixing vessels are stirred vessels such as stirred reactors and stirred tanks.
In einem folgenden Schritt konfektioniert man die im ersten Schritt des erfindungsgemäßen Ver- fahrens erhaltene Mischung. Darunter soll im Zusammenhang mit dem erfindungsgemäßen Verfahren verstanden werden, dass man die Mischung aus dem ersten Schritt so bearbeitet, dass sie in feste Partikel mit den gewünschten Abmessungen überführt wird. Bevorzugte Beispiele sind Pastillierungen, Verschuppungen, Vermahlungen und Kombinationen von mindestens zwei der vorhergehenden Maßnahmen. Wünscht man die im ersten Schritt des erfin- dungsgemäßen Verfahrens erhältliche Mischung zu vermählen, so lässt man sie zuvor erstarren. In a subsequent step, the mixture obtained in the first step of the process according to the invention is prepared. In the context of the process according to the invention, this is understood to mean that the mixture from the first step is processed so that it is converted into solid particles having the desired dimensions. Preferred examples are pastilles, flakes, grindings, and combinations of at least two of the foregoing. If it is desired to ground the mixture obtainable in the first step of the process according to the invention, they are allowed to solidify first.
Pastillieren kann man beispielsweise, indem man eine im ersten Schritt des erfindungsgemäßen Verfahrens erhaltene Mischung in eine Form mit entsprechenden Mulden gießt und die Mischung in der entsprechenden Form erkalten lässt. Anschließend entfernt man die erkaltete Mischung - eben die Pastillen - aus der Form und gießt erneut Mischung in die Form. In einer anderen Ausführungsform wählt man Kühlbänder zum Pastillieren. Pastillen können beispielsweise einen Durchmesser im Bereich von 4 bis 10 mm aufweisen. Verschuppen kann man beispielsweise, indem man eine Schuppenwalze verwendet. Die Größe der Schuppen kann von den Produkteigenschaften und den Maschineneinstellungen abhängen. In der Regel erhält man unregelmäßig geformte Schuppen. Als mittlere Abmessungen sind beispielsweise Längen im Bereich von 1 mm bis 2 cm, Breiten von 1 mm bis 1 ,5 cm und Dicken im Bereich von 0,5 mm bis 3 mm geeignet. Pastillation can be carried out, for example, by pouring a mixture obtained in the first step of the process according to the invention into a mold with corresponding wells and allowing the mixture to cool in the appropriate mold. Then remove the cooled mixture - just the lozenges - from the mold and poured again mixture into the mold. In another embodiment, cooling belts are selected for pastillation. Pastilles may for example have a diameter in the range of 4 to 10 mm. Scaling can be done, for example, by using a flaking roller. The size of the flakes may vary depending on the product characteristics and the machine settings. As a rule, irregularly shaped scales are obtained. As average dimensions, for example, lengths in the range of 1 mm to 2 cm, widths of 1 mm to 1, 5 cm and thicknesses in the range of 0.5 mm to 3 mm are suitable.
Beispiele für besonders gut geeignete Geräte zum Vermählen sind Schlagmühlen und Schneidemühlen. Beim Vermischen in einer Mühle vermahlt man gleichzeitig. Examples of particularly suitable equipment for grinding are impact mills and cutting mills. When mixing in a mill you grind simultaneously.
Man erhält eine konfektionierte und bei Zimmertemperatur feste Mischung von Komponente (a) und Komponente (b). This gives a ready-made and solid at room temperature mixture of component (a) and component (b).
Im nächsten Schritt des erfindungsgemäßen Verfahrens vermischt man in einer Mühle die konfektionierte und bei Zimmertemperatur feste Mischung von Komponente (a) und KomponenteIn the next step of the process according to the invention, the preformed and solid at room temperature mixture of component (a) and component is mixed in a mill
(b) im festen Zustand mit (b) in the solid state with
(c) Kieselsäure oder Silikat, im Rahmen der vorliegenden Erfindung auch Kieselsäure (c) bzw. Silikat (c) oder allgemeiner Komponente (c) genannt, und (c) silicic acid or silicate, in the context of the present invention also silica (c) or silicate (c) or more generally called component (c), and
(d) mindestens einem Hilfsmittel, kurz auch als Hilfsmittel (d) oder Komponente (d) bezeich- net, wobei Komponente (d) gewählt wird aus Alkalimetallzitrat, beispielsweise Trinatrium- zitrat, Alkalimetallcarbonat wie beispielsweise Kaliumcarbonat oder Natriumcarbonat, oder mindestens einem Chelatbildner, gewählt aus Verbindungen der allgemeinen Formel (II)
R3-CH(COOM )-N(CH2COOM )2 (II) in dem die Variablen wie folgt definiert sind: (d) at least one auxiliary, also referred to as auxiliary (d) or component (d), wherein component (d) is selected from alkali metal citrate, for example trisodium citrate, alkali metal carbonate such as potassium carbonate or sodium carbonate, or at least one chelating agent, selected from compounds of general formula (II) R 3 -CH (COOM) -N (CH 2 COOM) 2 (II) in which the variables are defined as follows:
R3 ist gewählt aus Ci-C4-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec.-Butyl, Isobutyl, bevorzugt sind Methyl, sec.-Butyl und Isobutyl und ganz besonders bevorzugt ist R3 Methyl; weiterhin Phenyl, Benzyl, CH2OH und CH2CH2COOM1, M1 ist ein Alkalimetall oder eine Kombination von mindestens zwei Alkalimetallen, beispielsweise Lithium, Natrium, Kalium, bevorzugt sind Kalium, Natrium und Kombinationen von Kalium und Natrium, beispielsweise in einem Molverhältnis im Bereich von 1 :2 bis 2:1 , und ganz besonders bevorzugt ist M1 Natrium. Kieselsäure (c) kann man wählen aus Fällungskieselsäuren und pyrogenen Kieselsäuren. R 3 is selected from C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, preferred are methyl, sec-butyl and isobutyl and very particularly preferably R 3 Methyl; furthermore phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 , M 1 is an alkali metal or a combination of at least two alkali metals, for example lithium, sodium, potassium, preferred are potassium, sodium and combinations of potassium and sodium, for example in a molar ratio in the range of 1: 2 to 2: 1, and most preferably M 1 is sodium. Silica (c) can be selected from precipitated silicas and fumed silicas.
Beispiele für Silikate (c) sind Natriumdisilikat und Natriummetasilikat, Zeolithe und Schichtsilikate, insbesondere solche der Formel a-Na2Si20s, ß-Na2Si20s und 5-Na2Si20s. In einer Ausführungsform der vorliegenden Erfindung setzt man als Hilfsmittel (c) entweder zwei verschiedene Kieselgele oder zwei verschiedene Silikate ein. Verschiedene Kieselgele bzw. verschiedene Silikate können sich jeweils in Partikelgröße, Oberflächenazidität oder Kristallstruktur unterscheiden. In einer anderen Ausführungsform der vorliegenden Erfindung setzt man als Hilfsmittel (c) eine Kieselsäure und ein Silikat ein. Examples of silicates (c) are sodium disilicate and sodium metasilicate, zeolites and phyllosilicates, especially those of the formula a-Na 2 Si 2 0s, β-Na 2 Si 2 0s and 5-Na 2 Si 2 0s. In one embodiment of the present invention, the auxiliary (c) used is either two different silica gels or two different silicates. Different silica gels or different silicates can each differ in particle size, surface acidity or crystal structure. In another embodiment of the present invention, the auxiliary (c) used is a silica and a silicate.
In einer anderen Ausführungsform der vorliegenden Erfindung setzt man nur ein Hilfsmittel (c) ein. In another embodiment of the present invention, only one adjuvant (c) is used.
In einer Ausführungsform der vorliegenden Erfindung hat Kieselsäure (c) einen mittleren Partikeldurchmesser (Volumenmittel) im Bereich von 5 bis 100 μηη, bevorzugt 5 μηη bis höchstens 20 μιη, bestimmt durch Laser-Beugung nach ISO 13320-1 (2009). In einer Ausführungsform der vorliegenden Erfindung hat Silikat (c) einen mittleren Partikeldurchmesser (Volumenmittel) im Bereich von 5 μηη bis höchstens 20 μηη, bestimmt durch Laser- Beugung nach ISO 13320-1 (2009). In one embodiment of the present invention, silica (c) has a mean particle diameter (volume average) in the range from 5 to 100 μm, preferably from 5 μm to at most 20 μm, determined by laser diffraction according to ISO 13320-1 (2009). In one embodiment of the present invention, silicate (c) has an average particle diameter (volume average) in the range of 5 μηη to at most 20 μηη, determined by laser diffraction according to ISO 13320-1 (2009).
Beim Vermischen findet ein Vermählen statt.
In einer Ausführungsform der vorliegenden Erfindung wählt man Mühlen für den dritten Schritt des erfindungsgemäßen Verfahrens aus Mühlen mit einem verhältnismäßig geringen Energieeintrag. Bevorzugt sind Schlag- und Schneidemühlen. In einer Ausführungsform der vorliegenden Erfindung ist der Anteil an Komponente (b) mindestens so hoch ist wie der Anteil an nicht-ionischem Tensid der allgemeinen Formel (I). When mixing a grinding takes place. In one embodiment of the present invention, mills for the third step of the process according to the invention are selected from mills having a relatively low energy input. Preference is given to impact and cutting mills. In one embodiment of the present invention, the proportion of component (b) is at least as high as the proportion of nonionic surfactant of general formula (I).
In einer Ausführungsform der vorliegenden Erfindung wählt man für das erfindungsgemäße Verfahren die Mengenverhältnisse wie folgt: In one embodiment of the present invention, the proportions for the process according to the invention are selected as follows:
(a) im Bereich von 15 bis 25 Gew.-% nicht-ionisches Tensid der allgemeinen Formel (I),(a) in the range of 15 to 25% by weight of nonionic surfactant of the general formula (I),
(b) insgesamt im Bereich von 5 bis 40 Gew.-% Komponente (b), (b) in total in the range from 5 to 40% by weight of component (b),
(c) insgesamt 1 bis 5 Gew.-% Kieselsäure oder Silikat, bevorzugt 2 bis 3 Gew.-%, und (C) a total of 1 to 5 wt .-% silica or silicate, preferably 2 to 3 wt .-%, and
(d) insgesamt im Bereich von 40 bis 70 Gew.-% Komponente (d), bevorzugt 42 bis 60 Gew.- %. (d) overall in the range of from 40 to 70% by weight of component (d), preferably from 42 to 60% by weight.
Man erhält ein gut rieselfähiges Granulat. Nach dem erfindungsgemäßen Verfahren erhältliche Granulate sind leicht zu verarbeiten, beispielsweise zu Tabletten („Tabs") für ADW und zu Klar- spültabs für ADW. Nach dem erfindungsgemäßen Verfahren erhältliche Granulate sind wenig hygroskopisch und neigen weniger zum Verkleben oder Verbacken. This gives a good flowable granules. Granules obtainable by the process according to the invention are easy to process, for example to tablets ("tabs") for ADW and to clear rinse tablets for ADW granules obtainable by the process according to the invention are less hygroscopic and less prone to sticking or caking.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft Granulate, kurz auch als erfindungsgemäße Granulate bezeichnet. Erfindungsgemäße Granulate weisen einen mittleren Teilchendurchmesser im Bereich von 0,5 bis 1 ,6 mm auf und enthalten (a) im Bereich von 15 bis 25 Gew.-% nicht-ionisches Tensid der allgemeinen Formel (I), Another aspect of the present invention relates to granules, also referred to as granules according to the invention for short. Granules according to the invention have an average particle diameter in the range from 0.5 to 1.6 mm and contain (a) in the range from 15 to 25% by weight of nonionic surfactant of the general formula (I)
R -CH(OH)-CH2-(AO)x-R2 (I) in dem die Variablen wie folgt definiert sind: R -CH (OH) -CH 2 - (AO) x R 2 (I) in which the variables are defined as follows:
R1 ist gewählt aus C4-C2o-Alkyl, R 1 is selected from C 4 -C 20 -alkyl,
R2 ist gewählt aus C8-C2o-Alkyl, R 2 is selected from C 8 -C 20 -alkyl,
AO sind jeweils gleich oder verschieden und gewählt aus C2-C4-Alkylen, AO are in each case identical or different and selected from C 2 -C 4 -alkylene,
x liegt im Bereich von 5 bis 100, x is in the range of 5 to 100,
(b) insgesamt im Bereich von 5 bis 25 Gew.-% zweiter Stoff, gewählt aus Polyethylenglykol und nicht-ionischen Tensiden, die von Tensiden der Formel (I) verschieden sind (b) overall in the range of from 5 to 25% by weight of second material selected from polyethylene glycol and nonionic surfactants other than surfactants of formula (I)
(c) insgesamt 1 bis 5 Gew.-% Kieselsäure oder Silikat, und (c) a total of 1 to 5% by weight of silica or silicate, and
(d) insgesamt im Bereich von 40 bis 70 Gew.-% Hilfsmittel, gewählt aus Alkalimetallzitrat, Alkalimetallcarbonat oder mindestens einem Chelatbildner, gewählt aus Verbindungen der allgemeinen Formel (II)
R3-CH(COOM )-N(CH2COOM )2 (Ii) in dem die Variablen wie folgt definiert sind: R3 ist gewählt aus Ci-C4-Alkyl, Phenyl, Benzyl, CH2OH und CH2CH2COOM1, (d) in total in the range from 40 to 70% by weight of auxiliaries selected from alkali metal citrate, alkali metal carbonate or at least one chelating agent selected from compounds of general formula (II) R 3 is -CH (COOM) -N (CH 2 COOM) 2 (Ii) in which the variables are defined as follows: R 3 is selected from C 1 -C 4 -alkyl, phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 ,
M1 ist ein Alkalimetall oder eine Kombination von mindestens zwei Alkalimetallen, wobei erfindungsgemäßes Granulat bei einer Temperatur von bis zu 60°C fest ist. Komponenten (a), (b), (c) und (d) sind vorstehend näher beschrieben. M 1 is an alkali metal or a combination of at least two alkali metals, granules according to the invention being solid at a temperature of up to 60 ° C. Components (a), (b), (c) and (d) are described in more detail above.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung weist erfindungsgemäßes Granulat eine Partikeldurchmesserverteilung wie folgt auf: dm liegt im Bereich von 0,5 bis 1 ,8 mm, d63,3 liegt im Bereich von 0,4 bis 1 ,8 mm und n liegt im Bereich von 0,7 bis 10, bestimmt jeweils mit Hilfe einer Siebanalyse nach DIN ISO 3310-1 (1992) und Auswertung gemäß DIN 66145 (1976). In a preferred embodiment of the present invention granules according to the invention have a particle diameter distribution as follows: d m is in the range from 0.5 to 1.8 mm, d63.3 is in the range from 0.4 to 1.8 mm and n is in the range from 0.5 to 1.8 mm Range from 0.7 to 10, determined in each case with the aid of a sieve analysis according to DIN ISO 3310-1 (1992) and evaluation according to DIN 66145 (1976).
Erfindungsgemäße Granulate lassen sich zu Spülmaschinentabs und insbesondere zu Klar- spültabs, aber auch zu Klarspülmittel für einen Geschirrspülautomaten oder als Komponente fr ein x-in-1 -Gerschirrspülmittel, beispielsweise ein 2-in-1 -Geschirrspülmitel oder ein 3-in-1 -Granules according to the invention can be made into dishwasher tablets and especially into rinse tablets, but also into rinse aid for an automatic dishwashing machine or as component for an x-in-1 ground dishwashing detergent, for example a 2-in-1 dishwashing detergent or a 3-in-1 detergent.
Geschirrspülmittel weiterverarbeiten. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher die Verwendung eines erfindungsgemäßen Granulats als oder zur Herstellung eines Klarspülmittels. In einer bevorzugten Variante der vorliegenden Erfindung handelt es sich bei dem Klarspülmittel um ein Klarspülmittel für einen Geschirrspülautomaten oder um eine Kom- ponente für ein x-in-1 -Geschirrspülmittel, beispielsweise ein 2-in-1-Geschirrspülmitel oder ein 3- in-1 -Geschirrspülmittel. Further processing dishwashing detergent. Another object of the present invention is therefore the use of a granulate according to the invention as or for producing a rinse aid. In a preferred variant of the present invention, the rinse aid is a rinse aid for an automatic dishwasher or a component for an x-in-1 dishwashing detergent, for example a 2-in-1 dishwashing or a 3-in-1 dishwashing detergent. 1 dishwashing detergent.
In einer Ausführungsform der vorliegenden Erfindung kann man erfindungsgemäßes Granulat ohne weitere Zusätze als Klarspüler in einer Geschirrspülmaschine einsetzen, insbesondere in x.in-1 -Geschirrspülern. In einer anderen Ausführungsform setzt man noch mindestens einen Zusatz hinzu, gewählt aus Wasser und Säuren, beispielsweise Zitronensäure. In one embodiment of the present invention, it is possible to use granules according to the invention without further additives as a rinse aid in a dishwashing machine, in particular in x.in-1 dishwashers. In another embodiment, at least one additive is added, selected from water and acids, for example citric acid.
Die Erfindung wird durch Arbeitsbeispiele weiter erläutert. The invention will be further explained by working examples.
Schmelzpunkte wurden durch dynamische Differenzkalorimetrie (DSC) bestimmt, Aufheizgeschwindigkeit von 10K/min ±1 K/min; Einwaage 6-7 mg; Spülgas 3 I N2/h, AI-Messtiegel, offen Melting points were determined by differential scanning calorimetry (DSC), heating rate of 10K / min ± 1 K / min; Initial weight 6-7 mg; Purge gas 3 IN 2 / h, AI measuring crucible, open
Verwendete Komponenten: Used components:
(a.1 ): n-C8Hi7-CH(OH)-CH2-(AO)22-iso-CiiH23 , Schmelzpunkt: 32°C (a.1): nC 8 Hi7-CH (OH) -CH 2 - (AO) 22 -iso-CiiH 23 , melting point: 32 ° C
(b.1 ): Polyethylenglykol, Mw 4.000 g/mol
(c.1 ): Fällungskieselsäure, mittlerer Partikeldurchmesser d50: 13,5 μηη (Laserbeugung), Oberfläche nach BET: 190 m2/g, bestimmt durch Stickstoffadsorption ISO 92777. (c.1 ) ist kommerziell erhältlich als Sipernat® 22 S (b.1): polyethylene glycol, M w 4,000 g / mol (c.1): precipitated silica, average particle diameter d50: 13.5 μm (laser diffraction), surface area according to BET: 190 m 2 / g, determined by nitrogen adsorption ISO 92777. (c.1) is commercially available as Sipernat® 22 S
(d.1 ): Trinatriumsalz der Zitronensäure als Dihydrat (d.1): trisodium salt of citric acid as dihydrate
Die Herstellung der festen Formulierung erfolgte jeweils wie folgt: The preparation of the solid formulation was in each case as follows:
Die Komponenten (a.1 ) und (b.1 ) wurden gemeinsam in einem Becherglas bei 70°C aufgeschmolzen und mit einem Propellerrührer vermischt. Anschließend wurde die Schmelze auf Aluminiumfolie (20 cm x 10 cm x 1 cm) gegossen und bei Zimmertemperatur zum Erstarren gebracht. Man erhielt wachsartige Platten. The components (a.1) and (b.1) were melted together in a beaker at 70 ° C and mixed with a propeller stirrer. Subsequently, the melt was poured onto aluminum foil (20 cm × 10 cm × 1 cm) and solidified at room temperature. Waxy plates were obtained.
Aus diesen wachsartigen Platten wurden mit Hilfe einer Schuppenwalze Pastillen hergestellt. Die verwendete Schuppenwalze hatte einen Durchmesser von 33 cm, eine Breite von 50 cm und wurde mit einer Drehzahl von 1 ,2 U/min betrieben. Die Kühlmitteltemperatur (Wasser) betrug 16 bis 22°C. Zur Herstellung der Pastillen ging man im Detail so vor, dass man die wachsartigen Platten in einen beheizbaren, 38 cm breiten Tropftrichter gegeben wurden, der am Boden mit 36 Löchern (Durchmesser 1 ,5 mm) versehen war. Über die Trichtertemperatur von 80 bis 100 °C wurde die Schmelzgeschwindigkeit der Platte so eingestellt, dass auf der Kühlfläche der Walze definierte Tropfen entstanden, die innerhalb einer Umdrehung erstarrten und dann durch ein über die Walze angebrachtes starres Messer von der Walze abgestreift wurden. From these waxy plates lozenges were produced by means of a flaking roller. The flake roll used had a diameter of 33 cm, a width of 50 cm and was operated at a speed of 1, 2 U / min. The coolant temperature (water) was 16 to 22 ° C. In detail, the wax-like plates were placed in a heatable, 38 cm wide dropping funnel, which was provided at the bottom with 36 holes (diameter 1, 5 mm). Through the hopper temperature of 80 to 100 ° C, the melt rate of the plate was set so that defined droplets formed on the cooling surface of the roller, which solidified within a revolution and then stripped by a mounted over the roller rigid knife from the roller.
Die so hergestellten Pastillen wurden in einer Schlagmühle (Messermühle) vermählen. Hierzu wurde die Mühle mit 2 Messern und einer Umfangsgeschwindigkeit von 14 m/s betrieben. Als Mahlsieb wurde ein Rundlochsieb mit einem Lochdurchmesser von 3,2 mm und einer freienThe lozenges thus produced were ground in a hammer mill (knife mill). For this purpose, the mill was operated with 2 knives and a peripheral speed of 14 m / s. As Mahlsieb was a Rundlochsieb with a hole diameter of 3.2 mm and a free
Oberfläche von 40% verwendet. In diese Mühle wurden die Pastillen, die Komponente (d.1 ) und Kieselsäure (c.1 ) gleichzeitig dosiert und vermählen. Surface of 40% used. In this mill, the lozenges, the component (d.1) and silica (c.1) were dosed and ground simultaneously.
Es wurden die folgenden erfindungsgemäßen Granulate und Vergleichsgranulate erhalten, sie- he Tabelle 1 . The following granules according to the invention and comparative granules were obtained, see Table 1.
Tabelle 1 : Erfindungsgemäße Granulate und Vergleichsgranulate Table 1: Inventive granules and comparative granules
Anteile von (a.1 ), (b.1 ), (c.1 ) und (d.1 ) in Gew.-%.
Der Lagertest betraf eine Lagerung bei 40°C über eine Zeit von 72 Stunden bei Feuchtigkeits- ausschluss. Er wurde wie folgt durchgeführt: 15 ml Granulat bzw. Vergleichsgranulat wurden in einen oben und unten geöffneten Zylinder gefüllt. Damit das Granulat nicht aus den Zylinder herausrieselte, stand dieser mit der unteren Öffnung auf einer Bodenplatte. Die obere Öffnung wurde mit einem Stempel versehen und dieser mit einem Gewicht von 500 g belastet und das Ganze für 72 h bei 40°C gelagert. Danach wurde geprüft, wie sich das Granulat durch die Lagerung bei einer Temperatur von 40°C und gleichzeitiger Gewichtsbelastung verändert hatte. Wenn diese Parameter ohne Einfluss waren, floss das Granulat nach Anheben des Zylinders aus der unteren Öffnung heraus. Neigt das Granulat zum Verkleben, dann bildete sich ein Pressling, der man vorsichtig mit dem Stempel aus den Zylinder drückte. Der Pressling wurde unter die Schale einer Balkenwaage gelegt. Auf dieser Schale stand ein Becherglas, das solange mit Wasser gefüllt wurde, bis der Pressling zerbrach. Aus dem so erhaltenen Messwert für die Wassermenge kann man auf die Lagerfähigkeit von Granulaten schließen. Produkte, die keinen Pressling bilden, zeigen sehr gute Lagereigenschaften (erfindungsgemäße Granulate G.1 und G.4). Proportions of (a.1), (b.1), (c.1) and (d.1) in% by weight. The storage test was storage at 40 ° C for 72 hours with exclusion of moisture. It was carried out as follows: 15 ml of granules or comparative granules were filled into a top and bottom open cylinder. So that the granules did not trickle out of the cylinder, it stood with the lower opening on a base plate. The upper opening was stamped and loaded with a weight of 500 g and stored for 72 h at 40 ° C. Thereafter, it was examined how the granules had changed by storage at a temperature of 40 ° C and simultaneous weight load. If these parameters had no influence, the granules flowed out of the lower opening after lifting the cylinder. If the granules tend to adhere, then a compact formed, which was carefully pressed out of the cylinder with a punch. The compact was placed under the shell of a beam balance. On this dish stood a beaker which was filled with water until the compact broke. From the measured value for the amount of water thus obtained, one can conclude on the shelf life of granules. Products which do not form a compact exhibit very good storage properties (granules G.1 and G.4 according to the invention).
Die Partikeldurchmesserverteilung der beispielhaften Granulate wurde wie folgt mittels Siebanalyse bestimmt: Siebmaschine: AS 200 control, Fa. Retsch, Analysensiebe nach DIN ISO 3310-1 , Höhe 25 mm; 0 200 mm The particle diameter distribution of the exemplary granules was determined as follows by sieve analysis: sieving machine: AS 200 control, Fa. Retsch, test sieves to DIN ISO 3310-1, height 25 mm; 0 200 mm
Amplitude: 0,6, Siebzeit: 2 min Amplitude: 0.6, sieving time: 2 min
Aus den durch die Siebanalyse erhaltenen Partikeldurchmesserverteilungen wurden die Kenn- großen dm, d63,3 und n ermittelt, mit denen die Granulometrie der Beispielgranulate beschrieben wird. From the particle diameter distributions obtained by the sieve analysis, the parameters d m , d63,3 and n were determined, which describe the granulometry of the example granules.
Aus der grafischen Auswertung der Partikeldurchmesserverteilung mittels eines Rosin, Rammler, Sperling und Bennet-Diagramms (RRSB-Verteilung) folgen d63,3 : charakteristische Partikelgröße n Gleichmäßigkeitskoeffizient (Exponent n) Für den Fall, dass der granulometrische Zustand des Haufwerks nicht durch eine RRSB- Verteilung beschrieben werden kann, z.B. bei Mischungen von Haufwerken unterschiedlicher Granulometrie, gelten die oben genannten Parameter auch für Abschnitte der Verteilung, die der RRSB-Verteilung folgen.
Beispiel (G.1) d< 0,4 mm: 22,6% From the graphical evaluation of the particle diameter distribution by means of a Rosin, Rammler, Sperling and Bennet diagram (RRSB distribution), d63,3 follows: characteristic particle size n uniformity coefficient (exponent n) In the event that the granulometric state of the aggregate is not affected by an RRSB Can be described, for example, in mixtures of heaps of different granulometry, the above parameters also apply to sections of the distribution that follow the RRSB distribution. Example (G.1) d <0.4 mm: 22.6%
d > 1,6 mm: 0% d> 1.6 mm: 0%
dm = 0,69 mmd m = 0.69 mm
n = 2,0 n = 2.0
V-G.2 kein messbares Granulat erhalten V-G.2 no measurable granules obtained
V-G.3 kein messbares Granulat erhalten V-G.3 received no measurable granules
Beispiel (G.4) d < 0,4 mm: 29,8% Example (G.4) d <0.4 mm: 29.8%
d > 1,6 mm: 10,6% dm = 0,71 mmd> 1.6 mm: 10.6% d m = 0.71 mm
n = 1,49
n = 1.49
Claims
Patentansprüche claims
1 . Verfahren zur Herstellung einer bei bis zu einer Temperatur von mindestens 60°C festen Formulierung, dadurch gekennzeichnet, dass man 1 . Process for the preparation of a formulation which is solid up to a temperature of at least 60 ° C, characterized in that
(a) mindestens ein nicht-ionisches Tensid der allgemeinen Formel (I) (a) at least one nonionic surfactant of the general formula (I)
R -CH(OH)-CH2-(AO)x-R2 (I) in dem die Variablen wie folgt definiert sind: R -CH (OH) -CH 2 - (AO) x R 2 (I) in which the variables are defined as follows:
R1 ist gewählt aus C4-C2o-Alkyl, R 1 is selected from C 4 -C 20 -alkyl,
R2 ist gewählt aus C8-C2o-Alkyl, R 2 is selected from C 8 -C 20 -alkyl,
AO sind jeweils gleich oder verschieden und gewählt aus C2-C4-Alkylen, AO are in each case identical or different and selected from C 2 -C 4 -alkylene,
x liegt im Bereich von 5 bis 100, x is in the range of 5 to 100,
(b) mit mindestens einem zweiten Stoff, gewählt aus Polyethylenglykol und nichtionischen Tensiden, die von Tensiden der Formel (I) verschieden sind, (b) at least one second material selected from polyethylene glycol and nonionic surfactants other than surfactants of formula (I),
im aufgeschmolzenen Zustand mischt, in the molten state,
konfektioniert, assembled,
im festen Zustand mit in the solid state with
(c) Kieselsäure oder Silikat und (c) silicic acid or silicate and
(d) mindestens einem Hilfsmittel, gewählt aus Alkalimetallzitrat, Alkalimetallcarbonat oder mindestens einem Chelatbildner, gewählt aus Verbindungen der allgemeinen Formel(d) at least one adjuvant selected from alkali metal citrate, alkali metal carbonate or at least one chelating agent selected from compounds of the general formula
(Ii) (Ii)
R3-CH(COOM )-N(CH2COOM )2 (II) in dem die Variablen wie folgt definiert sind: R 3 -CH (COOM) -N (CH 2 COOM) 2 (II) in which the variables are defined as follows:
R3 ist gewählt aus Ci-C4-Alkyl, Phenyl, Benzyl, CH2OH und CH2CH2COOM1 , R 3 is selected from C 1 -C 4 -alkyl, phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 ,
M1 ist ein Alkalimetall oder eine Kombination von mindestens zwei Alkalimetallen, in einer Mühle vermischt und vermahlt. M 1 is an alkali metal or a combination of at least two alkali metals, mixed in a mill and ground.
Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Formulierung frei ist Phosphaten und Polyphosphaten. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man die Konfektionierung wählt aus Pastillierungen, Verschuppungen, Vermahlungen und Kombinationen von mindestens zwei der vorhergehenden Maßnahmen.
Verfahren nach mindestens einem der vorangegangen Ansprüche, dadurch gekennzeichnet, dass Verbindung der allgemeinen Formel (I) einen Schmelzpunkt im Bereich von 25 bis 60°C aufweist. A method according to claim 1, characterized in that the formulation is free phosphates and polyphosphates. 3. The method according to claim 1 or 2, characterized in that one selects the confectioning of pastilles, flakes, Vermahlungen and combinations of at least two of the preceding measures. Method according to at least one of the preceding claims, characterized in that compound of the general formula (I) has a melting point in the range of 25 to 60 ° C.
Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man als Hilfsmittel (c) entweder zwei verschiedene Kieselsäuren oder zwei verschiedene Silikate einsetzt. Method according to one of claims 1 to 4, characterized in that one uses as auxiliary (c) either two different silicas or two different silicates.
Verfahren nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass man die Mengenverhältnisse wie folgt wählt: Process according to at least one of the preceding claims, characterized in that the proportions are chosen as follows:
(a) im Bereich von 15 bis 25 Gew.-% nicht-ionisches Tensid der allgemeinen Formel (I), (a) in the range of 15 to 25% by weight of nonionic surfactant of the general formula (I),
(b) insgesamt im Bereich von 5 bis 40 Gew.-% zweiter Stoff, (b) total in the range of from 5 to 40% by weight of second material,
(c) insgesamt 1 bis 5 Gew.-% Kieselsäure oder Silikat, und (c) a total of 1 to 5% by weight of silica or silicate, and
(d) insgesamt im Bereich von 40 bis 70 Gew.-% Hilfsmittel. (d) overall in the range of 40 to 70 weight percent adjuvant.
Verfahren nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Anteil an Komponente (b) mindestens so hoch ist wie der Anteil an nichtionischem Tensid der allgemeinen Formel (I). Method according to at least one of the preceding claims, characterized in that the proportion of component (b) is at least as high as the proportion of nonionic surfactant of the general formula (I).
Granulat mit einem mittleren Teilchendurchmesser im Bereich von 0,5 bis 1 ,6 mm, enthaltend Granules having an average particle diameter in the range of 0.5 to 1.6 mm, containing
(a) im Bereich von 15 bis 25 Gew.-% nicht-ionisches Tensid der allgemeinen Formel (I), (a) in the range of 15 to 25% by weight of nonionic surfactant of the general formula (I),
R -CH(OH)-CH2-(AO)x-R2 (I) in dem die Variablen wie folgt definiert sind: R -CH (OH) -CH 2 - (AO) x R 2 (I) in which the variables are defined as follows:
R1 ist gewählt aus C4-C2o-Alkyl, R 1 is selected from C4-C2o-alkyl,
R2 ist gewählt aus C8-C2o-Alkyl, R 2 is selected from C 8 -C 20 -alkyl,
AO sind jeweils gleich oder verschieden und gewählt aus C2-C4-Alkylen, AO are in each case identical or different and selected from C 2 -C 4 -alkylene,
x liegt im Bereich von 5 bis 100, x is in the range of 5 to 100,
(b) insgesamt im Bereich von 5 bis 25 Gew.-% zweiter Stoff, gewählt aus Polyethylengly- kol und nicht-ionischen Tensiden, die von Tensiden der Formel (I) verschieden sind(b) in total in the range of from 5 to 25% by weight of second material selected from polyethylene glycol and nonionic surfactants other than surfactants of formula (I)
(c) insgesamt 1 bis 5 Gew.-% Kieselsäure oder Silikat, und (c) a total of 1 to 5% by weight of silica or silicate, and
(d) insgesamt im Bereich von 40 bis 70 Gew.-% Hilfsmittel, gewählt aus Alkalimetallzitrat, Alkalimetallcarbonat oder mindestens einem Chelatbildner, gewählt aus Verbindungen der allgemeinen Formel (II) (d) in total in the range from 40 to 70% by weight of auxiliaries selected from alkali metal citrate, alkali metal carbonate or at least one chelating agent selected from compounds of general formula (II)
R3-CH(COOM )-N(CH2COOM )2 (II)
in dem die Variablen wie folgt definiert sind: R 3 -CH (COOM) -N (CH 2 COOM) 2 (II) where the variables are defined as follows:
R3 ist gewählt aus Ci-C4-Alkyl, Phenyl, Benzyl, CH2OH und CH2CH2COOM1 , R 3 is selected from C 1 -C 4 -alkyl, phenyl, benzyl, CH 2 OH and CH 2 CH 2 COOM 1 ,
M1 ist ein Alkalimetall oder eine Kombination von mindestens zwei Alkalimetallen, wobei das Granulat bei einer Temperatur von bis zu 60°C fest ist. M 1 is an alkali metal or a combination of at least two alkali metals, the granules being solid at a temperature of up to 60 ° C.
Granulat nach Anspruch 8, dadurch gekennzeichnet, dass es eine Partikeldurchmesserverteilung wie folgt aufweist: dm liegt im Bereich von 0,5 bis 1 ,8 mm, d63,3 liegt im Bereich von 0,4 bis 1 ,8 mm und n liegt im Bereich von 0,7 bis 10, bestimmt jeweils mit Hilfe einer Siebanalyse nach DIN ISO 3310-1 (1992) und Auswertung gemäß DIN 66145 (1976). Granules according to claim 8, characterized in that it has a particle diameter distribution as follows: d m is in the range of 0.5 to 1.8 mm, d63.3 is in the range of 0.4 to 1.8 mm and n is in the range of Range from 0.7 to 10, determined in each case with the aid of a sieve analysis according to DIN ISO 3310-1 (1992) and evaluation according to DIN 66145 (1976).
10. Verwendung eines Granulats nach Anspruch 8 oder 9 als oder zur Herstellung eines Klarspülmittels. 10. Use of a granulate according to claim 8 or 9 as or for the production of a rinse aid.
1 1. Verwendung nach Anspruch 10, dadurch gekennzeichnet, dass es sich bei dem Klarspülmittel um ein Klarspülmittel für einen Geschirrspülautomaten oder um eine Komponente für ein x-in-1 -Geschirrspülmittel handelt.
1 1. Use according to claim 10, characterized in that it is the rinse aid to a rinse aid for a dishwasher or a component for an x-in-1 dishwashing detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL16785417T PL3368645T3 (en) | 2015-10-26 | 2016-10-18 | Granulates, method for their manufacture and their application |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15191376 | 2015-10-26 | ||
| PCT/EP2016/074920 WO2017071984A1 (en) | 2015-10-26 | 2016-10-18 | Granulates, method for the production and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3368645A1 true EP3368645A1 (en) | 2018-09-05 |
| EP3368645B1 EP3368645B1 (en) | 2019-10-16 |
Family
ID=54541944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP16785417.3A Active EP3368645B1 (en) | 2015-10-26 | 2016-10-18 | Granulates, method for their manufacture and their application |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US10717952B2 (en) |
| EP (1) | EP3368645B1 (en) |
| JP (1) | JP6885936B2 (en) |
| KR (1) | KR20180074737A (en) |
| CN (1) | CN108350397B (en) |
| BR (1) | BR112018008210A2 (en) |
| ES (1) | ES2765237T3 (en) |
| PL (1) | PL3368645T3 (en) |
| RU (1) | RU2736331C2 (en) |
| WO (1) | WO2017071984A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7485797B2 (en) * | 2020-07-03 | 2024-05-16 | ザ プロクター アンド ギャンブル カンパニー | Particulate laundry composition |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995005440A1 (en) * | 1993-08-13 | 1995-02-23 | The Procter & Gamble Company | Granular automatic dishwashing detergent with long-chain amine oxides |
| WO1998011185A1 (en) * | 1996-09-11 | 1998-03-19 | The Procter & Gamble Company | Detergent composition |
| JPH1135999A (en) * | 1997-07-23 | 1999-02-09 | Lion Corp | Preparation of granular nonionic detergent composition |
| BR9807007A (en) * | 1997-11-26 | 2000-03-14 | Procter & Gamble | Multilayer detergent tablet having both compressed and uncompressed portions |
| JP2000192098A (en) * | 1998-12-25 | 2000-07-11 | Lion Corp | Tablet detergent composition |
| DE10019936A1 (en) * | 1999-12-04 | 2001-10-25 | Henkel Kgaa | Detergents and cleaning agents |
| RU2169175C1 (en) * | 1999-12-17 | 2001-06-20 | Общество с ограниченной ответственностью "Чистые технологии" | Detergent for cleaning surface from organic contaminants and method of preparing thereof |
| DE19962886A1 (en) | 1999-12-24 | 2001-07-05 | Cognis Deutschland Gmbh | Surfactant granules with an improved dissolution rate |
| JP2003105375A (en) * | 2001-09-28 | 2003-04-09 | Lion Corp | Granular detergent composition |
| DE10152142A1 (en) | 2001-10-23 | 2003-04-30 | Cognis Deutschland Gmbh | Solid washing, rinsing and cleaning agents |
| EP1956076A1 (en) * | 2007-02-02 | 2008-08-13 | Kemira Oyj | A cogranule for use in solid detergent compositions |
| DE102007019458A1 (en) | 2007-04-25 | 2008-10-30 | Basf Se | Phosphate-free machine dishwashing detergent with excellent rinse performance |
| DE102011084934A1 (en) | 2011-10-21 | 2013-04-25 | Henkel Ag & Co. Kgaa | Rinse aid and dishwashing detergent |
-
2016
- 2016-10-18 EP EP16785417.3A patent/EP3368645B1/en active Active
- 2016-10-18 CN CN201680062436.0A patent/CN108350397B/en not_active Expired - Fee Related
- 2016-10-18 BR BR112018008210-4A patent/BR112018008210A2/en active Search and Examination
- 2016-10-18 RU RU2018119305A patent/RU2736331C2/en active
- 2016-10-18 ES ES16785417T patent/ES2765237T3/en active Active
- 2016-10-18 WO PCT/EP2016/074920 patent/WO2017071984A1/en active Application Filing
- 2016-10-18 PL PL16785417T patent/PL3368645T3/en unknown
- 2016-10-18 KR KR1020187014363A patent/KR20180074737A/en unknown
- 2016-10-18 JP JP2018521634A patent/JP6885936B2/en active Active
- 2016-10-18 US US15/770,532 patent/US10717952B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| ES2765237T3 (en) | 2020-06-08 |
| US10717952B2 (en) | 2020-07-21 |
| CN108350397A (en) | 2018-07-31 |
| RU2018119305A3 (en) | 2019-11-28 |
| BR112018008210A2 (en) | 2018-10-23 |
| JP2018533656A (en) | 2018-11-15 |
| RU2736331C2 (en) | 2020-11-13 |
| WO2017071984A1 (en) | 2017-05-04 |
| RU2018119305A (en) | 2019-11-28 |
| PL3368645T3 (en) | 2020-04-30 |
| US20190055501A1 (en) | 2019-02-21 |
| EP3368645B1 (en) | 2019-10-16 |
| KR20180074737A (en) | 2018-07-03 |
| JP6885936B2 (en) | 2021-06-16 |
| CN108350397B (en) | 2021-02-26 |
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